J. M. D. Coey - Stuart S.P. Parkin (Eds.) - Handbook of Magnetism and Magnetic Materials (2021, Springer) (10.1007 - 978-3-030-63210-6)
J. M. D. Coey - Stuart S.P. Parkin (Eds.) - Handbook of Magnetism and Magnetic Materials (2021, Springer) (10.1007 - 978-3-030-63210-6)
J. M. D. Coey - Stuart S.P. Parkin (Eds.) - Handbook of Magnetism and Magnetic Materials (2021, Springer) (10.1007 - 978-3-030-63210-6)
Stuart S. P. Parkin
Editors
Handbook of
Magnetism
and Magnetic
Materials
Handbook of Magnetism and Magnetic
Materials
J. M. D. Coey • Stuart S. P. Parkin
Editors
Handbook of Magnetism
and Magnetic Materials
With 618 Figures and 157 Tables
123
Editors
J. M. D. Coey Stuart S. P. Parkin
School of Physics Max Planck Institute of Microstructure Physics
Trinity College Halle (Saale)
Dublin Germany
Ireland
This Springer imprint is published by the registered company Springer Nature Switzerland AG.
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Preface
This handbook aims to offer a broad perspective on the state of the art in
magnetism and magnetic materials. The discovery and dissemination of reliable
knowledge about the natural world is a complex process that depends on interactions
of individuals with shared values and presumptions. Information is the primary
product of their endeavour. It is contained in in papers, patents, reviews, handbooks
monographs and textbooks. This is a perpetual work in progress. Knowledge
percolates through this sequence, taking ever-more digestible and definitive forms
as it is consolidated or eliminated. Now information technology is facilitating this
dynamic. Whereas papers are replaced by more up-to-date papers with new sets
of references to trace their pedigree and textbooks may be updated perhaps after
10 years, handbooks are compendia of information that need updating on a shorter
timescale. This was impractical within the constraints of traditional publication, but
the greater flexibility of electronic publication now opens the possibility for authors
to update their contributions as time passes, and perspectives shift.
The book’s 34 chapters are organized into four parts. After an introduction to the
history and basic concepts in the field, there follow 12 chapters covering the funda-
mentals of solid state magnetism, and the phenomena related to collective magnetic
order. Eight chapters are then devoted to the main classes of magnetic materials –
elements, metallic compounds, oxides and other nonmetallic compounds, thin films,
nanoparticles and artificially engineered materials. Another six chapters treat the
methods for preparing and characterizing magnetic materials, and the final part is
devoted to some major applications.
No fewer than 85 authors have contributed to this handbook. It has taken
longer than we originally anticipated, and the patience of the early responders is
sincerely appreciated. The format for subsequent updating of the electronic text is
by individual chapter, which will avoid such difficulty in the future.
We are grateful to the staff at Springer, Claus Ascheron for initiating the
project, Werner Skolaut for his patience and encouragement, and Barbara Wolf for
efficiently bringing the handbook to hand.
Volume 1
Part I Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
vii
viii Contents
Volume 2
17 Magnetic Oxides and Other Compounds . . . . . . . . . . . . . . . . . . . . . . . 847
J. M. D. Coey
18 Dilute Magnetic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
Alberta Bonanni, Tomasz Dietl, and Hideo Ohno
19 Single-Molecule Magnets and Molecular Quantum Spintronics . . . 979
Gheorghe Taran, Edgar Bonet, and Wolfgang Wernsdorfer
20 Magnetic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1011
Sara A. Majetich
21 Artificially Engineered Magnetic Materials . . . . . . . . . . . . . . . . . . . . 1047
Christopher H. Marrows
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1679
About the Editors
xi
xii About the Editors
xv
xvi Contributors
Thomas Schrefl Christian Doppler Laboratory for Magnet Design Through Physics
Informed Machine Learning, Department of Integrated Sensor Systems, Danube
University Krems, Wiener Neustadt, Austria
Baogen Shen Institute of Physics, Chinese Academy of Sciences, Beijing, China
Ralph Skomski University of Nebraska, Lincoln, NE, USA
Yurii Skourski Hochfeld-Magnetlabor Dresden (EMFL-HLD), Helmholtz-
Zentrum Dresden-Rossendorf, Dresden, Germany
Andrei N. Slavin Department of Physics, Oakland University, Rochester, MI, USA
Plamen Stamenov School of Physics and CRANN, Trinity College, University of
Dublin, Dublin, Ireland
Philip Stamp Pacific Institute of Theoretical Physics, University of British
Columbia, Vancouver, BC, Canada
Dieter Suess University of Vienna Research Platform MMM Mathematics – Mag-
netism – Materials, and Physics of Functional Materials, Faculty of Physics,
University of Vienna,Wien, Austria
Jirong Sun Institute of Physics, Chinese Academy of Sciences, Beijing, China
Jonathan Z. Sun IBM T. J. Watson Research Center, Yorktown Heights, NY, USA
So Takei The Physics Program, The Graduate Center, CUNY, New York, NY, USA
Department of Physics, Queens College of the City University of New York,
Flushing, NY, USA
Wei Tang Materials Science and Engineering, Ames Laboratory, Ames, IA, USA
Gheorghe Taran Physikalisches Institute, KIT, Karlsruhe, Germany
Wolfgang Wernsdorfer Physikalisches Institute, KIT, Karlsruhe, Germany
Matthew Willard Materials Science and Engineering, Case Western Reserve
University, Cleveland, OH, USA
Sebastian Wimmer München, Department Chemie, Ludwig-Maximilians-
Universität, München, Germany
Lukas Wollmann Max-Planck-Institute für Chemische Physik fester Stoffe,
Dresden, Germany
D. Wu National Laboratory of Solid State Microstructures and Department of
Physics, Nanjing University, Nanjing, People’s Republic of China
Michael Ziese Fakultät für Physik und Geowissenschaften, Universität Leipzig,
Leipzig, Germany
Part I
Fundamentals
History of Magnetism and Basic Concepts
1
J. M. D. Coey
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Early History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
The Compass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
The Emergence of Modern Science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
The Electromagnetic Revolution [9] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Magnetostatics and Classical Electrodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
The Earth’s Magnetic Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
The Properties of Ferromagnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Magnetism of the Electron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
The Demise of Classical Physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Magnetic Phenomenology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Micromagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Magnetic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Magnetic Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Intermetallic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Model Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Amorphous Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Magnetic Fine Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Magnetic Recording . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Methods of Investigation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Materials Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Computational Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Spin Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Appendix: Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
J. M. D. Coey ()
School of Physics, Trinity College, Dublin, Ireland
e-mail: [email protected]
Abstract
Introduction
The attraction of ferrous objects to a permanent magnet has been a source of wonder
since the Iron Age. Feeble magnets are widespread in nature in the form of rocks
known as lodestones, which are rich in magnetite, an oxide mineral with ideal
formula Fe3 O4 . Rocky outcrops eventually get magnetized by huge electric currents
when lightning strikes, and these natural magnets were known and studied in ancient
Greece, Egypt, China, and Mesoamerica. Investigations of magnetic phenomena led
to the invention of steel magnets – needles and horseshoes – then electromagnets and
eventually the panoply of hard and soft materials that support the modern magnetics
industry. Magnetism in a rare example of a science with recorded history goes back
well over 2000 years [1, 2].
Theory and practice have been loose partners for most of that time. What people
are able to see and rationalize is inevitably conditioned by a priori philosophical
beliefs about the world. The scientific method of critically interrogating nature
by experimentation and then amassing and exchanging data and ideas among the
community of the curious came to be established only gradually. Mathematics
emerged as the supporting scaffold of natural philosophy in Europe in the seven-
teenth century, when precisely formulated natural laws and explanations began to
take root. Nevertheless, most of the progress that has been made in magnetism in
the past – from the discovery of horseshoe magnets or electromagnetic induction
1 History of Magnetism and Basic Concepts 5
to the development of Alnico – was based on intuition and experience, rather than
formal theory. That situation is changing.
The discovery of the electron in the closing years of the nineteenth century
impelled the great paradigm shift from classical to modern physics. Magnetism,
however familiar and practically important it had become, was fundamentally
incomprehensible in classical terms. Charged particles were theoretically expected
to exhibit no magnetism of any kind. It took 25 years and the insights of quantum
mechanics and relativity to resolve that conundrum. Magnetism then went on to play
a key role in clarifying basic concepts in condensed matter physics and Earth science
over the course of the twentieth century. Now it is a key player in the transformative
information technology of the twenty-first century.
Early History
Aristotle attributed the first reflections on the nature of magnetic attraction to Thales,
the early Greek philosopher and mathematician who was born in Miletus in Asia
Minor in 624 BC. Thales was an animist who credited the magnet with a soul,
on account of its ability to create movement, by attraction. This curious idea was
to linger until the seventeenth century. The magnet itself is believed to be named
after Magnesia, a city in Lydia in Asia Minor that was a good source of lodestone.
In the fifth century BC, when Empedokles postulated the existence of the four
elements – Earth, water, air, and fire – magnetism was associated with air. Special
effluvia somehow passing through the invisible pores in magnetic material were
invoked to explain the phenomenon, a theory echoed much later by Descartes in
a mechanistic picture that finally laid the magnet’s soul to rest. The Roman poet
Lucretius writing in the first century BC mentions magnetic induction (the ability
of a magnet to induce magnetism in pieces of nonmagnetic iron) and for the first
time notes the ability of magnets not just to attract but also to repel one another.
The Greek approach of developing a philosophical framework into which natural
observations were expected to fit was not conducive to open-minded exploration of
the natural world.
The Compass
The Chinese approach to the magnet was more practical. Their magnetism was
initially linked to practical concerns of geomancy and divination [3]. The art of
adapting the residences of the living and the tombs of the dead to harmonize
with local currents of the cosmic breath demanded knowledge of its direction. A
south-pointer consisting of a carved lodestone spoon that was free to rotate on a
polished baseplate (Fig. 1) was already in use at the time of Lucretius and may have
originated hundreds of years earlier. An important discovery, attributed to Zeng
Gongliang in 1064, was that iron could acquire a thermoremanent magnetization
when rapidly cooled from red heat in the Earth’s magnetic field. A short step
6 J. M. D. Coey
Fig. 1 Magnetic direction finders. (a) Baseplate and lodestone spoon of the south-pointer used in
China from about the first century BC (Needham, courtesy of Cambridge University Press). (b) A
Chinese floating compass from 1044. (c) Fifteenth-century Chinese and (d) Portuguese mariners’
compasses. (Boorstin, courtesy of Editions Robert Laffont)
led to the suspended compass needle, which was described by Shen Kuo around
1088, together with declination, the deviation of the needle from a north-south axis.
Floating compasses had also been developed by this time, often in the form of an
iron fish made to float in a bowl of water.
The compass appeared about a century later in Europe, where it was first
described by Alexander Neckam in 1190. The direction-finding ability of the
magnetic needle or fish was also exploited by Arabs and Persians from the thirteenth
century, both for navigation and to determine the sacred direction of Mecca [4].
Compasses (Fig. 1) were the enabling technology for the great voyages of discovery
of the fifteenth century, bringing the Ming admiral Cheng Ho to the coasts of Africa
in 1433 and Christopher Columbus (who rediscovered declination) to America in
1492, where he landed on the continent where the Olmecs may once have displayed
a knowledge of magnetism in their massive stone carvings of human figures and sea
turtles dating from the second millennium BC.
1 History of Magnetism and Basic Concepts 7
Before long, the landmasses and oceans of our planet were mapped and explored.
According to Francis Bacon, writing in Novum Organum in 1620 [5], the magnetic
compass was one of three things, along with printing and gunpowder had “changed
the whole face and state of things throughout the world.” All three were originally
Chinese inventions. The compass helped to provide us with an image of the planet
we inhabit. This was the first of three occasions when magnetism changed the world.
A landmark in the history of magnetism in Europe was the work of the French
crusader monk Petrus Peregrinus. His tract Epistola de Magnete [6] recounts
experiments with floating pieces of lodestone and carved lodestone spheres called
terella, which he wrote up in Southern Italy during the 1269 siege of Lucera. He
describes how to find the poles of a magnet and relates magnetic attraction to
the celestial sphere. The same origin had long been associated with the magnet’s
directional property in China [3]; we should not forget that before electric light,
people were acutely aware of the stars and scrutinized them keenly. Peregrinus’s
tract included an ingenious proposal for a magnetic perpetual motion device – a
theme that has been embraced by charlatans throughout the ages, right up to the
present day.
Much credit for the inauguration of the experimental method in a recognizably
modern form belongs to William Gilbert. Physician to the English Queen Elizabeth
I, Gilbert personally conducted a series of experiments on terellas, which led him to
proclaim that the Earth itself was a great magnet. The lodestone or steel magnets
aligned themselves not with the celestial sphere, but with the Earth’s poles. He
induced magnetism by cooling iron in the Earth’s field and then destroyed it by
heating or hammering. Gilbert was at pains to debunk the millennial accretion of
superstition that clung to the magnet, confidently advocating in a robust polemical
style reliance on the evidence of one’s own eyes. He described his investigations in
his masterwork De Magnete, published in 1600 [7]. It is arguably the first modern
scientific text.
Subsequent developments were associated with improvements in navigation and
the prestige of the great voyages of discovery. Gilbert’s theories dominated the
seventeenth century up until Edmond Halley’s 1692 shell model for the Earth’s
magnetic structure, which strongly influenced compass technology and navigation.
Naval interests were the principal drivers of magnetic research during this period,
and Halley was sponsored by the British Navy to survey and prepare charts of
the Earth’s magnetic field in the North and South Atlantic oceans (Fig. 2), This
was in the vain hope of addressing the pressing longitude problem, by pinpointing
magnetically the position of a vessel on the Earth’s surface.
The following century was marked by the professionalization of natural philos-
ophy (as physical science was then known in Europe) [8]. Accordingly, the natural
philosopher with his mantle of theory was rewarded with social status, access to
public funding, and credibility beyond that extended to artisans on the one hand and
8 J. M. D. Coey
quacks on the other, such as the colorful Anton Mesmer, who propagated theories of
animal magnetism in his salon in Paris or James Graham with his royal Patagonian
magnetic bed for nightly rental in a fashionable London townhouse. The English
entrepreneur Gowin Knight, representative of a new breed of natural philosopher,
greatly improved the quality of bar magnets and compasses, coupling scientific
endeavor with manufacturing enterprise and a keen sense of intellectual property.
An outstanding technical breakthrough of the eighteenth century was the 1755
discovery by the Swiss blacksmith Johann Dietrich that the horseshoe was an ideal
1 History of Magnetism and Basic Concepts 9
shape for a steel magnet [1]. His invention, a clever practical solution to the age-old
problem of self-demagnetization in bar magnets, was enthusiastically promoted by
his mentor, the Swiss applied mathematician Daniel Bernoulli, who garnered most
of the credit.
The late eighteenth century in Europe was a time of great public appetite for lectures
and demonstration of the latest scientific discoveries, not least in electricity and
magnetism. This effervescent age witnessed rapid developments in the harnessing
of electricity, with the 1745 invention of the Leyden jar culminating in Alessandro
Volta’s 1800 invention of the voltaic cell. Analogies between electrostatics and
magnetism were tantalizing, but the link between them proved elusive.
m = IA (1)
The form of the field represented by Eq. (2) and illustrated in Fig. 3 is identical
to that of an electric dipole, so m is often referred to as a magnetic dipole although
we have no evidence for the existence of independent magnetic poles. The dipole
moment is best represented by an arrow in the direction of m, although it is still
commonplace to see the north-seeking and south-seeking poles of a magnet denoted
by the letters N and S. Old habits die hard.
Magnetic moments tend to align with magnetic fields in which they are placed.
The torque on the dipole m is Γ = μ0 m × H, and the corresponding energy of the
1 History of Magnetism and Basic Concepts 11
Fig. 3 Contours of equal magnetic field produced by a magnetic dipole moment m, represented
by the grey arrow
=m×B (3)
E = −m.B (4)
The two rival descriptions of magnetization in solids following from the work of
Coulomb or Ampère, based either on magnetic poles or on electric currents, have
colored thinking about magnetism ever since (Fig. 4). The poles have no precise,
independent physical reality; they are fictitious entities that are a mathematically-
convenient way to represent the H-field, which is of critical importance in mag-
netism because it is the local H-field that determines the state of magnetization
of a solid. Currents are closer to reality; electric current loops exist, and they do
act like magnets. Although it is difficult to attribute the intrinsic spin moment of
the electron to a current, the amperian picture of the origin of magnetic fields is
generally adopted in modern textbooks.
Nineteenth-century electromagnetism owed much to the genius of Michael
Faraday. Guided entirely by observation and experiment, with no dependence on
formal theory, he was able to perfect the concept of magnetic field, which he
12 J. M. D. Coey
Fig. 4 Alternative
+++++ σ m+
coulombian (left) and
amperian (right) descriptions
of the magnetization of a
uniformly magnetized
cylinder, with a magnetic
dipole moment m in the
direction represented by the
jms
black arrow; σm ± is the
surface magnetic charge
density, jms is the surface
electric current density
-----
σ m-
∇.B = 0
ε0 ∇.E = ρ
(5)
(1/μ0 ) ∇ × B = j + ε0 ∂E/∂t
∇ × E = −∂B/∂t
The first and third equations express the idea that there are no sources of the
magnetic B-field other than time-varying electric fields and electric currents of
1 History of Magnetism and Basic Concepts 13
density j, whereas the second and fourth equations show that the electric field
results from electric charge density ρ and time-varying magnetic fields. Maxwell’s
equations are invariant in a moving frame of reference, although the relative
magnitudes of E and B are altered.
The famous wavelike solutions of these equations in the absence of charges and
currents are electromagnetic waves, which propagate in free space with velocity
c = 1/(ε0 μ0 )1/2 . In SI, the definition of the magnetic constant μ0 is linked to the
fine structure constant. To nine significant figures, it is equal to 4π 10−7 NA−2 . ε0
is then related to the definition of the velocity of light. Heinrich Hertz demonstrated
Maxwell’s electromagnetic waves experimentally in 1888, and he showed that their
behavior was essentially the same as that of light. Hertz could think of no practical
application for his work, yet within a few decades, it had become the basis of radio
broadcasting and wireless communication!
The mechanical effects of electric and magnetic fields were summarized by
Hendrik Lorentz in his expression for the force density FL :
F L = ρE + j × B (6)
The equivalent expression for the force on a particle of charge q moving with
velocity v is f = q(E + v × B).
Two further fields H and D are introduced in the formulation of Maxwell’s
equations in a material medium to circumvent the inaccessibility of the current and
charge distributions in the medium. We have no direct way of measuring the atomic
charges associated with the polarization of a ferroelectric material or the atomic
currents associated with the magnetization of a ferromagnetic material, so we define
H and D in terms of fields created by the measurable free charges ρ and free currents
j, with dipolar contributions from the magnetization M or polarization P of any
magnetic or dielectric material that may be present. The equations now read:
∇.B = 0
∇.D = ρ
(7)
∇ × H = j + ∂D/∂t
∇ × E = −∂B/∂t
They are further simplified in a static situation when the time derivatives are
zero. The new fields are trivially related to B and E in free space since B = μ0 H and
D = ε0 E, but in a material medium, the H-field is defined in terms of the B-field and
the magnetization M (the magnetic moment per unit volume) as H = B/μ0 – M or
B = μ0 (H + M) (8)
14 J. M. D. Coey
H M B
+++++
–––––
B = P0(H + M)
Fig. 5 B, H, and M for a uniformly magnetized ferromagnetic bar. Eq. (8) is represented by the
vector triangle. The H-field can be regarded as originating from a distribution of positive and
negative magnetic charge (south and north magnetic poles) on opposite faces
1 ∇ · M r − r 3 M · en r − r 2
H (r) = − d r + d r (9)
4π V |r − r |3 S |r − r |3
This formula gives H(r) both inside and outside the magnetic material. Outside
B(r) = μ0 H(r).
The amperian expression for the magnetic field produced by a distribution of
currents is based on the Biot-Savart expression for the field due to a current element,
including contributions from the current density jm = ∇ × M in the bulk, and
jms = M × en at the surface:
μ0 ∇ × M × r − r 3 (M × en ) × r − r 2
B (r) = d r + d r
4π V |r − r |3 S |r − r |3
(10)
This formula gives B(r) both inside and outside the magnetic material. The same
result can be obtained by appropriate integration of Eq. 2 over a magnetization
distribution M(r) [12].
For uniformly magnetized ellipsoids, the demagnetizing field Hd is related to the
magnetization by
H d = −N M (11)
where N is a tensor with unit trace [13]. It reduces to a simple scalar demagnetizing
factor 0 < N < 1 when the magnetization lies along a principal axis of the ellipsoid.
N ≈ 0 for a long needle magnetized along its axis, and N = 1 for a flat plate
magnetized perpendicular to the plane. A sphere has N = 1/3. For any shape
less symmetric than an ellipsoid, the demagnetizing field is nonuniform. There are
useful approximate formulae for square bars and cylinders [14], such as 1/(2n + 1)
√
and 1/[(4n/ π) + 1], respectively, but they should not obscure the fact that the
demagnetizing field in these shapes really is quite nonuniform. Here n is the ratio of
length to diameter. The demagnetizing field is the reason why for centuries magnets
were condemned to take awkward shapes of bars or horseshoes to avoid substantial
self-demagnetization and why the most successful electromagnetic machines of
the nineteenth century were built around electromagnets rather than permanent
magnets. The hardened steel magnets of the day showed little coercivity and were
easily demagnetized. Demagnetizing fields are also the cause of ferromagnetic
domains. The shape constraint on permanent magnets was not lifted until the middle
of the twentieth century. Permanent magnets then came to the fore in the design of
electric motors and magnetic devices. Fig. 6 illustrates a collection of magnets from
the eighteenth, nineteenth, and twentieth centuries.
The imaginative world of Maxwell and his followers in the latter part of the
nineteenth century when the electromagnetic revolution was in full swing was
16 J. M. D. Coey
Fig. 6 Magnets from four centuries; top, seventeenth-century lodestone, nineteenth-century elec-
tromagnet; bottom, eighteenth-century horseshoe magnet, twentieth-century alnico and Nd2 Fe14 B
magnets (not to scale)
actually far removed from our own [15]. They envisaged light and other Hertzian
waves as propagating in an all-pervasive aether, which was believed to possess
magical mechanical properties – it had to be a massless incompressible fluid,
transparent and devoid of viscosity, yet millions of times more rigid than steel!
Elaborate mechanical models were envisaged for the waves and fields. In due course
it came to be understood that reality was represented by the abstract mathematics,
which remained after all the mechanical props had been discarded.
The Earth’s field was the prime focus of attention of magnetism for over a millen-
nium, especially after it was understood that the magnetic field was of terrestrial
origin. By the beginning of the nineteenth century, the components of the field were
1 History of Magnetism and Basic Concepts 17
being recorded regularly in laboratories across the world. A comparison of the daily
magnetic records at Paris and Kazan, cities lying 4000 km apart, for the same day
in 1825, showed astonishingly similar short-term fluctuations. This inspired Carl
Friedrich Gauss to establish a worldwide network of 50 magnetic observatories,
coordinated from Göttingen, to make meticulous simultaneous measurements of the
Earth’s field, in the hope that if enough high-quality data could be collected, the
mystery of its origin and its fluctuations might be solved. This heroic pioneering
venture in international scientific collaboration amassed stores of data that were
enormous for that time. It inspired Gauss to develop spherical harmonic analysis,
from which he calculated that the leading, dipolar term accounted for about 90%
of the field and that the origin of the stable component was essentially internal.
Edward Sabine later spotted that the intensity of the short-term fluctuations tracked
the 11-year sunspot cycle, which we now know corresponds to reversals of the
solar magnetic field. But in its primary aim, Gauss’s Magnetische Verein must be
counted a failure. No amount of data, however copious and precise, could reveal a
deterministic origin of a phenomenon that was fundamentally chaotic. Piles of data
with no theory or hypothesis through which to view and be tested by them are not
very informative. This lesson was learned slowly.
The pole picture of the Earth’s magnetic field, albeit with poles that needed to
travel tens of kilometers every year to account for the secular variation, yielded
eventually in the academy if not in the popular imagination to one based on
electric currents driven by convection in the Earth’s liquid core. Joseph Larmor,
a dogged believer in the aether, was an early proponent of the geomagnetic dynamo.
He demonstrated the precession of a magnet in a magnetic field at a frequency
fL = γB/2π that bears his name. The precession is analogous to that of a spinning
top in a gravitational field; it is a consequence of the torque on a magnetic moment
expressed by Eq. 3. The constant γ, known as the gyromagnetic ratio, is the ratio of
the magnetic moment to its associated angular momentum. The proportionality of
these two quantities that at first sight appear quite dissimilar, the famous Einstein-de
Haas effect, was eventually demonstrated experimentally in 1915 (Fig. 7).
M
spontaneous magnetization
remanence
major loop
Fig. 8 The hysteresis loop of magnetization M against magnetic field H for a typical permanent
magnet, showing the initial magnetization curve from the equilibrium multidomain state and the
major loop. Ms is the saturation magnetization, Mr the remanent magnetization at zero field, and
Hc the coercive field required to reduce the magnetization to zero
The discovery of the electron in the closing years of the nineteenth century was a
huge step toward the modern understanding of magnetism. The elementary charged
particle with mass me = 9.109 10−31 kg and charge e = −1.602 10−19 C had been
named by the Irish scientist George Johnstone Stoney in 1891, several years before
Jean Perrin in France actually identified negatively charged particles in a cathode
ray tube and J. J. Thompson in England measured their charge to mass ratio e/me ,
by deflecting the electrons in a magnetic field and making use of Eq. 6. Another
Irish scientist, George Francis FitzGerald, suggested in 1900 that magnetism might
be due to rotational motion of these electrons. They turned out to be not only the
carriers of electric current but also the essential magnetic constituent of atoms and
solids.
H i = nW M (12)
χ = C/T (13)
μB = e/2me
or 9.274 × 10−24 Am2 , twice as large as the moment associated with a unit of
orbital angular momentum in Bohr’s model of the atom. The gyromagnetic ratio
of magnetic moment to angular momentum for the electron spin is γ ≈ e/me ,
so the Larmor precession frequency eB/2πme for the electron is 28 GHzT−1 .
22 J. M. D. Coey
The problem of the electron’s magnetism was finally resolved by Paul Dirac
in 1928 when he succeeded in writing Schrödinger’s equation in relativistically
invariant form, obtaining the non-relativistic electron spin in terms of the 2 × 2
Pauli matrices. Together with Dirac, Werner Heisenberg formulated the exchange
interaction represented by the famous Heisenberg Hamiltonian
H = –2J S i .S j (15)
to describe the coupling between the vector spins Si and Sj of two nearby many-
electron atoms i and j. The spin vectors S are the spin angular momenta in units of .
The value of the exchange integral J was closely related to Weiss’s molecular field
coefficient nW and depends strongly on interatomic distance. It can be positive, if it
tends to align the two spins parallel (ferromagnetic exchange), or negative if it tends
to align the pair antiparallel (antiferromagnetic exchange). The value of S is obtained
from the first of the three rules, discussed below, that were formulated by Friedrich
Hund around 1927 for finding the ground state of a multi-electron atom. The
exchange interactions among the electrons of the same atom are much stronger than
those between the electrons of adjacent atoms given by Eq. (15). The fundamental
insight that magnetic coupling of electronic spins is governed by electrostatic
coulomb interactions, subject to the symmetry constraints of quantum mechanics,
was the key needed to unlock the mysteries of ferromagnetism. Exchange is
discussed in Chap. 2, “Magnetic Exchange Interactions.”
The magnetic moment of an atom or ion is the sum of two contributions. One
arises from the intrinsic spin angular momentum of the atomic electrons. The other
comes from their quantized orbital angular momentum. The moments associated
with each type of angular momentum have to be summed according to the rules of
quantum mechanics. The moment associated with ½ of spin angular momentum is
practically identical to that associated with of orbital angular momentum, namely,
one Bohr magneton in each case. The quantum theory of magnetism is therefore the
quantum theory of angular momentum. Hund’s rules were an empirical prescription
for determining the total angular momentum of the many-electron ground state of
electrons belonging to the same atom or ion. Firstly, the rule is to maximize the
spin angular momentum S while respecting the Pauli principle that no two electrons
can be in the same quantum state. Secondly, the orbital angular momentum L is
maximized, consistent with the value of S, and thirdly the spin and orbital momenta
are coupled together to form the total angular momentum J = L ± S, according
to whether the electronic shell is more or less than half full. The total magnetic
moment (in units of μB ) is then related to the total angular momentum (in units of
) by a numerical Landé g-factor, which is 1 for a purely orbital moment and 2 for
pure spin.
The spin-orbit coupling, which arises in the atom from motion of the electron
in the electrostatic potential of the charged nucleus and gives rise to Hund’s third
rule, is another key interaction. Of fundamentally relativistic character, it emerges
naturally from Dirac’s relativistic quantum theory of the electron, and it turns out to
be at the root of many of the most interesting phenomena in magnetism, including
1 History of Magnetism and Basic Concepts 23
magneto-optics, magnetocrystalline anisotropy, and the spin Hall effect. The spin-
orbit interaction for a magnetic ion is represented by the Hamiltonian L.S, where
L is the orbital angular momentum of the many-electron atom in units of and
is the atomic spin-orbit coupling constant. Like the exchange constant J , has
dimensions of energy.
Felix Bloch in 1930 described the spin waves that are the quantized elementary
excitations of a ferromagnetic array of atoms whose spins are coupled by Heisen-
berg exchange. These excitations have an angular frequency ω and a wavevector
k that are related by the dispersion relation ω = Dk2 , where D is the spin wave
stiffness constant. It is proportional to J .
The first quantum theories of magnetism regarded the electrons as localized
on the atoms or ions, but an alternative magnetic band theory of ferromagnetic
metals was developed by John Slater and Edmund Stoner in the 1930s. It accounted
for the non-integral, delocalized spin moments found in Fe, Co, and Ni and their
alloys, although the theory in its original form greatly overestimated the Curie
temperatures. The delocalized, band electron model of Slater and the localized,
atomic electron model of Heisenberg were two distinct paradigms for the theory
of magnetism that persisted until sophisticated computational methods for treating
the many-body interelectronic correlations in the ground state of multi-electron
atoms were devised toward the end of the twentieth century. The differences
between the two approaches are epitomized in the calculation of the paramagnetic
susceptibility. Pauli found a small temperature-independent susceptibility resulting
from Fermi-Dirac statistics for delocalized electrons, whereas Léon Brillouin had
used Boltzmann statistics and the Bohr model to derive the Curie law susceptibility
of an array of atoms with localized electrons.
The sixth Solvay Conference, held in Brussels in October 1930 (Fig. 9), was
devoted to magnetism [21]. It followed four years of brilliant discoveries in
theoretical physics, which set out the modern electronic theory of condensed matter.
Yet the immediate impact on the practical development of functional magnetic
materials was surprisingly slight. Dirac there made the perceptive remark “The
underlying physical laws necessary for the mathematical theory of a large part of
physics and the whole of chemistry are completely known, and the difficulty is only
that the exact application of these laws leads to equations much too complicated to
be soluble.”
Magnetic Phenomenology
Fig. 9 The 1930 Solvay Conference on Magnetism Back row: Herzen, Henriot, Verschaffelt,
Manneback, Cotton, Errera, Stern, Piccard, Gerlach, Darwin, Dirac, Bauer, Kapitza, Brioullin,
Kramers, Debye, Pauli, Dorfman, van Vleck, Fermi, Heisenberg. Front row: de Donder, Zeeman,
Weiss, Sommerfeld, Curie, Langevin, Einstein, Richardson, Cabrera, Bohr, de Haas
T C ,qp T qp TN T qp T fN T
M M M
B B
B A B
A
TC T TN T T fN T
A
A
Fig. 10 Schematic temperature dependences of the inverse susceptibility (top) and (sub)lattice
magnetization (bottom) of a ferromagnet (left), an antiferromagnet (center), and a ferrimagnet
(tight)
Micromagnetism
Fig. 11 Two types of 180◦ domain walls: a) the Bloch wall and b) the Néel wall
interaction; the effect of chemical bonding with the ligands of an atom is the ligand
field interaction. The two effects are comparable in magnitude for 3d ions [22].
Magnetocrystalline anisotropy arises from the interplay of the crystal/ligand field
and spin-orbit coupling. The simplest case is for uniaxial (tetragonal, hexagonal,
rhombohedral) crystals, where the leading term in the energy density is of the form
Ea = K1 sin2 θ + . . . .. (16)
where θ is the angle between M and the symmetry axis. Two opposite easy
directions lie along the crystal axis if the anisotropy constant K1 is positive, but
there are many easy directions lying in an easy plane perpendicular to the crystal
axis (θ = π/2) when K1 is negative. Anisotropy arises also from overall sample
shape, due to the demagnetizing energy ½MHd , which gives another contribution in
sin2 θ that depends on the demagnetizing factor N with
1
K1 sh = μ0 Ms 2 (1 − 3N ) (17)
4
Magnetic Materials
The traditional magnetic materials were alloys of the ferromagnetic metals, Fe,
Co, and Ni. The metallurgy and magnetic properties of these alloy systems were
the focus of investigations of technical magnetism in the first half of the twentieth
century, when useful compositions were developed such as Permendur, Fe50 Co50 ,
the alloy with the highest magnetization (1.95 MAm−1 ); Permalloy Fe20 Ni80 , which
has near-zero anisotropy and magnetostriction, together with very high relative
permeability (μr = (1 + χ) ≈ 105 ); and Invar Fe64 Ni36 a composition with near-
28 J. M. D. Coey
Fig. 12 Unit cells of the ferromagnetic elements Fe (body-centered cubic, left), Ni (face-centered
cubic, center), and Co, Gd (hexagonal close-packed, right) [29], with kind permission from
Cambridge University Press
zero thermal expansion around room temperature. The early investigations are well
summarized in Bozorth’s 1950 monograph [23]. The fourth ferromagnetic element
at room temperature is the rare earth gadolinium. The crystal structures of these
elemental ferromagnets are illustrated in Fig. 12.
An important practical advance in the story of permanent magnet development
was the thermal processing of a series of Al-Ni-Co-Fe alloys, the Alnico magnets,
that was initiated in Japan in 1932 by Tokushichi Mishima. Their coercivity relied
on achieving a nanostructure of aligned acicular (needle-like) regions of Co-Fe in
a matrix of nonmagnetic Ni-Al. It was the shape of the ferromagnetic regions that
gave the alloys some built-in magnetic anisotropy (Eq. 17), but it still had to be
supplemented with global shape anisotropy by fabricating the Alnico into a bar or
horseshoe in order to avoid self-demagnetization. The mastery of coercivity that
was acquired over the course of the twentieth century (Fig. 13) was spectacular,
and burgeoning applications in technical magnetism of soft and hard magnetic
materials were the direct consequence. The terms “soft” and “hard” were derived
originally from the magnetic steels that were used in the nineteenth century. The
most useful figure of merit for the hard, permanent magnets is the maximum energy
product |BH|max , equal to twice the energy in the stray field produced by a unit
volume of magnet. The SI unit is kJm−3 . Energy product doubled every 12 years
for most of the twentieth century, thanks to the discovery in the 1960s of rare
earth cobalt intermetallic compounds and the discovery of new rare earth iron-
based materials in the 1980s. Comparable progress with decreasing hysteresis losses
in soft, electrical steels continued to the point where they became a negligible
fraction of the resistive losses in the copper windings of electromagnetic energy
converters. Ultrasoft amorphous magnetic glasses were developed in the 1970s.
Applications of soft and hard magnetic materials are discussed in Chaps. 29, “Soft
Magnetic Materials and Applications,” and 28, “Permanent Magnet Materials and
Applications” respectively.
A good working knowledge of the quantum mechanics of multi-electron atoms
and ions had been developed by the middle of the twentieth century, mainly from
1 History of Magnetism and Basic Concepts 29
Nd-Fe-B
Fig. 13 The development of coercivity over the ages and in the twentieth century
Magnetic Oxides
The focus on localized electron magnetism in the 1950s and 1960s led to systematic
investigations of exchange interactions in insulating compounds where the spin
30 J. M. D. Coey
The drawback of any oxide magnetic material is that its magnetization is never
more than a third of that of metallic iron. This is unavoidable because most of the
unit cell volume is occupied by large, nonmagnetic O2− anions, with the high-spin
ferric iron Fe3+ or other magnetic ions confined to the interstices in the oxygen
lattice. To make matters worse, a ferrimagnetic structure reduces the magnetization
further. There are relatively few ferromagnetic oxides; CrO2 is one example. It is
not an insulator, but a half metal, with a gap in the minority-spin conduction band.
A search for insulating ferromagnetic oxides in the 1950s led to the investi-
gation of ABO3 compounds with the perovskite structure. Here the magnetic B
cations occupy the 1a octahedral sites, and the nonmagnetic A cations occupy
the 12-coordinated 1b sites in the ideal cubic structure. It proved to be possible
to obtain ferromagnetism provided the A cations are present in two different
valence states. This works best in mixed-valence manganites [26], with composition
(La3+ 2+
0.7 M0.3 )MnO3 where M = Ba, Ca, or Sr. The resulting mixture of Mn
3+ (3d4 )
4+ 3
and Mn (3d ) on B sites leads to electron hopping with spin memory from
one 3d3 core to another. This is the ferromagnetic double exchange interaction,
envisaged by Clarence Zener in 1951. Similar electron hopping occurs for Fe2+
and Fe3+ in the octahedral sites of magnetite. A consequence is that the oxides,
though ferromagnetic, are no longer insulating, and the Curie temperatures are not
particularly high – they do not exceed 400 K. A notable feature of the mixed-valence
manganites, related to their hopping conduction, is the “colossal magnetoresistance”
observed near the Curie point, where there is a broad maximum in the resistance
that can be suppressed by applying a magnetic field of several tesla. All four
oxide structures are presented in Fig. 14. They illustrate the importance of crystal
chemistry for determining magnetic properties.
Fig. 14 Crystal structures of magnetic oxides: perovskite (top left), spinel (bottom left), garnet
(center), magnetoplumbite (right). The oxygen coordination polyhedral around the magnetic
cations (tetrahedrons, blue, or octahedrons, brown) is illustrated. The spheres are large nonmag-
netic cations. Unit cells are outlined in black. Magnetoplumbite is hexagonal, and the others are
cubic [31], with kind permission from APS
32 J. M. D. Coey
Intermetallic Compounds
Fig. 15 Crystal structures of ferromagnetic intermetallic compounds: YFe2 (cubic, left) SmCo5
(hexagonal, top centre), Co2 MnSi (cubic, bottom centre), Nd2 Fe14 B (tetragonal, right). Fe and Co
Mn are the small brown/red, blue, and scarlet spheres. Rare earths are the large spheres. Si and B
are grey and black
Model Systems
Magnetism has proved to be a fertile proving ground for condensed matter theory.
The first mean-field theory was Weiss’s molecular field of magnetism, later
generalized by Lev Landau in the USSR in 1937. There followed more sophisticated
theories of phase transitions, with magnetism providing much of the data to support
them. The single-ion anisotropy of rare earth ions due to the local crystal field
reduces the effective dimensionality of the magnetic order parameter from three
to two for easy-plane (xy) anisotropy or from three to one for easy-z-axis (Ising)
anisotropy. Magnetically ordered compounds can be synthesized with an effective
spatial dimension of one (chains of magnetic atoms), two (planes of magnetic
atoms), or three (networks of magnetic atoms), as well as ladders and isolated
motifs. Magnetism has provided a treasury of materials that show continuous
phase transitions as a function of temperature or quantum phase transitions at zero
temperature as a function of pressure or magnetic field, as well as topological phases
such as the two-dimensional xy model, investigated by David Thouless, Michael
Kosterlitz, and Duncan Haldane. It is frequently possible to realize magnetic
materials that embody the essential electronic or structural features of the theoretical
models.
An early theoretical milestone was Lars Onsager’s 1944 solution of the two-
dimensional Ising model, where spins are regarded as one-dimensional scalars
that can take only values of ±1. The behavior of more complex and realistic
systems such as the three-dimensional Heisenberg model near its Curie temperature
was solved numerically using the renormalization group technique developed by
Kenneth Wilson in the 1970s. The ability to tailor model magnetic systems, with
an effective spatial dimension of 1 or 2 due to their structures of chains or planes
of magnetic ions and an effective spin dimension of 1, 2, or 3 determined by
magnetocrystalline anisotropy due to the combination of the crystal/ligand field and
the spin-orbit interaction, was instrumental in laying the foundation of the modern
theory of phase transitions. The theory is based on universality classes where
power-law temperature variations of the order parameter and its thermodynamic
derivatives with respect to temperature or magnetic field in the vicinity of the phase
transition are characterized by numerical critical exponents that depend only by the
dimensionality of the space and the magnetic order parameter.
Another fecund line of enquiry was “Does a single impurity in a metal bear a
magnetic moment?” This was related to Jun Kondo’s formulation of a problem
concerning the scattering of electrons by magnetic impurities in metals and its
eventual solution in 1980. In the presence of antiferromagnetic coupling between
an impurity and the conduction electrons of a metallic host, the combination enters
a nonmagnetic ground state below the Kondo temperature TK . The Kondo effect
is characterized by a minimum in the electrical resistivity. The study of magnetic
impurities in metals focused attention on the relation between magnetism and
electronic transport, which has proved extremely fruitful, leading to several Nobel
Prizes and the emergence in the 1990s of spin electronics.
1 History of Magnetism and Basic Concepts 35
where a is a constant, Jsd is the exchange coupling between the localized impurity
and the conduction electrons, and ξ is twice the product of r and the Fermi
wavevector. It was studied intensively in the 1970s in dilute alloys such as AuFe
or CuMn, known as spin glasses (the host is in bold type, and the impurity in
italics). The impurity in these hosts retains its moment at low temperatures, and
the RKKY exchange coupling J (∇) between a pair of spins is as likely to be
ferromagnetic (positive) as antiferromagnetic (negative). The impurity spins freeze
progressively in random orientations around a temperature Tf that is proportional to
the magnetic concentration. The nature of this transition to the frozen spin glass state
was exhaustively debated. A related issue, the long-range exchange interactions
associated with the ripples of spin polarization created by a magnetic impurity in
a metal, led to an understanding of complex magnetic order in the rare earth metals
( Chap. 14, “Magnetism of the Elements”).
The magnetism of electronic model systems such as a chain of 1s atoms with an
on-site coulomb repulsion U when two electrons occupy the same site, formulated
by John Hubbard in 1963, has proved to be remarkably complex. Control parameters
in the Hubbard model are the band filling and the ratio of U to the bandwidth, and
they lead to insulating and metallic, ferromagnetic, and antiferromagnetic solutions.
Amorphous Magnets
An important question, related to the dilute spin glass problem, was what effect does
atomic disorder have on magnetic order and the magnetic phase transition in mag-
netically concentrated systems? Here a dichotomy emerges between ferromagnetic
and antiferromagnetic interactions. The answer for materials with ferromagnetic
exchange and a weak local electrostatic (crystal field) interaction is that the atomic
disorder has little effect.
Techniques for rapidly cooling eutectic melts at rates of order 106 Ks−1
developed around 1970 produced a family of useful amorphous ferromagnetic alloys
based on Fe, Co, and Ni, with a minor amount of metalloid such as B, P, or Si. These
metallic glasses, frequently in the form of thin ribbons obtained by melt spinning,
were magnetically soft and proved that ferromagnetic order could exist without a
crystal lattice. There are no crystal axes, and weak local anisotropy due to the local
electrostatic interactions averages out. The magnetic metallic glasses are mechani-
cally strong and have found applications in transformer cores and security tags.
36 J. M. D. Coey
where the attempt frequency 1/τ0 was taken to be the natural resonance frequency,
∼109 Hz. When the particles are superparamagnetic, the magnetization of particles
smaller than a critical size fluctuates rapidly above a critical blocking temperature.
The magnetization at lower temperatures, or for larger particles, does not fluctuate
on the measurement timescale, and the particles are then said to be blocked. The
blocking criterion for magnetic measurements at room temperature is defined,
somewhat arbitrarily, as /kB T ≈ 25, corresponding to τ ≈ 100 s and ≈ 1 eV
(see Chap. 20, “Magnetic Nanoparticles”). The 10-year stability criterion is
/kB T ≈ 40. Cooling an ensemble of particles through the blocking temperature
Tb = Ku V/25kB in a magnetic field leads to a relatively stable thermoremanent
magnetization. The typical size of iron oxide particles that are superparamagnetic at
room temperature is 10 nm.
The magnetization of baked clay becomes blocked on cooling through Tb in the
Earth’s magnetic field. From the direction of the thermoremanent magnetization
of appropriately dated hearths of pottery kilns, records of the historical secular
variation of the Earth’s field could be established, a topic known as archeomag-
netism. Application of the same idea of thermoremanent magnetization to cooling
of igneous rocks in the Earth’s field provided a direct and convincing argument
for geomagnetic reversals and continental drift; rocks cooling at different periods
experienced fields of different polarities (Fig. 16), which followed an irregular
sequence on a much longer timescale than the secular variation. The reversals could
be dated using radioisotope methods on successive lava flows. This gave birth to the
subfield of paleomagnetism and in turn allowed dating of the patterns of remanent
magnetization picked up in oceanographic surveys conducted in the 1960s that
established the reality of seafloor spreading. The theory of global plate tectonics
has had far-reaching consequences for Earth science [29].
Superparamagnetic particles have found other practical uses. Ferrofluids, the
colloidal suspensions of nanoparticles in oil or water with surfactants to inhibit
agglomeration, are just one. They behave like anhysteretic ferromagnetic liquids.
Individual particles or micron-sized polymer beads loaded with many of them
may be functionalized with streptavidin and used as magnetic labels for specific
biotin-tagged biochemical species, enabling them to be detected magnetically and
separated by high-gradient magnetic separation based on the Kelvin force on a
particle with moment m, fK = (m.∇)B. Medical applications of magnetic fine
particles include hyperthermia (targeted heating by exposure to a high-frequency
magnetic field) and use as contrast agents in magnetic resonance imaging. However
the most far-reaching application of magnetic nanoparticles so far has been in
magnetic recording.
38 J. M. D. Coey
Fig. 16 Polarity of the thermoremanent magnetization measured across the floor of the Atlantic
ocean (left). Current polarity is dark; reversed polarity is light. The pattern is symmetrical about the
mid-ocean ridge, where new oceanic crust is being created. Random reversals of the Earth’s field
over the past 5 My, which are dated from other igneous lava flows, determine the chronological
pattern (right) that is used to determine the rate of continental drift, of order centimeters per year.
(McElhinney, Palaeomagnetism and Plate Tectonics [29], courtesy of Cambridge University Press)
Magnetic Recording
Particulate magnetic recording enjoyed a heyday that lasted over half a century,
beginning with analog recording on magnetic tapes in Germany in the 1930s through
digital recording on the hard and floppy discs that were introduced in the 1950s and
1960s, before eventually being superseded by thin-film recording in the late 1980
[27]. Particulate magnetic recording [30] was largely based on acicular particles of
γFe2 O3 often doped with 1–2% Co. Elongated iron particles were also used, and
acicular CrO2 was useful for rapid thermoremanent reproduction of videotapes on
account of its low Curie temperature. Magnetic digital tape recording with hard
ferrite particulate media continues to be used for archival storage.
The trend with magnetic media has always been to cram ever more digital
data onto ever smaller areas. This has been possible because magnetic recording
technology is inherently scaleable since reading is done by sensing the stray
field of a patch of magnetized particles. It follows from Eq. 2 that since the
dipole field decays as 1/r3 and the moment m ∼ Mr3 , the magnitude of B is
unchanged when everything else shrinks by the same scale factor – at least until
the superparamagnetic limit KV/kB T ≈ 40 is reached, at which point the magnetic
records become thermally unstable. To continue the scaling to bit sizes below
1 History of Magnetism and Basic Concepts 39
Fig. 17 Exponential growth of magnetic recording density over 50 years. The lower panel shows
the magnetized magnetic medium with successive generations of read heads based on anisotropic
magnetoresistance (AMR), giant magnetoresistance (GMR), and tunnel magnetoresistance (TMR)
100 nm, granular films of a highly anisotropic tetragonal Fe-Pt alloy are used
to maintain stability of the magnetic records on ever-smaller oriented crystalline
grains. The individual grains are less than 8 nm in diameter. Over the 65-year history
of hard disc magnetic recording, the bit density has increased by eight orders of
magnitude, at ever-decreasing cost (Fig. 17). Copies cost virtually nothing, and the
volume of data stored on hard discs in computers and data centers doubles every
year, so that as much new data is recorded each year as was ever recorded in all
previous years of human history. This data explosion is unprecedented, and the
third magnetic revolution, the big data revolution, is sure to have profound social
and economic consequences. Although flash memory has displaced the magnetic
hard discs from personal computers. The huge data centres, which are the physical
embodiment of the ‘cloud’ where everything we download from the interenet is
stored continue to use hard disc drives.
40 J. M. D. Coey
Methods of Investigation
Materials Preparation
Silicon steel has been produced for electromagnetic applications by hot rolling
since the beginning of the twentieth century. Annual production is now about 15
million tonnes, half of it in China. Permanent magnets, soft ferrites, and specialized
magnetic alloys are produced in annual quantities ranging from upward of a hundred
to a million tonnes. All such bulk applications of magnetism are highly sensitive to
the cost of raw materials. This effectively disqualifies about a third of the elements
in the periodic table and half of the heavy transition elements from consideration
as alloy additives in bulk material. Newer methods such as mechanical alloying
of elemental powders and rapid quenching from the melt by strip casting or melt
spinning have joined the traditional methods of high-temperature furnace synthesis
of bulk magnetic materials.
The transformation of magnetic materials science that has gathered pace since
1970 has been triggered by the ability to prepare new materials for magnetic devices
in thin-film form. The minute quantity of material needed for a magnetic sensor
or memory element, where the layers are tens of nanometers thick, means that
any useful stable element can be considered. Platinum, for example, may sell for
$30,000 per kilogram, yet it is an indispensable constituent of the magnetic medium
in the 400 million hard disc drives shipped each year that sell for about $60 each.
1 History of Magnetism and Basic Concepts 41
Experimental Methods
thin-film devices has been matched by the development of the sensitive analytical
methods needed to characterize them. Hysteresis in thin films is conveniently
measured by MOKE or by anomalous Hall effect (AHE) when the films are
magnetized perpendicular to their plane. Magnetic fields and measurements are
discussed in Chap. 22, “Magnetic Fields and Measurements” and other chapters
in Part 3.
An important consequence of the increasing availability of commercial super-
conducting magnets from the late 1960s was the development of medical diagnostic
imaging of tissue based on proton relaxation times measured by NMR. Thousands
of these scanners in hospitals across the world provide doctors with images of the
hearts, brains, bones, and every sort of tumor.
Computational Methods
After about 1980, computer simulation began to emerge as a third force, besides
experiment and theory, to gain insight into the physics of correlated electrons in
magnetic systems. Contributions are mainly in two areas. One is calculation of
the electronic structure, magnetic structure, magnetization, Curie temperature, and
crystal structure of metallic alloys and compounds by using the density functional
method. Magnetotransport in thin-film device structures can also be calculated. Here
there is potential to seek and evaluate new magnetic phases in silico, before trying
to make them in the laboratory. This magnetic genome program is in its infancy;
success with magnetic materials to date has been limited, but the prospects are
enticing.
The other area where computation has become a significant source of new insight
is micromagnetic simulation. The domain structure and magnetization dynamics of
magnetic thin-film structures and model heterostructures are intensely studied, both
in industrial and academic laboratories. Simulation overcomes the surface limitation
of experimental domain imaging. Software is generally based on finite element
methods or the Landau-Lifshitz-Gilbert equation for magnetization dynamics.
Spin Electronics
it is scattered. But angular momentum is not conserved, and spin flip scattering
is common in metals. Perhaps one scattering event in 100 changes the electron
spin state, so the spin diffusion length ls should be about ten times the mean free
path λ of the electron in a solid. When electronic device dimensions were many
microns, there was no chance of an electron retaining the memory of any initial spin
polarization it may have had, unless the device itself was ferromagnetic. Anisotropic
magnetoresistance, where the scattering depends slightly on the relative orientation
of the current and magnetization because of spin-orbit coupling, can be regarded
as the archetypical spin electronic process. The relative magnitude of effect in
permalloy, for instance, is only ∼2%, but the alloy is extremely soft, on account
of simultaneously vanishing anisotropy and magnetostriction, so a permalloy strip
with current flowing at 45◦ to the magnetic easy axis along the strip for maximum
sensitivity – which can be achieved by a superposed “barber pole” pattern of highly
conducting gold – makes a simple, miniature sensor for low magnetic fields, with
a reasonable signal-to-noise ratio. AMR sensors replaced inductive sensors in the
heads used to read data from hard discs in 1990, and the annual rate of increase of
storage density improved sharply as a result.
Meanwhile, research activity on thin-film heterostructures where the layer
thickness was comparable to the spin diffusion length began to pick up as more
sophisticated thin-film vacuum deposition tools were developed. Spin diffusion
lengths are 200 nm in Cu, or about ten times the mean free path, as expected, but
they are shorter in the ferromagnetic elements and sharply different for majority-
and minority-spin electrons. The mean free path for minority-spin electrons in Co
is only 1 nm. Particularly influential and significant was the work carried out in
1988 in the groups of Peter Grunberg in Germany and Albert Fert in France on
multilayer stacks of ferromagnetic and nonferromagnetic elements that led to the
discovery of giant magnetoresistance (GMR). The effect depended on electrons
retaining some of their spin polarization as they emerged from a ferromagnetic
layer and crossed a nonmagnetic layer before reaching another ferromagnetic layer.
Big changes of resistance were found when the relative alignment of the adjacent
ferromagnetic iron layers in an Fe-Cr multilayer stack was altered from antiparallel
to parallel by applying a magnetic field (Fig. 18). At first, large magnetic fields and
low temperatures were needed to see the resistance changes, but the structure was
soon simplified to a sandwich of just two ferromagnetic layers with a copper spacer
that became known as a spin valve. Spin valves worked at room temperature, and
they were sensitive to the small stray fields produced by recorded magnetic tape or
disc media. In order to make a useful sensor, it was necessary to pin the direction
of magnetization of one of the ferromagnetic layers while leaving the other free to
respond to an in-plane field (Fig. 19).
It was here that the phenomenon of exchange bias came to the rescue. First
discovered in Co/CoO core shell particles by Meiklejohn and Bean in 1956, it was
extended to antiferromagnetic/ferromagnetic thin-film pairs in Néel’s laboratory
in Grenoble in the 1960s. By pinning one ferromagnetic layer with an adjacent
antiferromagnet (initially NiO), a useful GMR sensor could be produced with
a magnetoresistance change of order 10%. Exchange-biased GMR read heads
1 History of Magnetism and Basic Concepts 45
developed by Stuart Parkin and colleagues went into production at IBM in 1998 – a
remarkably rapid transfer from a laboratory discovery to mass production. Exchange
bias was the first practical use of an antiferromagnet. The Nobel Physics Prize was
awarded to Fert and Grunberg for their work in 2007.
Subsequent developments succeeded in eliminating the influence of the stray
field of the pinned layer on the free layer by means of a synthetic antiferromagnet.
This was another sandwich stack, like the slimmed-down spin valve, except the
spacer was not copper, but an element that transferred exchange coupling from one
ferromagnetic layer to the other. Ruthenium proved to be ideal, and a layer just
0.7 nm thick was found to be ideal for antiferromagnetic coupling [32].
GMR’s tenure as read-head technology was to prove as short-lived as that of
AMR. A new pretender with a much larger resistance change was based on the
magnetic tunnel junction (MTJ), a modified spin valve where the nonmagnetic
metal spacer is replaced by a thin layer of nonmagnetic insulator. Electron tunneling
across an atomically thin vacuum barrier had been a striking prediction of quantum
mechanics implicit in the idea of the wavefunction. The thin barrier was at first made
of amorphous alumina, but it was replaced by crystalline MgO after it was found in
2004 that junctions where the MgO barrier acts as a spin filter exhibit tunneling
magnetoresistance (TMR) in excess of 200% [33, 34] (Fig. 19). The adoption of
46 J. M. D. Coey
B B
I
free free
pinned pinned
af af
ΔR
I
ΔR
MR = (R↑↓−R↑↑)/R↑↑
B B
Spin valve sensor Magnetic tunnel junction (MTJ)
Fig. 19 Magnetic bilayer spin-valve stacks used as sensor (left) or as a memory element (right). In
each case, the magnetization lies in-plane, and the lower ferromagnetic reference layer is pinned by
exchange bias with the purple underlying antiferromagnetic layer, while the upper ferromagnetic
free layer changes its orientation in response to the applied magnetic field. The change in stack
resistance is plotted as a function of applied field. The magnetoresistance ratio MR is defined as the
normalized resistance change between parallel and antiparallel orientation of the two ferromagnetic
layers
TMR sensors in read heads in 2005 was accompanied by a change from in-plane to
perpendicular recording on the magnetic medium.
Despite the changing generations of readers, the hard disc writer remained
what is always had been, a miniature electromagnet that delivers sufficient flux
to a patch of magnetic medium to overcome its coercivity and write the record.
The extreme demands of magnetic recording have driven contactless magnetic
sensing to new heights of sensitivity and miniaturization requiring increasingly
hard magnetic media and new ways of writing them. Thin-film GMR and TMR
structures have also taken a new life as magnetic switches for nonvolatile memory
and logic. Most prominent is magnetic random access memory (MRAM), where
huge arrays of memory cells are based on magnetic tunnel junctions. Magnetic
sensing is discussed in Chaps. 31, “Magnetic Sensors,” and 22, “Magnetic
Fields and Measurements.”
Magnetic thin-film technology has now advanced to the point where uniform
layers in synthetic antiferromagnets and magnetic tunnel junctions only a few atoms
thick are routinely deposited on entire 200 or 300 mm silicon wafers. A corollary
of the short spin diffusion length of electrons in metals is the short distance – a
few atomic monolayers – necessary for an electron to acquire spin polarization on
transiting a ferromagnetic layer. Spin-polarized electron currents are central to spin
electronics.
1 History of Magnetism and Basic Concepts 47
The relation between magnetism and the angular momentum of electrons was
unveiled in Larmor precession and the Einstein-de Haas experiment over a hundred
years ago, but only in the present century has it become commonplace to associate
electric currents with short-range flows of angular momentum. A spin-polarized
current carrying its angular momentum into a ferromagnetic thin-film element can
exert torque in two ways. It can create an effective magnetic field, causing Larmor
precession of the magnetization of the element, and it can exert spin transfer torque,
described by John Slonczewski in 1996 that counteracts damping of the precession
and can be used to stabilize high-frequency oscillations or switch the magnetization
without the need for an external magnetic field. Spin torque switching is effective
for elements smaller than 100 nm in size, and unlike switching by current-induced
“Oersted” fields, it is scalable – an essential requirement for electronic devices. Luc
Berger showed that spin torque can also be used to manipulate domain walls.
A recurrent theme in the recent development of magnetism is the role of the spin-
orbit interaction. It is critically important in thin films [35], being responsible not
only for the Kerr effect, magnetocrystalline anisotropy, and anisotropic magnetore-
sistance but also for the anomalous Hall effect and the spin Hall effect, whereby
spin-orbit scattering of a current passing through a heavy metal or semiconductor
produces a buildup of electrons with opposite spin on opposite sides of the
conductor. This transverse spin current created by spin-orbit scattering enables the
injection of angular momentum into an adjacent ferromagnetic layer and the change
of its magnetization direction, an effect known as spin-orbit torque. Conversely,
the inverse spin Hall effect is the appearance of a voltage across the heavy metal on
pumping spin-polarized electrons into it from an adjacent ferromagnet, for example,
by exciting ferromagnetic resonance.
The origin of the intrinsic anomalous Hall effect was an open question in
magnetism, for well over a hundred years. A consensus is now building that it is due
to the geometric Berry phase acquired by electrons moving adiabatically through a
magnetic medium. The phase can be acquired from a non-collinear spin structure
in real space or from topological singularities in the band sturcture in reciprocal
space. Circular micromagnetic defects, known as skyrmions are also topologically
protected.
Another manifestation of spin-orbit interaction is the Rashba effect; when an
electric current is confined at an interface or surface, it tends to create a spin
polarization normal to the direction of current flow. One of the most remarkable
surface phenomena, arising from work by Haldane in 1988, is the possibility of
topologically protected spin currents. A special feature of the band structure ensures
that electrons at the surface or edges of some insulators or semiconductors are in
gapless states. Electrons in these states can propagate around the surface without
scattering, and they exhibit a spin order that winds around the surface as the
direction of electron spin is usually locked at right angles to their linear momentum.
Electrons at surfaces and interfaces can behave quite differently from electrons in
the bulk, and interfaces are at the heart of electronic devices. The introduction
of topological concepts into the discussion of spin-polarized electronic transport
48 J. M. D. Coey
and magnetic defects is providing new insight into magnetism at the atomic and
mesoscopic scales.
Conclusion
Magnetism since 1945 has been an area rich in discovery and useful applications,
not least because of the tremendous increase in numbers of scientists and engineers
working in the field. Magnet ownership for citizens of the developed world has
skyrocketed from 1 or 2 magnets in 1945 to 100–200 60 years later or something
of order a trillion if we count the individual magnetic bits on a hard disc in
a desktop computer. Countless citizens throughout the world during this period
already experienced magnetism’s bounty at first hand in the form of a cassette tape
recorder, and nowadays they can access the vast stores of magnetically recorded
information in huge data centers via the Internet using a handheld device.
Magnetism is therefore playing a crucial role in the big data revolution that is
engulfing us, by enabling the permanent data storage, from which we can make
instant copies at practically no cost. It may deliver more nonvolatile computer
memory if MRAM proves to a winning technology and possibly facilitate data
transfer at rates up to the terahertz regime with the help of spin torque oscillators.
There are potential magnetic solutions to the problems of ballooning energy
consumption and the data rate bottleneck. There is potential to implement new
paradigms for computation magnetically. While there is no certainty regarding the
future form of information technology, improved existing solutions often have an
inside track. Magnetism and magnetic materials may be a good bet.
There have been half a dozen paradigm shifts – radical changes in the ways of
seeing and understanding the magnet and its magnetic field – during its 2000-year
encounter with human curiosity. Implications of the big data revolution for human
society are only beginning to come into focus, but they are likely to be as profound as
on the previous two occasions when magnetism changed the world. This Handbook
is a guide to what is going on.
Acknowledgments The author is grateful to Science Foundation Ireland for continued support,
including contracts 10/IN.1/I3006, 13/ERC/I2561 and 16/IA/4534.
Appendix: Units
By the middle of the nineteenth century, it was becoming urgent to devise a standard
set of units for electrical and magnetic quantities in order to exchange precise
quantitative information. The burgeoning telegraph industry, for example, needed
a standard of electrical resistance to control the quality of electrical cables. Separate
electrostatic and electromagnetic unit systems based on the centimeter, the gram and
the second had sprung into existence, and Maxwell and Jenkin proposed combining
them in a coherent set of units in 1863. Their Gaussian cgs system was adopted
1 History of Magnetism and Basic Concepts 49
follow the Sommerfeld convention in this Handbook. The magnetic field strength H
is not measured in units of Tesla in any generally accepted convention, but it can be
so expressed by multiplying by μ0 .
At the present time, Gaussian cgs units remain in widespread use in research
publications, despite the obvious advantages of SI. The use of the cgs system in
magnetism runs into the difficulty that units of B and H, G and Oe, are dimensionally
different but numerically the same; μ0 = 1, but it normally gets left out of the
equations, which makes it impossible to check whether the dimensions balance.
Table 1 lists the conversion factors and units in the two systems. The cgs equivalent
of Eq. 8 is B = H + 4πM. The cgs unit of charge is defined in such a way that
ε0 = 1/4πc and μ0 = 4π/c so factors of c appear in Maxwell’s equations in place
of the electric and magnetic constants. Convenient numerical conversion factors
between the two systems of units are provided in Table 1.
Theoretical work in magnetism is sometimes presented in a set of units where
c = = kB = 1. This simplifies the equations, but does nothing to facilitate
quantitative comparison with experimental measurements.
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Université Libre de Bruxelles (1995)
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23. Bozorth, R.M.: Ferromagnetism. McGraw Hill, New York (1950) (reprinted Wiley – IEEE
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25. Smit, J., Wijn, H.P.J.: Ferrites; Physical Properties of Ferrrimagnetic Oxides. Philips Technical
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Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Quantum-Mechanical Origin of Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
One-Electron Wave Functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Electron-Electron Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Stoner Limit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Heisenberg Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Hubbard Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Specific Exchange Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
Intra-Atomic Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Indirect Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Itinerant Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Bethe-Slater Curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Metallic Correlations and Kondo Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Exchange and Spin Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Curie Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Magnetic Order and Noncollinearity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Spin Waves and Anisotropic Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Antiferromagnetic Spin Chains . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Dimensionality Dependence of Quantum Antiferromagnetism . . . . . . . . . . . . . . . . . . . . . . . 94
Frustration, Spin Liquids, and Spin Ice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
R. Skomski ()
University of Nebraska, Lincoln, NE, USA
e-mail: [email protected]
Abstract
Introduction
Fig. 1 Interatomic exchange and magnetic order: (a) antiferromagnetism (AFM) and (b) ferro-
magnetism (FM)
molecular fields required in the theory (several 100 teslas) are much higher than
typical magnetostatic interaction fields, which are only of the order of 1 tesla.
Equating the thermal energy kB T with the Zeeman energy μo μB H yields the
conversion μB /kB = 0.672 K/T, meaning that low-temperature thermal excitations
of about 1 kelvin destroy any magnetic order caused by magnetic fields of about
1 T. The weakness of Zeeman and other magnetic interactions reflects the relativistic
character of magnetism: The ratio of magnetic and electrostatic interactions is of the
order of 1/α 2 , where α = 1/137 is Sommerfeld’s fine structure constant.
Aware of the smallness of purely magnetic interactions, Werner Heisenberg
concluded in 1928 that ferromagnetic order must be of electrostatic origin, realized
on a quantum-mechanical level [1]. He found that the Coulomb repulsion between
electrons
1 e2
U (r 1 , r 2 ) = (1)
4πεo | r 1 − r 2 |
in combination with the Pauli principle yields a strong effective field consistent
with experiment. The Pauli principle forbids the occupancy of an orbital by two
electrons of parallel spin. In real space, it yields an exchange hole, that is, electrons
with parallel spins (↑↑) stay away from each other, while electrons with antiparallel
spin (↑↓) can come arbitrarily close, which carries a Coulomb-energy penalty. In a
nutshell, this is the origin of ferromagnetic exchange. A different consideration is
that even electrons of antiparallel spin (↑↓) avoid each other to some extent due to
their Coulomb repulsion, which is known as the correlation hole. The correlation
hole weakens the trend toward ferromagnetism.
Consider two electrons 1 and 2 in two atomic orbitals L (for left) and R (for
right). The real-space part of the wave function is
56 R. Skomski
1
± (r 1 , r 2 ) = √ (φL (r 1 )φR (r2 ) ± φR (r 1 )φL (r 2 )) (2)
2
where the upper and lower signs correspond to ↑↓ and ↑↑, respectively.
Using Eq. (2) to evaluate the Coulomb interaction EC = Ψ ± ∗ U Ψ ± dr1 dr2
yields an energy splitting of ±JD . The integral
±JD = φL∗ (r 1 )φR∗ (r 2 )U (r 1 , r 2 )φR (r 1 )φL (r 2 )dV1 dV2 (3)
Well-separated atoms are described by atomic wave functions of on-site energy Eat ,
but in molecules and solids, the wave functions of neighboring atoms overlap and
yield interatomic hybridization. This section focuses on two s electrons in atomic
dimers, such as H2 and hypothetical Li2 (Fig. 2). Most features of this model can be
generalized to solids, although solids exhibit additional many-electron effects. The
one-electron Hamiltonian corresponding to Fig. 2 is
2 2
H.1 (r) = ∇ + VL (r) + VR (r) (4)
2me
where L and R stand for right and left, respectively, and VL/R (r) = Vo (| r – RL/R | )
are the atomic potentials. In the case of hydrogen-like atoms of radius Rat = ao /Z,
the atomic ground state has the eigenfunction φ(r)∼ exp (–r/Rat ) and the energy
Eat = Z2 e2 /8πεo ao . The vicinity of the second atom means that the atomic wave
functions φ L (r) = |Lo > and φ R (r) = |Ro > overlap, which is described by the overlap
Fig. 2 Symmetric and antisymmetric wave functions: (a) atomic wave function, (b) Wannier
function, (c) antibonding state |σ *>, and (d) bonding state |σ >
58 R. Skomski
integral
The overlap causes interatomic hopping and yields a level splitting into bonding and
antibonding states. The respective energies are Eo ± T , where T is the hopping
integral. The hybridized eigenfunctions (Fig. 2(c-d)) are |σ > ∼ |Lo > + |Ro >
(bonding) and |σ ∗ > ∼ |Lo > – |Ro > (antibonding), both having So -dependent
normalizations. The label σ refers to the ss σ -bond between the two s orbitals and
leads to T < 0 in this specific model. The on-site energy Eo differs from the atomic
energy Eat by the crystal-field energy ECF ≈ <Lo |VR |Lo >.
1 1
|L> = √ |σ > + |σ ∗ > and |R> = √ |σ > − |σ ∗ > (7)
2 2
Figure 2(b) shows one of these Wannier functions. The two wave functions (c-d)
correspond to rudimentary wave vectors k = 0 (bonding) and k = π/a (antibonding).
Solids are very similar in this regard, except that k varies continuously (band
structure).
It is instructive to discuss the parameters involved for large interatomic dis-
tances R [2]. In this extreme-tight-binding limit, So = ½ (R/Rat )2 exp(–R/Rat ),
ECF = 2(Rat /R)Eat , and T = So ECF . Since ECF decreases only slowly, scaling
as 1/R, the asymptotic behavior of T is governed by the exponential decay of So .
In terms of the Wannier functions |L > and |R>, the one-electron Hamiltonian of
Eq. (4 ) assumes the very simple matrix structure
Eo T
H1 = (8)
T Eo
2 Magnetic Exchange Interactions 59
1 1
|σ > = √ (|L> + |R>) and |σ ∗ > = √ (|L> − |R>) (9)
2 2
Equations (8, 9) remove the overlap integral from explicit consideration and
constitute a great scientific and practical simplification.
Electron-Electron Interactions
H (r 1 , r 2 ) = H1 (r 1 ) + H1 (r 2 ) + U (r 1 , r 2 ) (10)
where a physically unimportant zero-point energy has been ignored. The Coulomb
parameter U is the extra energy required to put a second electron onto a given atom
(R or L), essentially
e2 n(r 1 ) n(r 2 )
U= dr 1 dr 2 (12)
4πεo | r1 − r2 |
where n(r) = nL/R (r). Unlike JD , which decrease exponentially with interatomic
distance, U is an atomic parameter and more or less independent of crystal structure.
Both U and T tend to be large, several eV, whereas JD is rather small, typically of
the order of 0.1 eV. This indicates that JD is not the only or even the most important
contribution to interatomic exchange. For example, the exchange in the H2 molecule
is antiferromagnetic, in spite of JD being positive.
Equation (11) can be diagonalized analytically. There are two low-lying states
1 1
|↑↑> = √ |LR> − √ |RL> (13)
2 2
60 R. Skomski
cos χ sin χ
|↑↓> = √ (|LR> + |RL>) + √ (|LL> + |RR>) (14)
2 2
where tan (2χ ) = –4T /U [4]. Equation (14) is a superposition of two Slater
determinants, described by the mixing angle χ . The corresponding energy levels
are
U U2
E↑↓ = +D − 4T 2 + (16)
2 4
Defining an effective exchange as J = E↑↑ –E↑↑ /2 yields
U U2
J = JD + − T2+ (17)
4 16
This equation shows that interatomic hopping (T ) reduces the net exchange
interaction. The effect comes from the admixture of |LL> and |RR> to |LR> + |RL>
(Eq. (14)) which is ignored in Eq. (2).
Stoner Limit
U
J = + JD − |T | (18)
4
This equation predicts ferromagnetism for sufficiently small hopping T and roughly
corresponds to the Stoner theory [5] of itinerant transition-metal magnets (Sec-
tion “Itinerant Exchange”). Since U
JD , the driving force behind Stoner
ferromagnetism is the Coulomb integral U , not the direct exchange JD [6]. The
interatomic hopping competes against the electron-electron interactions described
by the Stoner parameter I = U /4 + JD , whereas a refined calculation for transition
metals yields I = U /5 + 1.2 Jat [7]. Here Jat is the intra-atomic exchange, which
merges with the interatomic exchange in the itinerant limit.
Equation (18) yields a very simple and scientifically successful explanation,
namely, that ferromagnetism occurs when the one-electron level splitting, ±|T | in
the model of Section “Electron-Electron Interactions”, is sufficiently small com-
pared to the nearly crystal-independent Coulomb parameter U . Figure 3 illustrates
the physics behind this mechanism. The Coulomb repulsion U favors the FM config-
uration, but the FM alignment carries a one-electron energy penalty. More precisely,
2 Magnetic Exchange Interactions 61
Fig. 3 Origin of magnetism in the independent-electron picture. The one-electron level splitting
into bonding (σ ) and antibonding (σ *) states favors ↑↓ spin pairs, whereas the Coulomb repulsion
between the two |σ > electrons yields ↑↑ coupling so long as the Coulomb energy is larger
than the one-electron level splitting. The independent-electron nature of this picture is seen from
two features. First, the electrons occupy one-electron levels (σ and σ *). Second, the Coulomb
interaction can be interpreted as an effective field (Stoner exchange field)
and
Correlations
1
|σ σ > = (|LL> + |LR> + |RL> + |RR>) (22)
2
This wave function has an ionic character of 50%, that is, the electrostatically
unfavorable configurations |LL> and |RR> provide half the weight. Since the
electrons equally occupy all two-electron states, Eq. (22) lacks a correlation hole.
The Coulomb penalty associated with the unfavorable ionic contribution leads to an
overestimation of the AFM energy and therefore to an overestimation of the trend
toward ferromagnetism.
In reality, electron correlations lead to a partial suppression of the |LL> and
|RR > occupancies, described by the mixing angle χ in Eq. (14). The Heisenberg
limit, Ψ + in Eq. (2) and χ = 0 in Eq. (14), has |Ψ AFM > ∼ |LR> + |RL>, which
corresponds to an ionic character of 0% and to a fully developed correlation
hole. The Heisenberg model is said to be overcorrelated, as opposed to the
undercorrelated independent-electron approach. An interesting approach is the use
of Coulson-Fischer wave functions, that is, of Slater determinants constructed not
from |L> and |R> but from combinations such as |L> + λ |R>, where λ ≈ |T |/U for
small hopping [10]. This unrestricted Hartree-Fock approximation contains a part
of the correlations at the expense of symmetry breaking in the Hamiltonian [9]. The
approximation is sufficient to reproduce the correct AFM wave function, Eq. (14),
for the H2 model of Eq. (11), but this finding cannot be generalized to arbitrary
many-electron systems. Near the equilibrium H-H bond length of about 0.74 Å, the
electrons are delocalized, described by Eq. (22) and λ = 1, but above 1.20 Å, the
electrons localize very rapidly and λ approaches zero.
Correlations primarily affect AFM spin configurations [6]. For example, the FM
wave function |σ σ ∗ > – |σ ∗ σ > = |LR> – |RL>, Eq. (13), is independent of T and
U and therefore unaffected by correlations. The reason for the absence of ionic
configurations in Eq. (13) is the Pauli principle, which creates the exchange hole
and forbids |LL > and |RR > occupancies with parallel spin. Correlations effects are
most important in half-filled bands, where ferromagnetism means that all bonding
and antibonding real-space orbitals are occupied by ↑ electrons and the net energy
2 Magnetic Exchange Interactions 63
gain due to interatomic hybridization is zero. Electrons (or holes) added to half-
filled bands do not suffer from this constraint and make ferromagnetism easier to
achieve.
Solid-state correlations are multifaceted and yield many more or less closely
related magnetic phenomena, such as spin-charge separation (Section “Antiferro-
magnetic Spin Chains”), wave-function entanglement, and the fractional quantum-
Hall effect (FQHE). The determination of correlations is demanding even- or
medium-sized molecules or clusters, because the number of configurations to be
considered increases exponentially with system size. For example, the complete
description of a single CH4 molecule (10 electrons) requires the diagonalization of
a matrix containing 43,758 × 43,758 determinants [9]. Some methods to describe
correlations [9–13] are microstate approaches, such as those in this chapter, self-
energy methods, the evaluation of matrix elements between Slater determinants
(known as the configuration interactions, CI), dynamical mean-field theory (DMFT)
[14, 15], and the Bethe ansatz [16, 17]. Unlike LSDA+U, the DMFT is a
true correlation approach, because the electrons keep their individuality and the
mean-field character refers to the spatial aspect of the correlations only. Some
other correlation approaches, such as the Hubbard model, are briefly discussed in
Section “Hubbard Model”.
Heisenberg Model
2T2
J = JD − (24)
U
1
|AFM> = (|LR> + |RL>) (|↑↓> − |↓↑>) (25a)
2
and a FM triplet
1
|FM ↑↑> = √ (|LR> − |RL>) |↑↑> (25b)
2
1
|FM0> = (|LR> − |RL>) (|↑↓> + |↓↑>) (25c)
2
64 R. Skomski
1
|FM ↓↓> = √ (|LR> − |RL>) |↓↓> (25d)
2
reproduces the eigenfunctions and the singlet-tripletsplitting of Eq. (25), so that the
Heisenberg Hamiltonian can be written as H=–2 J S x ⊗ S x +S y ⊗ S y +S z ⊗ S z ,
in vector notation, H = –2 J S 1 · S 2 . An alternative approach is to apply angular-
momentum algebra to S = S 1 + S 2 , using S 2 = S 1 2 + 2 S 1 · S 2 + S 2 2 and
S 1 2 = S 1 2 = 3/4, and exploiting that S 2 = S(S + 1) is equal to 2 (S = 1,
↑↑), and S 2 = 0 (S = 0, ↑↓). Considering atomic spins of arbitrary size S ≥ 1/2,
performing a lattice summation over all spin pairs (compare Fig. 1), and including
an external magnetic field, the Heisenberg Hamiltonian becomes
H = −2 Jij S i · S j − g μo μB S1 · H i (27)
i>j i
where the Jij are often treated as parameters. Solutions of the Heisenberg model
will be discussed in Sections “Spin Waves and Anisotropic Exchange”, “Antiferro-
magnetic Spin Chains”, and “Dimensionality Dependence of Quantum Antiferro-
magnetism”.
Some definitions of J involve a factor of 2, depending on whether the summation
is over all atoms (subscript ij) or only over pairs of atoms (subscript i > j). Even
opposite signs are sometimes chosen, using J > 0 and J < 0 for AFM and FM
interactions, respectively. The most common definition of J , used in Eq. (27), is
actually an exchange per electron, not per atom. The AFM-FM energy difference per
pair of atoms, E(Sz = 0) – E(Sz = 2S), is equal to 4 S (S + 1/2) J and diverges in
the classical limit (S = ∞). The divergence is removed by introducing renormalized
atomic exchange constants Jat = 2S 2 J or Jat = 2S (S + 1). In the classical limit
(S = ∞), Jat = Jat and H = −Jat s 1 · s 2 , where the unit vector s = S/S = M/Ms
describes the local magnetization direction. The classical energy splitting between
the ↑↑ and ↑↓ states, namely, ±Jat , is formally the same as that for S = 1/2, ±J .
2
Biquadratic exchange, H = –B S · S , as well as other higher-order
terms, may arise for several reasons, for example, in T /U expansions of the full
Hamiltonian [3]. In the case of spin 1/2 interactions, they do not yield new physics,
2 Magnetic Exchange Interactions 65
2
because S · S = 3/16 − 1
2 S · S , but biquadratic exchange effects are
nonzero for S ≥ 1.
Hubbard Model
Completely ignoring the small direct exchange JD in equations such as (11, 12, 13,
14, 15, 16, 17, 18) leads to the Hubbard model. Generalized to solids, the Hubbard
Hamiltonian is
+ +
H = i,j Tij ĉi↑ ĉj↑ + ĉi↓ ĉ↓ + U i n̂i↑ n̂i↓ (28)
where n̂ = ĉ+ ĉ [18, 19]. In the Hubbard model, correlation effects are described by
the Coulomb interaction U . Equation (21) indicates that the Hubbard model does not
predict ferromagnetism in half-filled bands, but this argument cannot be generalized
to arbitrary bands and band fillings.
The bare Coulomb interaction is very high, about 20 eV for the iron-series
elements, but this value is reduced to about 4 eV due to intra-atomic correlations and
screening by conduction electrons. The screening (Sections “Itinerant Exchange”
and “Metallic Correlations and Kondo Effect”) depends on the crystal structure,
and eg orbitals tend to have slightly higher U values than t2g orbitals, so that U
varies somewhat for a given element. Table I shows typical U values for the three
transition-metal series [20]. Note that the effects of U are complemented by the
moderately strong intra-atomic exchange Jat , also listed in Table I. Approximate
values for U in some main-group elements are 8.0 eV (C), 3.1 eV (Ga), and 4.2 eV
(As). In rare earths, U is equal to and best obtained from the spectroscopic Slater-
Condon parameter F0 . It is of the order 10 eV and somewhat increases with number
of 4f electrons.
The Hubbard U yields a number of correlation effects. One of them is the
suppression of metallic conductivity for large values of U (Mott localization),
which reflects the splitting of metallic bands into upper and lower Hubbard bands
with opposite spin directions. The effect is very similar to the Coulson-Fischer
Fig. 4 Hubbard interpretation of band gaps: (a) Mott-Hubbard insulator, (b) charge-transfer
insulator, (c) simple interpretation of Hubbard-Mott transition, and (d) refined Hubbard transition
involving a correlated metal phase known as the Brinkman-Rice (BR) phase
The involvement of Coulomb integral (U ), and exchange integral (JD ), and one-
electron level splitting (T ) is a common feature of exchange interactions, but the
interplay between these quantities varies greatly among magnetic solids.
2 Magnetic Exchange Interactions 67
Intra-Atomic Exchange
Atomic wave functions inside a given atom are orthogonal, so that the ferro-
magnetic exchange is not weakened by one-electron level splittings involving
hopping between different orbitals (T = 0). On the other hand, one-electron energy
differences between shells and subshells are typically large, several eV. In terms of
Fig. 3, these energy differences provide a forbiddingly one-electron level splitting.
Ferromagnetic intra-atomic exchange is therefore almost exclusively limited to
the nearly degenerate electrons in the partially filled inner subshells of transition-
metal atoms, namely, 3d, 4d, and 5d electrons in the iron, palladium, and platinum
series, respectively, 4f electrons in rare-earth (lanthanide) atoms, and 5f electrons
in actinides.
Hund’s Rules Intra-atomic exchange and spin-orbit coupling give rise to the
hierarchy of three Hund’s rules [23]. The rules, which are empirical but have a
sound physical basis, determine the magnetic ground state of atoms or ions. Hund’s
first rule reflects intra-atomic exchange and states that the total spin S is maximized
so long as the Pauli principle is not violated. The number of one-electron orbitals
per subshell is 2 l + 1, which yields 5 orbitals per d-shell and 7 orbitals per f-shell.
In the first half of each series, all spins are ↑, and for half-filled shells, the total spin
moment is therefore 5 μB (d-shells) and 7 μB (f -shells). Additional electrons are ↓
due to the Pauli principle. For example, Co2+ has a 3d7 electron configuration and
the spin structure 3d (↑↑↑↑↑↓↓).
because the other two terms have zero spin. The term contains (2 L + 1) (2S + 1) = 9
Slater determinants, for example, |↑ ↑ ◦>, where Lz = 1 and Sz = 1. Hund’s third
rule predicts J = L – S = 0, corresponding to a nonmagnetic ground state. The p2
ground-state wave function is a superposition of three Slater determinants described
by Clebsch-Gordan coefficients C(L, Lz , S, Sz |J, Jz ) [2, 25]. Explicitly
1 1 1
|ψ> = √ |↑ ◦ ↓> + √ |↓ ◦ ↑> − √ |◦ ↑↓ ◦> (29)
3 3 3
The involvement of two or more Slater determinants indicates that correlations are
not necessarily be important even in seemingly simple systems.
Hund’s rules are obeyed fairly accurately by rare-earth ions in metallic and
nonmetallic environments. For example, the ground-state multiplets of rare-earth
ions obey J = |L ± S|, whereas excited multiplets have relatively high energies, with
notable exceptions of Eu3+ and Sm3+ , where the splitting is only about 0.1 eV [26].
One reason for the applicability of the rules is that the 4f -shell radii of about 0.5 Å
are much smaller than the atomic radii of about 1.8 Å. This enhances the spin-orbit
coupling and reduces the interaction with surrounding atoms. By contrast, Hund’s
rules are often violated in 3d, 4d, and 5d transition metals, where orbital moments
are quenched.
J (J + 1) = L (L + 1) + 2L · S + S (S + 1) (30)
3 1 S (S + 1) − L (L + 1)
g= + (31)
2 2 J (J + 1)
which yields g = 1 – S/(J + 1) and g = 1 + S/J for the first and second
halves of the lanthanide series, respectively. To account for spin-only character of
2 Magnetic Exchange Interactions 69
Indirect Exchange
The net exchange is tedious to calculate [27], but a transparent physical picture
emerges if one assumes that U and JD compete against T and that the outcome of
this competition is largely determined by T , similar to Eq. (24). For one 3d level
per transition-metal atom (M) and one oxygen 2p level (O), Eq. (8) becomes
⎛ ⎞
EM Tpd(L) 0
H = ⎝ Tpd(L) EO Tpd(R) ⎠ (32)
0 Tpd(R) EM
Here, EM and EO are the atomic on-site energies, and Tpd(R/L) describes the hopping
between M and O atoms. When Tpd(R) = Tpd(L) , a unitary transformation using
⎛ ⎞
√1 0 √1
2 2
⎜ ⎟
=⎝ 0 1 0 ⎠ (33)
√1 0 √1
2 2
⎛ √ ⎞
√EM 2Tpd 0
Q+ HQ = ⎝ 2Tpd EO 0 ⎠ (34)
0 0 EM
The transformation couples the wave functions of the two transition-metal atoms.
One of the coupled M levels is nonbonding (bottom-right matrix element), whereas
the other one (top left) hybridizes with the oxygen, thereby creating a level splitting
between the two coupled M orbitals. In the Heisenberg limit, Tpd is small, and the
diagonalization of Eq. (34) yields the transition-metal level splitting ±Teff , where
Teff = Tpd 2 /|EM –EO |.
Substitution of Teff into Eq. (24) yields the effective transition-metal exchange
2 Tpd 4
Jeff = JD − (35)
U (EM − EO )2
Since JD is small, the hopping normally wins, and the exchange in most oxides is
therefore antiferromagnetic. However, the non-s character of the 2p and 3d orbitals
causes Tpd to depend on the type of d orbital (eg or t2g ) and on the bond angle.
Figure 5 compares a 180◦ bond (a) with a 90◦ bond (b). In (a), the two p-d bonds
differ by the sign of the involved 2p wave-function lobe, but Tpd(R) = −Tpd(L)
leaves Eq. (35) unchanged. In (b), Tpd(R) = 0 by symmetry, because the hopping
contributions of the two oxygen lobes (+ and –) cancel each other. This implies
Tpd(R) = 0 in Eq. (32), and the two transition-metal orbitals are no longer coupled
(Teff = 0).
2 Magnetic Exchange Interactions 71
Double Exchange Intra-atomic exchange favors parallel spin alignment, and elec-
trons retain a “spin memory” while hopping between atoms. This process translates
into a ferromagnetic exchange contribution first recognized by Zener [28, 31].
Double exchange occurs in mixed valence oxides, such as Fe3 O4 . This oxide
contains Fe3+ and Fe2+ ions on B-sites. The latter can be considered as Fe3+ ions
plus an extra electron that can hop more or less freely between the d5 ion cores.
Itinerant Exchange
The magnetism of 3d, 4d, and 5d elements and alloys is fairly well described by the
independent-electron approximation, which corresponds to the use of a single big
Slater determinant. The electrons move in the solid, and the corresponding hopping
competes against the electrostatic electron-electron interaction.
The simplest approach is to replace the crystal potential V(r) by a charge-
neutralizing homogeneous background V(r) = const. (jellium model). The only
free parameter describing the corresponding homogeneous but not necessarily free
electron gas is the electron density n. It is convenient to parameterize n in terms
of the average inter-electronic distance rs = (3/4πn)1/3 and to relate rs to the free-
electron Fermi wave vector kF = (9π/4)1/3 /rs . Typical values of kF ao are 0.34 (Cs),
0.72 (Cu), and 1.03 (Be) [8]. The inverse magnetic susceptibility of the jellium
is [32]
2 Magnetic Exchange Interactions 73
χp π 1
=1− + 2 (0.507 ln (kF ao ) − 0.162) (37)
χ kF ao kF ao 2
χp
= 1 − I D(EF ) (38)
χ
2 2
H=− ∇ + j Vo (r − r j ) (39)
2me
74 R. Skomski
Very weak itinerant ferromagnets (VWIFs), such as ZrZn2 (Tc = 17 K), barely
satisfy the Stoner criterion, and their behavior is qualitatively different from that
of strong and weak ferromagnets [35, 36]. Thermal excitations act as local spin
perturbations that can be described by the wave-vector-dependent susceptibility
χ (k) [3]. For VWIFs, a good approximation is
χo
χ= (40)
|I D (EF ) − 1 + f (k)|
Tc 2 Tc
2
+ =1 (41)
TS TJ
2 Magnetic Exchange Interactions 75
This equation interpolates between the Heisenberg limit TJ (spin rotations) and the
Stoner limit Ts (moment reduction).
Strongly exchange-enhanced Pauli paramagnets, such as Pt, are close to the
onset of ferromagnetism and have I – 1/(EF ) 0. Magnetic impurities create spin-
polarized clouds of radius ξ in these materials. The corresponding radial dependence
M(r) of the magnetization combines a pre-asymptotic exponential decay (r ξ )
with RKKY oscillations for large distances (r ξ ). The exponential decay length
ξ is described by Eq. (40), in close analogy to VWIFs. For example, magnetic
surfaces of Co2 Si nanoparticles spin-polarize the interior of the particles with a
penetration depth ξ [38]. Spin polarized clouds in strongly exchange-enhanced
Pauli paramagnets are also known as a paramagnons [3]. Left to themselves,
these quasiparticles slowly decay, and by considering the time dependence of the
fluctuations, f (k) → f (k, ω) in Eq. (4), one can show that the relaxation time diverges
at the phase transition (critical slowing down).
Bethe-Slater Curve
Fig. 7 Crystallographic
motifs and density of states:
(a) square and (b) equilateral
triangle. The density of states
is largest in the middle (a)
and near the top of the level
distribution (b). The atomic
orbitals (red) are of the
s-type, but in [42], it can be
seen that 3d electrons behave
similarly, and the present
figure can be generalized to
three-dimensional lattices
1
Vi (r) = VLSDA (r) + U − ni (42)
2
Fig. 9 LSDA+U for bcc Fe: (a) magnetic moment, (b) weak ferromagnetism and (c) strong
ferromagnetism. The direct exchange and double-counting corrections are ignored in this figure
Table 2 Kondo Cr Mn Fe Co
temperatures (in kelvin) for
Rh – 10 50 1000
some transition-metal
impurities in nonmagnetic Pd 100 0.01 0.02 0.1
hosts (gray column) [59, 65] Pt 200 0.1 0.3 1
Cu 1.0 0.01 22 2000
Ag 0.2 0.04 3 –
Au 0.01 0.01 0.3 200
Zn 3 1.0 90 –
Al 1200 530 5000 –
impurity spins with conduction electrons [9, 58]. Below the Kondo temperature
TK , the interaction couples the conduction electrons to the impurity spins, which
enhances the electrical resistivity. Some Kondo temperatures for Cr, Mn, Fe and Co
in various matrices are shown in Table 2.
⎛ ⎞
U − E T T 0
⎜ T 0 0 T ⎟
H=⎜
⎝
⎟ (43)
T 0 0 T ⎠
0 T T E
Since U
T , the |ff > state (energy U − E) does not play any role in the ground-
state determination. In the absence of hybridization (T = 0), the ground state would
be degenerate, |f c> ± |c f >, both states having the energy E = 0 and containing
one localized and one delocalized electron. The first excited antiferromagnetic state,
|cc> = |c↑ c↓ >, has the energy E = E, meaning that the localized electron becomes
a conduction electron.
The hopping integral T does not affect the ferromagnetic state |f c>−|c f >,
because a localized ↑ electron cannot hop into a delocalized orbital that already
contains a ↑ electron. However, the localized ↑ electron can hop into a delocalized
orbital containing an electron of opposite spin, which lowers the energy of the
antiferromagnetic state. The corresponding singlet (↑↓) ground state has an energy
of –2T 2 /E = –2JK , roughly translating into a Kondo-temperature of TK =
2T 2 /kB E. Above TK , the |↑↓> and |↑↑> states are populated with approximately
equal probability, the two electrons effectively decouple, and the resistivity drops.
In reality, there are many conduction electrons, so an integration over all k-states
is necessary [58]. The main contribution comes from electrons near the Fermi level,
2 Magnetic Exchange Interactions 83
which form a Kondo screening cloud of size ξ proportional to 1/TK and yield a
Kondo temperature TK = (W/kB ) exp (−1/ [2 JK D(EF )]). Due to its exponential
dependence on JK and (EF ), TK varies greatly among systems [59]. Table II shows
some examples. TK is lowest for impurities in the middle of the 3d series and largest
for nearly filled or nearly empty 3d shells, as exemplified by TK = 5000 K for
Ni in Cu. The dependence JK ∼ 1/S indicates that Kondo exchange become
less effective in the classical limit. Heavy-fermion compounds, such as UPt3 and
CeAl2 , can be considered as Kondo lattices where conduction electrons interact
with localized 4f or 5f electrons [9].
Exchange affects spin structure and magnetic order in many ways. It determines
the ordering temperature, gives rise to a variety of collinear and noncollinear
spin structures, and influences micromagnetism through the exchange stiffness
A. Exchange phenomena include quantum-spin-liquid behavior, high-temperature
superconductivity, and Dzyaloshinski-Moriya interactions.
Curie Temperature
In spite of its simplicity, the Heisenberg model (27) is very difficult to solve,
especially in two and three dimensions. A great simplification is obtained by using
the identity
2 S(S + 1)
Tc = zJ (46)
3 kB
Depending on the sign of the interatomic exchange, there are several types of mag-
netic order. Figure 11 shows some examples. Often there are two or more sublattices
[4, 54], and the division into sublattices can be of structural or magnetic origin.
Ferrimagnetism (FiM) normally reflects chemically different sublattices, such as
Fe and Dy sublattices in Dy2 Fe14 B. Antiferromagnetism (AFM) is also caused by
negative interatomic exchange constants, but the different sublattices are chemically
and crystallographically equivalent. For example, CoO crystallizes in the rock-salt
structure, but the Co forms two sublattices of equal and opposite magnetization.
Ferromagnetism is frequently encountered in metals (Fe, Co, Ni) and alloys (PtCo,
SmCo5 , Nd2 Fe14 B), the latter having different ferromagnetic sublattices. CrO2 is a
ferromagnet, but most oxides and halides are antiferromagnetic (MnO, NiO, MnF2 )
or ferrimagnetic (Fe3 O4 , BaFe12 O19 ).
Many oxides of chemical composition MFe2 O4 crystallize in the spinel struc-
ture, which contains one cation per formula unit on tetrahedral sites [...] (M2+ ,
sublattice A) and two cations per formula unit on octahedral sites {...} (Fe3+ ,
sublattice B). The exchange between the A and B sublattices is negative, which
yields a ferrimagnetic spin structure. The cation distribution over the A and B sites
depends on both chemical composition and magnet processing. For example, Fe3 O4
crystallizes in the so-called “inverse” spinel structure [Fe3+ ] {Fe2+ Fe3+ }(O2− )4
[65]. The total magnetization, measured in μB per formula unit, is therefore
[−5] + {5 + 4} = 4.
In the classical limit, the mean-field Curie temperature is given by the lowest
eigenvalue of the N × N matrix in the equation
Here JAA/BB and JAB/BA are the classical intra- and intersublattice exchange
constants, respectively, and the factor 3 reflects the classical limit of the Brillouin
functions. The solution of Eq. (48) is
1
Tc = (JAA + JBB ) ± (JAA − JBB )2 + 4 JAB JBA (49)
6 kB
The two sublattices often have different numbers of atoms, so that JAB = JAB
in general, but the two intersublattice exchange constants enter Eq. (49) in the
form of the product JAB JBA , and it is sufficient to consider J ∗ = (JAB JBA )1/2 .
For one-sublattice ferromagnets, where JBB = J ∗ = 0, Tc is equal to JAA /3kB .
86 R. Skomski
Various scenarios exist for two-sublattice magnets. In the simplest AFM case, the
two intrasublattice exchange interactions JAA = JBB = 0 and J ∗ <0, yielding the
Néel temperature TN = –Tc = |J ∗ |/3kB .
A rule of thumb for the exchange in transition-metal alloys is the switch rule:
The exchange is negative for interactions between late and early transition-metal
atoms but positive otherwise. For example, Co and Pt are both late transition-metal
elements, so the Co and Pt moments in CoPt are parallel. While the switch rule
includes alloys containing heavy transition-metal atoms (3d-4d and 3d-5d alloys),
it is not very reliable for elements in the middle of the series [64]. It also describes
impurities in host lattices and RE-TM intermetallic compounds, because rare earths
count as early transition metals, with one 5d electron contributing to the exchange
[65].
With the exception of very weak itinerant ferromagnets, intersublattice inter-
actions in metals are well described by the Heisenberg model, and equations
like (49) provide good estimates of the ordering temperature [62]. For example,
transition-metal-rich rare-earth permanent magnets have JTT
J ∗ ≈ JRT and
JRR ≈ 0, so that the rare-earth contribution
to the Curie temperature is given by
Tc ≈ (JTT /3kB ) 1 + J ∗2 /JTT 2 . As a function of the number of 4f electrons, it
peaks in the middle of the lanthanide series, because J ∗2 involves the de Gennes
factor (Section “Intra-Atomic Exchange”)
further complicated by different types of disorder that can occur. Chemical disorder
means atomic substitutions with little or no changes in atomic positions. Bond and
topological
disorders involve substantial changes in atomic positions and in Jij =
|r i − r j | , but in the latter case, there is no continuous transformation connecting
the ordered and disordered lattices [67].
where J and J are the exchange interaction between neighboring layers, respec-
tively. The energy (50) is minimized by the ansatz θ n + 1 = θ n + δ, where δ ∼ 1/k
is the magnetization rotation between subsequent layers:
J + 4J cos δ sin δ = 0 (51)
Fig. 12 Dzyaloshinski-Moriya Interactions in (a–b) crystals and (b–c) thin films. The red atoms
are magnetic, whereas the blue and white atoms are nonmagnetic but have weak (white) and strong
(blue) spin-orbit coupling
crystal without inversion symmetry (point group C2v ). The fictitious crystal has
an equiatomic MT composition, where M is a magnetic or nonmagnetic metallic
element and T is a transition-metal element. The structure yields a spin spiral in the
x-z plane, that is, perpendicular to the net DM vector. B20-ordered cubic crystals
such as MnSi (point group T) are unique in the sense that their space group (P21 3)
is achiral due to the 180◦ character of the 21 screw axis but becomes chiral through
the incorporation of a chiral MnSi motifs.
Figure 12(c–d) shows the effect of Dzyaloshinski-Moriya interactions in thin
films with perpendicular anisotropy and fourfold (C4v ) or sixfold (C6v ) symmetry
(side view). When a patch of magnetic material is deposited on a material with
strong spin-orbit coupling, for example, Co on Pt, the modified spin structure is
reminiscent of a hedgehog. Such DM interactions are of interest in the context of
magnetic skyrmions. For example, bubble domains in thin films have a nonzero
skyrmion number and therefore yield a topological Hall effect (THE) [76], but DM
interactions change the spin structure of the bubble and the THE, thereby adding
new physics.
1 + − +
S i · S i+1 = Si Si+1 + Si− Si+1 + Sz,i Sz,i+1 (52)
2
The Sz operators measure the spin projections, Sz |↑>= + 12 |↑> and Sz |↓>=
− 12 |↓>, but leave the wave function unchanged. The spin-flip operators S + and S −
rise and lower the spin by one unit, respectively: S + |↓>=|↑> and S − |↑>=|↓>.
Since the S = 1/2 Heisenberg model has only two spin states, S + |↑>= 0 and
S − |↓>= 0, or symbolically S + S + = 0 and S − S − = 0. The products of
S + and S − in Eq. (52) have the effect of interchanging spins of opposite sign:
|↑↓ > becomes |↓↑ > and vice versa.
The ferromagnetic state, symbolically |0 > = |↑↑↑↑↑↑↑↑...>, is an eigenstate
of the Hamiltonian, because each of the spin-flip terms contains an S + operator
that creates a zero. One might naively expect that a single switched spin creates an
excited eigenstate, for example, |i > = |↑↑↑↓↑↑↑↑...>, where Ri is the position
of the flipped spin. However, the spin-flip operators move the flipped spin and
thereby create wave functions |i + 1 > and |i–1>. The low-lying eigenstates
of the ferromagnetic chain are actually plane-wave superpositions of single-spin
90 R. Skomski
flips, |ψ k > = exp.(ik·Rj ) |j>. These wave-like excited states are the spin waves
or magnons. Each magnon corresponds to one switched spin, but the reversal is
delocalized rather than confined to a single atom (Fig. 13). The corresponding
excitation energy is E = 4(1 – cos(k a)). For arbitrary crystals and spins [63]
E(k) = 2Sj J R j 1– cos k · R j (53)
z
E(k) = SJ R 2 k 2 (55)
3
For sc, bcc, and fcc lattices, Eq. (55) is equivalent to Eq. (54). In good approxima-
tion, it can also be applied to slightly noncubic structures. For example, elemental
cobalt has R = 2RCo , where RCo = 1.25 Å nm is the atomic radius of fcc and hcp Co.
Strongly anisotropic structures, such as multilayers, require an explicit evaluation of
Eq. (53).
It is common to write this relation as E = D k2 , where D is the spin-wave
stiffness. In micromagnetism, it is convenient to write the exchange energy as
E = A [∇s]2 dV (56)
where A is the exchange stiffness. Comparison of Eqs. (54) and (56) yields
2 Magnetic Exchange Interactions 91
J
A = 2 c S2 (57)
a
where c is the number of atoms per unit cell (c = 1 for sc, c = 2 for bcc, c = 4 for
fcc). Similar to Eq. (54), Eq. (57) cannot be used for arbitrary crystals, whose lattice
constants can be very large, and for dilute magnets [90]. In terms of the interatomic
distance, the rule of thumb is A ≈ zS 2 J /5R. Values of spin wave stiffness D and
exchange stiffness A for some common magnets are given in Table 3.
J ŝ · ŝ → J ŝx · ŝ x + ŝy · ŝ y + Jz ŝz · ŝ z (58)
The exchange anisotropy J = Jz –J /Jz , which has the same relativistic
origin as magnetocrystalline anisotropy and the Dzyaloshinski-Moriya interaction
(Section “Magnetic Order and Noncollinearity”),
is normally
very small compared
to the average or “isotropic” exchange Jo = 2J + Jz /3. However, J becomes
non-negligible when Jo is very small, for example, in some compounds with low
Curie temperature [80].
92 R. Skomski
Experimental Methods
There are many methods to investigate exchange, directly and indirectly, some of
which are briefly mentioned here. Magnetic measurements are used to determine
Curie temperatures Tc ∼ J , from which exchange constants can be deduced. The
low-field magnetization of antiferromagnets is zero, but high fields tilt the AFM
sublattices and yield a small magnetization M(H ) ∼ H /J .
2 Magnetic Exchange Interactions 93
The exchange may also be deduced from the low-temperature M(T) curves,
because the Bloch law involves the exchange stiffness. Magnetic force and, to
a much lesser extent, anomalous magneto-optic microscopies used to investigate
magnetic domain structures, which contain implicit information about the exchange
stiffness. A direct method to probe exchange is magnetic resonance.
Neutron diffraction and, to a much lesser extent, X-ray diffraction (XRD) are
important methods to probe spin structure. The magnetic XRD signal is much
weaker than the neutron-diffraction signal. Interatomic exchange can be probed
by a variety of methods, such as X-ray magnetic dichroism, which also allows
a distinction of L and S contributions to the atomic moments. Electron-transport
measurements are frequently used to gauge and confirm exchange effects.
and
However, the spin-flip terms in Eq. (52) do not transform Eqs. (59) and (60) into
each other but create pairs of parallel spins (spinons), for example
Using the Néel states to evaluate Eq. (27) yields an AFM ground-state energy of
−0.5 J per atom, compared to the exact Bethe result of −2 J (ln 2 − 1/4) =
−0.886 J [8]. Systems with such complicated ground states are also known as
quantum spin liquids (QSL). The underlying physics is very similar to the spin
mixing discussed below Fig. 10 but now involves an infinite number of spins.
The derivation of the Heisenberg model, Section “Hubbard Model”, was based
on the neglect of interatomic hopping. Strictly speaking, this is meaningful only
when U is large and the band is half-filled. In more- or less-than-half-filled bands,
a fraction of the electrons can move almost freely. Such magnets have both charge
and spin degrees of freedom, and the corresponding extension of the Heisenberg
chain is known as the Tomonaga-Luttinger model or Luttinger liquid [87, 88]. A
typical wave function is |↑↓↑↑↓◦↑↓>, which contains one hole. The model has a
number of interesting features. For example, spin and charge excitations move with
different velocities, the former being slower, because spin excitations have lower
94 R. Skomski
Mermin theorem are of thermodynamic origin, whereas the present ones are
zero-temperature quantum fluctuations. These fluctuations, which are largest for
S = 1/2, are a correlation effect and therefore difficult to treat in density-functional
calculations.
One example is high-temperature superconductivity (HTSC) in La2-x Srx CuO4 ,
which involves 3d9 states in the Cu-O planes of the oxides [9] and where spin-1/2
quantum fluctuations trigger the formation of Cooper pairs. The parent compound
La2 CuO4 is a strongly correlated antiferromagnetic semiconductor, but Sr doping
drives the system toward a phase transition. The denominator in Eq. (40) becomes
small, meaning that spin fluctuations (antiferromagnetic paramagnons) are strongly
enhanced by Sr doping. Furthermore, both spin-charge separation [9] and critical
slowing down cause the spin fluctuations to evolve very sluggishly, so that they can
play the role of phonons in BCS superconductors.
A number of exotic topics in physics are more or less closely related to exchange
interactions. This subsection discusses both classical and quantum-mechanical
implications of frustration, as well as some related micromagnetic questions.
Fig. 14 Classical frustration in rings of N atoms: (a) frustrated state (N = 3), (b) ground state
(N = 3), and (c) graphical solution (Frost’s cycle) for N = 5
FM ground state has n = 0 and the energy −2J . However, the figure shows
that energy eigenvalues are not necessarily symmetric with respect to changing
the sign of J . For odd values of N, the AFM ground state is double degenerate
and characterized by nearest-neighbor spin angles (1–1/N) 180◦ , as opposed to the
180◦ expected for ideal antiferromagnetism. The incomplete antiparallelity leads to
a ground-state energy 2J cos (π/N), higher than that of an ideal antiferromagnet
(2J ). This analysis shows exchange in antiferromagnets is different from exchange
in ferromagnets, even in the classical limit.
The quantum-mechanical ground state of the AFM spin-1/2 Heisenberg triangle
is obtained by using Eq. (52) to evaluate the matrix elements between the states
|↑↑↓>, |↑↓↑>, and |↓↑↑>. It is sufficient to consider Sz = 1/2, since none of
the terms in Eq. (52) changes the total spin projection Sz . For example, spin
configurations such as |↑↑↑ > (Sz = 3/2) and |↑↑↓ > (Sz = 1/2) do not mix.
Furthermore, Sz = − 1/2 is equivalent to Sz = +1/2 and does not need separate
consideration. For the three states with Sz = 1/2, the Hamiltonian is
⎛ ⎞ ⎛ ⎞
100 111
3
H = J ⎝0 1 0⎠ − J ⎝1 1 1⎠ (63)
2
001 111
The diagonalization of this matrix is trivial and yields one FM eigenstate (1, 1, 1)
of energy – 3J /2 > 0 and two AFM eigenstates of energy 3J /2 < 0, for example,
|Ψ 1 > = (2, −1, −1) and |Ψ 2 > = (0, 1, −1). Explicitly
1
|1 >= √ (2| ↑↑↓ >−| ↑↓↑ >−| ↓↑↑ >) (64a)
6
and
2 Magnetic Exchange Interactions 97
1
|2 > = √ (| ↑↓↑ >−| ↓↑↑ >) (64b)
2
Since the two AFM states are degenerate, |Ψ > = c1 |Ψ 1 > + c2 |Ψ 2 > is also an
eigenstate; complex numbers c1/2 mean a spin component in the y-direction.
Alternatively, Eq. (64b) is a product of the type (|↑↓>− |↓↑>)⊗|↑> and contains a
maximally entangled AFM singlet |↑↓>− |↓↑>. According to Eq. (63), the corners
of the triangle are equivalent, so that the singlet may be placed on any of the three
bonds.
The spin-1/2 Heisenberg square has the spin projections Sz = (0, ±1, ±2). In the
antiferromagnetic ground state (Sz = 0), there are six spin configurations, namely,
the two Néel states |↑↓↑↓> and |↓↑↓↑>, as well as six non-Néel states with pairs
of parallel spins, such as |↑↑↓↓>. Classically, non-Néel states are not expected to
appear in the ground state, but the diagonalization of the corresponding 6 × 6 matrix
yields an AFM ground-state singlet with a strong admixture of non-Néel character,
namely
1 1 1
|>= | ↑↓↑↓ >+ | ↓↑↓↑ >− √ (| ↑↑↓↓ >+ . . . ) (65)
2 2 8
The total weight of the non-Néel configurations in the ground state is 50%. This
ground state is rather complicated but, unlike Eq. (64), not frustrated.
Fig. 15 Frustrated lattices in two dimensions: (a) triangular lattice and (b) Kagome lattice
be ruled out, but they have never yet been observed in the universe. Solid-state
“monopoles”
are no monopoles, because they are formed from dipoles and do not
violate B·dA = 0. For illustrative purposes, the magnetic charges near the ends of
a long bar magnet may be regarded monopoles, but these are not real monopoles but
merely the ends of long dipoles. Figure 16 compares a magnetic dipole (a) with a
putative magnetic monopole (b). The configuration (b) may be created in the form of
a magnetic-dipole layer or by some radial magnetization distribution in a magnetic
material. In any case, it requires compensating south-pole charges inside the sphere,
so that B · dA = 0. As a consequence, the magnetic field is actually zero outside
the sphere, so that the finite-length arrows in (b) are without physical basis.
In the context of new materials, it is important to keep in mind that exchange
interactions are described in terms of Hamiltonians. The equation of motion of any
system is more fundamentally governed by the Lagrangian and its time integral, the
action. The difference can be ignored in flat spaces but is important in curved and
periodic spaces, where it corresponds to the Berry phase. The contributions of the
phase are basically of a ‘zero-Hamiltonian’ type and ignored in this chapter.
2 Magnetic Exchange Interactions 99
Acknowledgments This chapter has benefited from help in details by P. Manchanda and R.
Pathak and from discussions with B. Balamurugan, C. Binek, X. Hong, Y. Idzerda, A. Kashyap,
P. S. Kumar, D. Paudyal, T. Schrefl, D. J. Sellmyer, and A. Ullah. The underlying research
in Nebraska has been supported by DOE BES (DE-FG02-04ER46152) NSF EQUATE (OIA-
2044049), the NU Collaborative Initiative, HCC and NCMN.
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Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
Phenomenology of Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
Lowest-Order Anisotropies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
Anisotropy and Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Tetragonal, Hexagonal, and Trigonal Anisotropies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Higher-Order Anisotropy Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Anisotropy Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Crystal-Field Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
One-Electron Crystal-Field Splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Crystal-Field Expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Many-Electron Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Spin-Orbit Coupling and Quenching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Rare-Earth Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
Rare-Earth Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Operator Equivalents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
Single-Ion Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Temperature Dependence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
Transition-Metal Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
Spin-Orbit Matrix Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Crystal Fields and Band Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Itinerant Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
R. Skomski ()
University of Nebraska, Lincoln, NE, USA
e-mail: [email protected]
P. Manchanda
Howard University, Washington, DC, USA
A. Kashyap
IIT Mandi, Mandi, HP, India
e-mail: [email protected]
Abstract
Introduction
Magnetic anisotropy means that the energy of a magnetic body depends on the
direction of the magnetization with respect to its shape or crystal axes. It is a quantity
of great importance in technology. For example, it is crucial for a material’s ability to
serve as a soft or hard magnet; governs many aspects of data storage and processing,
3 Anisotropy and Crystal Field 105
such as the areal density in the magnetic recording; and affects the behavior of
microwave and magnetic-cooling materials.
In the simplest case of uniaxial anisotropy, the energy depends on the polar angle
θ but not on the azimuthal angle φ of the magnetization direction:
Ea = V K1 sin2 θ + K2 sin4 θ + K3 sin6 θ (1)
Here the Kn are the n-th anisotropy constants and V is the crystal volume. The first
anisotropy constant K1 is often the leading consideration. Ignoring K2 and K3 , the
anisotropy energy is equal to K1 V sin2 θ , and two cases need to be distinguished.
K1 > 0 yields energy minima at θ = 0 and θ = 180◦ , that is, the preferential
magnetization direction is along the z-axis (easy-axis anisotropy). When K1 < 0,
the energy is minimized for θ = 90◦ (easy-plane anisotropy).
The magnitudes of the room-temperature anisotropy constants K1 vary from less
than 5 kJ/m3 in very soft magnets to more than 17 MJ/m3 in SmCo5 . A variety of
rare-earth-free transition-metal alloys have anisotropies between 0.5 and 2.0 MJ/m3 .
YCo5 , where the Y is magnetically inert, has K1 = 5.0 MJ/m3 .
This chapter deals with the phenomenological description and physical origin of
anisotropy. A key question is how magnetic anisotropy depends on crystal structure
and chemical composition. The main contribution to the anisotropy energy of
most materials is magnetocrystalline anisotropy (MCA), which involves spin-orbit
coupling, a relativistic interaction [1]. This mechanism involves two steps. First, the
electrons that carry the magnetic moment interact with the lattice, via electrostatic
crystal field and exchange interactions. Second, the spin-orbit coupling (SOC)
ensures that the spin magnetization actually takes its orientation from the lattice.
In the absence of spin-orbit coupling, anisotropic arrangements of atoms do not
introduce magnetocrystalline
anisotropy. A good example is the Heisenberg model,
H = –ij J R i –R j S i · S j , which is magnetically isotropic even if the exchange-
bond distribution (Ri – Rj ) is highly anisotropic, for example, in thin films and
nanowires.
Magnetocrystalline anisotropy is not the only contribution. Magnetostatic dipolar
interactions are important in some nanostructured materials and also in materials
where the magnetocrystalline anisotropy is zero by coincidence. Shape anisotropy
(Sect. “Néel’s Pair-Interaction Model”) is a dipole contribution of importance
in some permanent magnets (alnicos), and in magnets with a noncubic crystal
structure, there is also a small dipole contribution to the MCA. The latter is
particularly important in Gd-containing magnets, because Gd3+ ions do not exhibit
anisotropic crystal-field interactions (Sect. “Crystal-Field Theory”) but has a large
dipole moment (S = 7/2).
Magnetic anisotropy is most widely encountered in ferro- and ferrimagnets, but it
is also present in antiferromagnets (Sect. “Magnetoelastic Anisotropy”), disordered
magnets (Sect. “Random Anisotropy in Nanoparticles, Amorphous, and Granular
Magnets”), paramagnets, and diamagnets. An example of an anisotropic diamagnet
is graphite, where the magnitude of the susceptibility is 40 times higher along the
hexagonal c-axis than in the basal plane [2], due to the high mobility of the electrons
in the graphene-like carbon sheets that make up the graphite structure.
106 R. Skomski et al.
Anisotropies in bulk materials and this films are closely related to the orbital
moment L (see below) and therefore to the Bohr-van Leeuwen theorem, which
suggests that a magnetic field acting on electrons does not change the magnetization
of solids. In fact, the field leaves the energy of the electrons unchanged, because the
Lorentz force is perpendicular to the velocity, but nevertheless changes the orbital
moment. Note that the definition and physical interpretation of orbital moments
in solids is a rather recent development, associated with the discoveries of Berry
phase and bulk-boundary correspondence. Berry-phase effects are importantant
in curved and periodic spaces and can be considered as geometrical constant-
energy phenomena. Furthermore, magnetization processes reflect the rotation rather
than creation of atomic moments. Neither the concept of spin roatation nor the
Berry phase where known in the early 20th century, when the theorem was
formulated.
Depending on the relative strength of the spin-orbit coupling compared to the
interatomic interactions (crystal field, exchange, hopping), there are two important
limits. The magnetocrystalline anisotropy of high-performance permanent magnets,
such as SmCo5 and Nd2 Fe14 B, is largely provided by the rare-earth 4f electrons
[3, 4]. These electrons are close to the nucleus (R ≈ 0.5 Å), which means that they
exhibit a strong spin-orbit coupling (of the order of 200 meV) but do not exhibit
much interaction with the crystalline environment (of the order of 10 meV). The
orbits of the 4f electrons, as well as the charge distribution n4f (r), are determined
by Hund’s rules. Specifically, Hund’s first rule, which has its origin in the Pauli
principle, states that the total spin S is maximized. The remaining degeneracy with
respect to total orbital moment L is removed by Hund’s second rule, which means
that the orbital moment L is maximized due to intra-atomic exchange. Finally,
Hund’s third rule describes how the spin-orbit interaction rigidly couples orbital-
moment vector L to the spin vector S.
Due to Hund’s third rule, a change in the magnetization angles θ and φ
yields a rigid rotation of the charge distribution n4f (r). Figure 1 explains how this
Phenomenology of Anisotropy
M = Ms sin θ cos φ ex + sin θ sin φ ey + cos θ ez (2)
The respective directions x, y, and z with unit vectors ex , ey , and ez often correspond
to the crystallographic a-, b-, and c-axes in crystals of high symmetry.
108 R. Skomski et al.
Lowest-Order Anisotropies
The first- (or second-)order anisotropy constant K1 often provides a good description
of the anisotropy of magnetic substances where higher-order anisotropy constants
are negligible. There are, however, many exceptions to this rule. For example, the
relative magnitudes of the different Kn depend on crystal structure and temperature,
and the φ-dependence of the anisotropy cannot be neglected in many cases. On
the other hand, simplifications arise because many anisotropy constants are zero
by crystal symmetry. Figure 2 shows the corresponding hierarchy: the number of
anisotropy constants decreases in the direction of the arrows.
Fig. 2 Relations between crystal systems; the arrows point in directions of increasing symmetry
and decreasing numbers of anisotropy constants. The arrows also suggest how degeneracies may
arise. For instance, stretching a cubic crystal so that c > a = b creates a tetragonal crystal, whereas
stretching a hexagonal crystal so that a > b creates an orthorhombic crystal
3 Anisotropy and Crystal Field 109
Let us start with the lowest-order anisotropy. Expansion of the magnetic energy
in spherical harmonics shows that there are five second-order terms Y2 m , corre-
sponding to five anisotropy coefficients κ 2 m , namely, κ 2 −2 , κ 2 −1 , κ 2 0 , κ 2 1 , and
κ 2 2 . However, three Euler angles are necessary to fix the anisotropy axes ex , ey ,
and ez relative to the crystal axes, so there remain only two independent anisotropy
constants. Explicitly
Ea (θ, φ)
= K1 sin2 θ + K1 sin θ cos 2φ
2
(3)
V
Ea K1 c K c
2
= 4 x 2 y 2 + y 2 z2 + z2 x 2 + 6 x 2 y 2 z2 (4)
V r r
where x/r = cosα x , y/r = cosα y , and z/r = cosα z are the direction cosines of the
magnetization. From the power-law behavior of r in Eq. (4), we see that K1 c and
K1 c are fourth- and sixth-order anisotropy constants, respectively. K1 c > 0 favors
the alignment of the magnetization along the [001] cube edges, which is called iron-
type anisotropy, while K1 c < 0 corresponds to an alignment along the [98] cube
diagonals and is referred to as nickel-type anisotropy . The subscript “c” is often
omitted, but when uniaxial and cubic anisotropies need to be distinguished, then it
is better to use Ku and/or K1 c to distinguish the respective anisotropy constants.
The number of anisotropy constants rapidly increases with increasing order and
decreasing symmetry . By definition, Ea (−M) = Ea (M), so that we need even-
order spherical harmonics only (gray rows in Table 16). The maximum number of
anisotropy constants is therefore 5 (up to second order), 14 (up to the fourth order),
and 27 (up to the sixth order). Since the anisotropy axes do not necessarily corre-
110 R. Skomski et al.
Table 1 Crystal systems, point groups, space groups, Strukturbericht notation, and prototype
structures for some compounds of interest in magnetism. Not all the examples are ferromagnetic
Crystal system Point group Space group Examples
Monoclinic C2h (2/m) C2/m D015 (AlCl3 ): DyCl3
Monoclinic C2h (2/m) C2/c B26 (tenorite): CuO
Orthorhombic D2h (mmm) Pnma C37 (Co2 Si): Co2 Si; D011 (cementite):
Fe3 C; goethite: α-FeO(OH); orthorhombic
perovskite: SrRuO3
Tetragonal D4h (4/mmm) P4/mmm L10 (CuAu): PtCo, FePd, FePt, MnAl, FeNi
Tetragonal D4h (4/mmm) P42 /mnm Rutile (C4): CrO2 , MnF2 , TiO2 ; Nd2 Fe14 B
Tetragonal D4h (4/mmm) I4/mmm ThMn12 (D2b ): Sm(Fe11 Ti); Al3 Ti (D022 ):
Al3 Dy, GaMn3
Trigonal D3 (32) P32 12 D04 (CrCl3 ): CrCl3 (P31 12)
Trigonal D3d (3m) R3m C19 (α-Sm): Sm, NbS2 ; Th2 Zn17 : Sm2 Co17 ,
Sm2 Fe17 N3
Trigonal D3d (3m) R3c D51 (corundum): α-Fe2 O3
Hexagonal C6v (6 mm) P63 mc B4 (wurtzite): MnSe
Hexagonal D6h (6/mmm) P63 /mmc A3 (hcp): Co, Gd, Dy; B81 (NiAs): MnBi,
FeS; C7 (MoS2 ): TaFe2 ; C14 (MnZn2
hexagonal laves phase): TaFe2 , Fe2 Mo; C36
(MgNi2 hexagonal laves): ScFe2 ; D019
(Ni3 Sn): Co3 Pt*; PbFe12 O19
(magnetoplumbite): BaFe12 O19 , SrFe12 O19 ;
Th2 Ni17 : Y2 Fe17
Hexagonal D6h (6/mmm) P6/mmm D2d (CaCu5 ): SmCo5
Cubic T (23) P21 3 FeSi (B20): MnSi, CoSi, CoGe
Cubic Th (m3) Pa3 Pyrite (C2): FeS2
Cubic Td (43m) F43m C1b (half-Heusler): MnNiSb
Cubic Td (43m) I43m A12 (α-Mn): Mn
Cubic Oh (m3m) Fm3m A1 (fcc): Ni; B1 (NaCl): CoO, NiO, EuO,
US; D03 (AlFe3 ): Fe3 Si; L21 (cubic
Heusler): AlCu2 Mn; D8a (Th6 Mn23 ):
Dy6 Fe23
Cubic Oh (m3m) Im3m A2 (bcc): Fe, Cr
Cubic Oh (m3m) Pm3m B2 (CsCl): NiAl, FeCo, AlCo, B3
(zincblende): CuCl, MnS, GaAs; E21 (cubic
perovskite): BaTiO3 ; L12 (AuCu3 ): Fe3 Pt
Cubic Oh (m3m) Pn3m C3 (cuprite): CuO2
Cubic Oh (m3m) Fd3m C15 (cubic Laves phase): SmFe2 , TbFe2 ,
UFe2 , ZrZn2 ; H11 (spinel): Fe3 O4
Cubic Oh (m3m) Ia3d Fe3 Al2 Si3 O12 (garnet): Y3 Fe5 O12 ,
Gd3 Fe5 O19
112 R. Skomski et al.
crystal field may have very low site symmetry, with local easy axes unrelated to the
a- and b-axes (gray). However, since the local easy axes obey the fourfold rotation
symmetry, the sum of all local anisotropy contributions is fourth-order, and there
is no second-order in-plane contribution. The in-plane anisotropy is of the type
cos(4φ – 4φ o ), and in the present example, the angle φ o ≈ 40◦ is equal to the angle
between the dashed local easy axes and the crystal axes. Going from C4(h) to C4v
introduces vertical mirror planes. These two planes ensure that each local easy axis
of angle φ o has a counterpart with –φ o , so that the net anisotropy directions are now
parallel to the crystal axes.
The picture outlined in Fig. 2 and Table 1 focuses on crystallographic point
groups. A more general approach would be to consider magnetic point groups, as
exemplified by the noncubic (tetragonal) electronic structure of magnets having a
cubic crystal structure and a layered antiferromagnetic spin structure. However, the
layers can lie in any of the equivalent cubic lattice planes, so the magnetic anisotropy
remains cubic.
or cos6φ terms. Up to the sixth order, the anisotropy of magnets with a tetragonal
crystal structure is described by
Ea
= K1 sin2 θ + K2 sin4 θ + K2 sin4 θ cos 4φ + K3 sin6 θ + K3 sin6 θ cos 4φ (5)
V
Without further modification, this equation can be used for the space groups C4v ,
D4 , D4h , and D2d . In particular, all tetragonal compounds listed in Table 1 belong
to the highly symmetric point group D4h . The point groups C4 , C4h , and S4 have
a lower symmetry and require consideration of fourth-order angular shifts φ o . The
anisotropy of orthorhombic crystals differs from Eq. (5) by additional second-order
terms, similar to the K2 term in Eq. (3).
The corresponding anisotropy energy expression for trigonal symmetry is
Ea
V = K1 sin θ + K2 sin θ + K2 sin θ cos θ cos (3 φ)
2 4 3
(6)
+ K3 sin φ + K3 sin θ cos (6φ) + K3 sin3 θ cos3 θ cos (3
6 6
φ)
Without modification, this equation can be used for the trigonal point groups
C3v , D3 , and D3d as well as for hexagonal crystals, which can be considered as
degenerate trigonal crystals (Fig. 2). Hexagonal point symmetry is ensured by
putting K2 = K3 = 0, and no further modification is necessary for the point groups
C6v , D6 , D6h , and D3h . The lower-symmetry point groups C3 , C3h , and S3 (trigonal)
and C6 , C6h , C3h , and S6 (hexagonal) require the consideration of an angular
shift φ o in each φ-dependent term. Note that the relationship between trigonal,
rhombohedral, and hexagonal crystals is complicated. The term rhombohedral
denotes the translational symmetry (Bravais lattice), whereas the closely related
term trigonal refers to the point symmetry. Some trigonal crystals have hexagonal
rather than rhombohedral translation symmetry. The trigonal space groups whose
names begin with P (for primitive) are hexagonal, whereas those starting with R
are rhombohedral. For example, Table 1 shows that α-Sm and Sm2 Co17 belong to
the space group R3m and are both trigonal and rhombohedral. Translationally, the
difference between hexagonal (P) and rhombohedral (R) is similar to the difference
between primitive (P) and body-centered (I) cubic crystals, the rhombohedral cell
having two extra lattice points.
Equations (5) and (6) also describe cubic crystals, which can be considered as
degenerate tetragonal or trigonal crystals (Fig. 2). Stretching a cubic crystal along
the [001]-axis yields a tetragonal crystal, whereas stretching it along the [111] cube
diagonal yields a rhombohedral crystal. The tetragonal symmetry axis (θ = 0) is
therefore parallel to the cubic [001] direction, and the anisotropy constants obey
K1 = K1 c , K2 = − 7K1 c /8 + K2 c /8, K2 = – K1 c /8 – K2 c /8, K3 = – K2 c /8, and K3
= K2 c /8. In the trigonal case, θ = 0 refers to the [111] direction, and the √ in lowest-
order anisotropy constants are K1 = − 3K1 c /2, K2 = 7K1 c /12, and K2 = 2K1 c /3.
114 R. Skomski et al.
Equations (5) and (6) are relatively easy to use in experimental magnetism and
theoretical micromagnetism. However, unlike spherical harmonics, the energy terms
in these equations are nonorthogonal and mix anisotropy contributions of different
orders 2n. For example, uniaxial anisotropy, Eq. (1), has the following presentation
in terms of spherical harmonics:
0 0
Ea
= κ22 3cos2 θ − 1 + κ84 35 cos4 θ − 30cos2 θ + 3
0
V (7)
+ κ16
6
231 cos6 θ − 315 cos4 θ − 105 cos2 θ − 5
Comparison of Eqs. (1) and (7) shows that K1 contains not only second-order
(κ 2 0 ) but also fourth-order (κ 4 0 ) and sixth-order (κ 6 0 ) contributions. In more detail,
K1 = – 3κ 2 0 /2 – 5κ 4 0 – 21κ 6 0 /2, K2 = 35κ 4 0 /8 + 189κ 6 0 /8, and K3 = −231κ 6 0 /16.
In many cases, the only important anisotropy contribution is K1 = −3κ 2 0 /2,
but in some cases κ 2 0 = 0 and K1 are dominated by fourth-order terms. An
important example is Nd2 Fe14 B (tetragonal) in a narrow temperature range below
room temperature, where κ 4 0 causes the sign of K1 to change (Fig. 14(d) in
Sect. “Temperature Dependence” and Ref. 7).
Anisotropy contributions of the same order tend to have similar magnitudes,
which is important for understanding experimental data. For example, the two uni-
axial anisotropy constants K1 and K2 provide a consistent fourth-order description
of hexagonal crystals but not of tetragonal crystals, because the non-uniaxial K2
term in Eq. (5) is also of the fourth order. For second-order uniaxial anisotropies,
see Sect. “Lowest-Order Anisotropies”.
Higher-order anisotropy constants may have drastic effects if K1 ≈ 0 by
coincidence, for example, due to competing sublattice contributions. For example,
uniaxial anisotropy with K1 < 0 and K2 > − K1 /2 yields easy-cone magnetism,
where the negative K1 makes the c-axis an unstable magnetization direction but the
positive K2 prevents the magnetization from reaching the basal plane (a-b-plane). In
this regime, the preferred magnetization direction lies on a cone around the c-axis,
described by the angle θ c = arcsin (|K1 |/2K2 ). The temperature dependences of
K1 and K2 are generally very different; K2 usually negligible at high temperatures.
As a consequence, the preferential magnetization direction may change as a
function of temperature, which is known as a spin-reorientation transition. A similar
film thickness-dependent transition is observed in films where surface and bulk
anisotropy contributions compete.
The ratio K1 /μo Ms has the dimension of a magnetic field, which makes it
possible to compare anisotropies with applied magnetic fields and coercivities. It is
customary to define the corresponding anisotropy field of K1 -only uniaxial magnets
as
2K1
Ha = (8)
μo Ms
3 Anisotropy and Crystal Field 115
The anisotropy field is defined in a formal way and does not actually exist inside a
magnet; it is equal to the external field that creates a certain effect on the magnet.
Subject to shape anisotropy corrections (Sect. “Magnetostatic Anisotropy”), the
anisotropy field establishes an upper limit to the coercivity Hc . In practice, Hc Ha ,
which is known as Brown’s paradox. An approximate relation is Hc = α Ha , where
α 1 is the Kronmüller factor [8, 9].
The inclusion of higher-order anisotropies gives rise to different nonequivalent
anisotropy field definitions. For example, using Eq. (1) and comparing the energies
for θ = 0 and θ = 90◦ lead to Ha = 2(K1 + K2 + K3 )/µo Ms . The initial slope of the
perpendicular magnetization curves yields the same Ha , whereas the nucleation field
of uniaxial magnets is not affected by K2 and K3 , so that Eq. (8) remains valid for
uniaxial magnets of arbitrary order. In cubic magnets, the anisotropy fields for iron-
type anisotropy (K1 > 0) are described by Eq. (8), whereas nickel-type anisotropy
(K1 < 0) yields Ha = − 4 K1 /3μo Ms (Table 2).
Anisotropy Measurements
M2 M4
η = K1 + K2 − μo MH (9)
Ms 2 Ms 4
where M = Ms sinθ . Minimizing the energy, ∂η/∂M = 0, and dividing the result by
μo M yields
116 R. Skomski et al.
H 2 K1 4 K2
= + M2 (10)
M μo Ms 2 μo Ms 4
Plotting H/M as a function of M2 yields K1 and K2 from the intercept and slope of
the straight line, respectively.
Approach to saturation. Samples are often polycrystalline. In the ideal case
of noninteracting grains with second-order uniaxial anisotropy, the corresponding
random-anisotropy problem can be solved explicitly. The approach to saturation
obeys
Ha 2
M(H ) = Ms 1− (11)
15H 2
In practice, this method requires the fitting of the three parameters: Ms , the
sought-for Ha = 2 K1 /μo Ms , and a high-field susceptibility that must be used
to ensure that ∂M/∂H = 0 for H = ∞. Note that Eq. (11) does not predict
the sign of K1 , because both easy-axis and easy-plane ensembles yield the same
asymptotic behavior. Note that Eq. (11) is essentially a random-anisotropy relation
(Sect. “Random Anisotropy in Nanoparticles, Amorphous, and Granular Magnets”).
Torque magnetometry. A single-crystalline magnetic sample experiences a
mechanical torque –∂Ea /∂α, where α is a magnetization angle relative to the crystal
axes. The angle α is varied with the help of a rotating magnetic field, and the torque
is monitored as a function of the field direction, for example, by measuring the
twisting angle of a filament to which the sample is attached. The interpretation
of the torque depends on the crystalline orientation of the sample, but if the
torque axis is parallel to a magnetocrystalline symmetry axis, the corresponding
anisotropy constants are readily obtained as Fourier components of the torque
curves [13].
Magnetic circular dichroism. Single-ion anisotropy is closely related to the
orbital moment and approximately proportional to the latter in iron-series transition-
metal magnets (Sect. “Perturbation Theory”). A direct way to probe orbital (and
spin) moments on an atomic scale is X-ray magnetic circular dichroism (XMCD).
Circular dichroism means that circularly polarized photons pass through the sample
and that the absorption is different for left- and right-polarized light [14–16]. This is
because the orbital moment reflects atomic-scale circular currents that interact with
light. Furthermore, due to spin-orbit coupling, the light also interacts with spin, so
that XMCD can also be used to simultaneously measure the spin moment.
Crystal-Field Theory
Fig. 4 Angular dependence of 3d wave orbitals: (a) real eigenfunctions and (b) top view on a
mixture of states constructed from m > ∼ exp (ιmφ) with m = ±2. Red and yellow areas in
(a) indicate regions of positive and negative wave functions ψ, respectively, and the darkness
in (b) indicates the electron density ψ*ψ. The wave functions shown in this figure are all
eigenfunctions of the free atoms, but in solids (b), the crystal field, symbolized by ligands (black
dots), favors real wave functions (top), whereas spin-orbit coupling favors complex wave functions
| ± m > (bottom). Details of this “quenching” behavior will be discussed in Sect. “Spin-Orbit
Coupling and Quenching”
the inner shells, which often carry a magnetic moment, interact with the crystalline
environment. The crystal-field (CF) interaction of the Sm3+ ion in Fig. 4 is
one example, but a similar picture is realized in 3d ions, especially in oxides.
Itinerant magnets, such as 3d metals, require additional considerations, because their
electronic structure is largely determined by interatomic hopping (band formation).
Crystal-field theory had its origin in the study of transition-metal complexes
in the last decade of the nineteenth century [17]. An example was the distinc-
tion between violet and green [Co(NH3 )6 ]3+ Cl3 3− , which indicates energy-level
differences of stereochemical origin. The quantitative crystal-field theory dates
back to Bethe [18], who treated the atoms as electrostatic point charges. Since
then, the crystal-field theory has been extended to include quantum mechani-
cal bonding effects in a generalization are known as ligand-field (LF) theory
[19]. As emphasized by Ballhausen [17], the latter is quantitatively superior
to Bethe’s CF theory but leaves the main conclusions of the latter unchanged.
In practice, the terms are often used interchangeably: the atoms surrounding a
magnetic ion are called ligands in both complexes and solids, and the term ligand
field is sometimes used. Physically, both electrostatic and hybridization effects
contribute to the crystal field (ligand field), even in oxides. The focus of this
section is on the traditional electrostatic crystal-field theory, but some interatomic
118 R. Skomski et al.
The wave functions and charge distributions of the electrons are obtained from the
Schrödinger equation. Hydrogen-like 3d wave functions are listed in Appendix C.
The angular parts of the wave functions follow from the spherical character of the
intra-atomic potential and are the same for Fe-series 3d, Pd-series 4d, and Pt-series
5d electrons. However, the radial parts differ for the three series, and they also
depend on non-hydrogen-like details of the atomic potentials. Figure 4 shows the
angular distribution of the five 3d orbitals ψ μ (r). In a free atom, the five orbitals
are degenerate, but in solids and molecules, they undergo crystal-field interactions
described by the Hamiltonian:
HCF = V (r) n(r) dV (12)
where V (r) is the crystal or ligand-field potential and n(r) = ψ ∗ (r)ψ(r) refers to
the d or f orbital(s) in question.
To understand crystal-field effects, it is necessary to consider the shape of the
orbitals. Atomic wave functions and charge distributions such as those shown in
Figs. 4 and 1, respectively, have characteristic prolate, spherical, or oblate shapes.
The larger the magnitude of the quantum number m = lz , the more oblate or flatter
the orbitals, as we can in Fig. 4. This is because large orbital moments, m = ± 2
in Fig. 4 , correspond to a pronounced circular electron motion in the plane perpen-
dicular to the quantization axis (z-axis). By contrast, the prolate |z2 > orbital, which
has m = 0 has its electron cloud close to the z-axis. In a crystalline environment, the
different orbital shapes correspond to different electrostatic interactions. Crystal-
field charges are negative [20], so that the interaction between the 3d or 4f electronic
charge clouds and those of the surrounding atoms is repulsive. As a consequence,
the prolate |z2 > orbital prefers to point in interstitial directions between the atomic
neighbors, rather than towards them. The opposite is true for the oblate orbitals with
m = ± 2.
The electrostatic repulsion between the 3d electrons and those of the neighboring
atoms removes the degeneracy of the five 3d levels and yields the famous eg -t2g
splitting in an environment with cubic symmetry. Figure 5(a) shows the |z2 > orbitals
in a cubal environment where the central atom is coordinated by 8 neighbors.
The |z2 > orbital points in an electrostatically favorable direction and has a very
low energy. The charge distribution of the |x2 -y2 > orbital also points in directions
away from the neighboring atoms or ligands, and it can be shown that the
|x2 -y2 > and |z2 > have the same energy, forming a so-called eg doublet. The |xy>,
|xz>, |yz> orbitals are equivalent by symmetry and form a t2g triplet. The charge
3 Anisotropy and Crystal Field 119
distributions of the triplet orbitals are closer to the ligands, so that the triplet energy
is higher than the doublet energy.
The opposite splitting is realized in an octahedral environment, Fig. 5(b), where
the central atoms are coordinated by six ligand atoms. In this environment, the |x2 -
y2 > and |z2 > orbitals point directly towards the neighboring atoms, whereas the |xy>,
|xz>, |yz> orbitals point in interstitial directions. The tetrahedral environment (c)
has no inversion symmetry but is otherwise very similar to the cubal environment.
Basically, the cubic e-t2 crystal-field splitting is reduced by a factor 2, because
there are only four neighbors. Symmetries lower than cubic partially or completely
remove the eg and t2g degeneracies. Figure 5(d) illustrates this for a tetragonally
distorted cubal environment. Compared to (a), the ligands move towards the basal
plane, which lowers the energy of the |z2 > orbital but raises that of the |x2 -
y2 > orbital. As a consequence, these states no longer form a doublet. Similarly,
the |xz> and |yz> orbitals become somewhat more favorable compared to the
|xy > orbital, because their charge distribution has a substantial out-of-plane
component. This splits the t2g triplet, but |xz> and |yz> remain degenerate, because
the x and y directions are equivalent in a tetragonal crystal.
Figure 6 summarizes the eg -t2g splitting and the evolution of the levels due
to a symmetry-breaking tetragonal distortion. It is important to note that half-
filled (and full) 3d shells have spherical charge distributions and do not interact
with anisotropic crystal fields. Equivalently, the CF interaction leaves the center
of gravity of the 3d levels unchanged. This can be used to gain some quantitative
information about the level splitting. For example, the eg -t2g splitting, also known
120 R. Skomski et al.
as 10Dq, consists of an energy shift of +6Dq for the doublet and a –4Dq shift for
the triplet.
Table 3 lists the crystal-field splittings for the most symmetric point groups in
each crystal system and for axial symmetry. The levels are described by Mullikan
symmetry labels, using t and e for triplets and doublets, respectively [24]. Singlets
are denoted by a or b, depending on whether the reference axis is an n-fold rotation
axis (a) or not (b). The subscripts 1, 2, and 3 indicate C2 symmetries around crystal
axes, and primes ( ) and double-primes ( ) refer to horizontal mirror symmetry
and antisymmetry, respectively. The subscript g (German gerade “even”) denotes
inversion symmetry, which exists for the cubal coordination, Fig. 5(a), but not for
the otherwise very similar tetrahedral coordination, Fig. 5(c). However, the inversion
symmetry of the 3d wave functions means that there are no levels with subscript u
(German ungerade “odd”), so that no confusion arises by dropping the subscript
g [25]. In each crystal system, the complexity of the symmetry labels decreases
with decreasing symmetry. For example, the eg -t2g splitting is limited to the highly
symmetric point group Oh : the respective cubic compounds FeS2 (space group
Th ), MnNiSb (space group Td ), and FeSi (space group T) have eg -tg , e-t2 , and
e-t splittings.
3 Anisotropy and Crystal Field 121
Table 3 Crystal-field splittings of 3d electrons. The colors indicate the crystal-field multiplet
structure: one doublet and one triplet (red), one singlet and two doublets (yellow), three singlets
and one doublet (green), and five singlets (blue). The listed point groups are the most symmetric
ones in each crystal system – less symmetric point groups yield modified symbols, such as missing
subscripts g. In linear molecules (point groups D∞h and C∞v ), the multiplets a1 , e1 , and e2 are
also known as + , , and , respectively
122 R. Skomski et al.
Crystal-Field Expansion
e
N
qi
V (r) = − (13)
4πεo | Ri − r |
i=1
This sum is easily converted into a sum of spherical harmonics by exploiting the
identity:
1 4 π rl
= Y1 m∗ (Θ, Φ) Y1 m (θ, φ) (14)
|R−r | l (2 l + 1) R l+1 |m|<l
so long as R > r. Strictly speaking, the l-summation extends from zero to infinity,
but the symmetry of n(r) in Eq. (12) means that the only relevant terms are l = 2, 4
(d-orbitals) and l = 2, 4, 6 (f -orbitals).
Inserting Eq. (14) into Eq. (13) and summing over all ligands leads to the
cancellation of Yl m (θ , φ) terms that are incompatible with the symmetry of the
crystal. For example, cubic crystals have
V (r) = 20A4 0 x 4 + y 4 + z4 − 3r 4 /5 (15a)
and to any linear combination of Eqs. (15a) and (15b). The structure of this equation
mirrors that of Eq. (4) for the anisotropy of cubic magnets. A third version of Eq.
(15) will be discussed in the context of operator equivalents.
Uniaxial crystal fields are described by
V (r) = A2 0 3 z2 − r 2 + A4 0 35 z4 − 35 z2r 2 + 3 r 4
(16)
+A6 0 231 z6 − 315 z4 r 2 + 105 z2 r 4 − 5 r 4
3 Anisotropy and Crystal Field 123
From Eq. (14) we see that the small parameter in the ligand-field expansion is
r/R, that is, the ratio of d-shell radius to interatomic distance. For this reason,
A4 0 is typically smaller than A2 0 by a factor of order (r/R)2 , or about one order
of magnitude. Exceptions are, for example, weakly distorted cubic structures.
Another way of interpreting crystal fields is to expand V (r) into a Taylor series
with respect to x, y, and z. The nonzero expansion coefficients are the crystal-field
parameters Al m , where l denotes the l-th spatial derivative of V (r). In particular,
A2 0 ∼ ∂ 2 V (r) /∂z2 or, in terms of the electric field, A2 0 ∼ ∂Ez /∂z. This means
that A2 0 is essentially an electric field gradient .
The point-charge model accurately describes the symmetry of the crystal field
[20] and yields semiquantitatively correct numerical predictions for a variety of
systems. It was originally developed for insulators but also approximates rare-earth
ions in metals where the electrostatic interaction is screened by conduction electrons
[21]. This surprisingly broad applicability has its origin in the superposition princi-
ple of crystal-field interactions, which states that the effects of different ligand atoms
are additive in very good approximation [20]. Experimentally, crystal-field effects
are measured most directly by spectroscopy, for example, optical spectroscopy or
inelastic neutron scattering, but there are also indirect measurements, such as rare-
earth anisotropy measurements (Table 4).
Many-Electron Ions
Table 5 Basic branching table for crystal-field splittings of many-electron ions. Both ground-
state and excited terms are included, and the table is not restricted to d electrons. For example, the
free-ion triplet of a single p electron (P) remains unaffected by a cubic crystal field but exhibits a
singlet-doublet splitting in tetragonal and trigonal crystals
Term Cubic CF Tetragonal CF Trigonal CF
S A A A
P T A+E A+E
D E+T A + 2B + E A + 2E
F A+2T A + 2B + 2E 3A + 2E
G A+E+2T 3A + 2B + 2E 3A + 3E
H E+3T 3A + 2B + 3E 3A + 4E
3 Anisotropy and Crystal Field 125
where ρ(r) is the electron charge density. The corresponding term splittings are
large, 1.8 eV for Co2+ , and often dominate the behavior of the ion. The term
energies E(L, S) can be calculated in a straightforward way, by applying the lowest-
order perturbation theory to Eq. (17), E(L, S)=< (L,S) | U | (L, S) >[17, 27].
However, the ground-state term is more easily obtained from Hund’s rules. The
first rule states that the total spin S= i si is maximized. In the above 3d2 example,
there are two terms with maximum S, namely, 3 F and 3 P, both having S=1. Hund’s
second rule acts as a tiebreaker, by favoring large L= i li . Since F and P mean L=3
and L=1, respectively, 3 F is the ground-state term of the 3d2 configuration. Table 6
shows some basic properties of 3d ions; 4f ions will be discussed in the context of
rare-earth anisotropy (Sect. Crystal-Field Theory).
Hund’s first rule yields another simplification: in the ground-state term of the
3d5 configuration, there are five ↑ electrons which occupy the five available orbitals,
lz = −2, ... +1, +2. This yields L = lz = 0, meaning that empty, half-filled, and
completely filled 3d shells are all S-type ions. This principle carries over to magnetic
anisotropy: from Table 5 we see that S states do not undergo crystal-field splitting
but remain in their highly symmetric degenerate A state. The corresponding charge
distribution is spherical, and the ion does not contribute to the magnetocrystalline
anisotropy (except via admixture with a higher excited state). Figure 7 shows the
level splittings of the ground-state terms of the 3d ions in an octahedral crystal field.
Note the half-shell symmetry of the splittings: aside from the sign, there are only
two nontrivial cases, namely, one electron or hole (d1 , d4 , d6 , d9 ) and two electrons
or holes (d2 , d3 , d7 , d8 ).
The crystal-field interaction is normally weaker than the intra-atomic exchange.
However, very strong crystal fields may negate Hund’s rules and cause a transition to
a low-spin state. For example, octahedrally coordinated Fe2+ has the configuration
3d6 , and, according to Fig. 7, a T2g ground state, that is, t2g (↑↑↑↓)-eg (↑↑). The
two ↑ electrons in the eg -doublet experience a competition between electron-
electron interaction, which favors parallel spin alignment, and the CF, which
favors t2g occupancy. In very strong crystal fields, the electronic structure becomes
t2g (↑↑↑↓↓↓)-eg (empty), and the ion loses its magnetic moment. This is an example
of a high-spin low-spin transition. Aside from d6 , the three ions d4 , d5 , and d7
undergo a high spin low spin in strong octahedral crystal fields, leading to spin
moments of 2 μB (d4 ) and 1 μB (d5 , d7 ).
It is instructive to plot the term energies as a function of the crystal field,
using the eg -t2g splitting 10Dq to quantify the crystal field in an Orgel diagram.
An extension of the Orgel diagram is the Tanabe-Sugano diagram , where both
the crystal field (Dq) and the term energies are divided by the Racah parameter
B [24]. This parameter links Hund’s second rule, namely, the maximization
of L, to the underlying intra-atomic electron-electron interaction and satisfies
E(3 P) – E(3 F) = 15B. The ground-state energy is used as the energy zero, which
helps to visualize transitions. Figure 8 shows a Tanabe-Sugano diagram where the
ground-state term changes from high spin 5 T2g (blue line) to low spin 1 A1g (red
line).
Any splitting ±E of a degenerate state lowers the energy by about E if the
level is only partially occupied. For example, the tetragonal lattice distortion of
Fig. 6 means that the eg doublet splits into a low-lying a1g state and a b1g state
and a single electron in the eg doublet moves to the a1g level. The resulting crystal-
field energy gain competes against the mechanical energy necessary to tetragonally
distort the crystal. However, the former is linear in strain ε, whereas the latter is
quadratic, so that the CF should always create a small distortion. This is known as
the Jahn-Teller effect.
3 Anisotropy and Crystal Field 127
Fig. 8 Tanabe-Sugano diagram for a 3d6 ion [24]. The energy unit Dq is one tenth of the eg -t2g
splitting and B is the Racah parameter [28]. The vertical line indicates a transition from a high-spin
state (blue) to a low-spin state (red)
v2 1 1
me c 2 1+ 2
= me c 2 + me v 2 − me v 4 (18)
c 2 8
128 R. Skomski et al.
Fig. 9 Spin-orbit coupling in a free ion (schematic). The orbiting spin acts like a current loop and
creates a magnetic field that acts on the spin. The nucleus does not actively participate in the spin-
orbit coupling but merely serves to curve the trajectory of the electron: a circular racetrack would
do equally well
3
Hso = 2 2
s · ∇V × k (19)
2me c
This equation shows that the spin-orbit coupling favors a spin direction perpen-
dicular to both potential gradient and direction of motion. For example, electrons
in thin films experience a Rashba effect [30], and there is a small interstitial
contribution to the magnetocrystalline anisotropy [31]. The Rashba effect means
that electrons of wave vector k move in the film plane and experience a potential
gradient perpendicular to the film, which naturally occurs due to broken inversion
symmetry at thin-film surfaces and interfaces. According to Eq. (19), the spin then
prefers to lie in the plane, in one direction perpendicular to k. In the opposite in-
plane spin direction, the energy is enhanced, which is referred to as Rashba splitting
of the electron levels.
The potential gradient is most pronounced near the atomic nuclei, and for
hydrogen-like 1/r potentials
2 Ze2
Hso = l·s (20)
2
2me c 4πεo r 3
2
Using Appendix C, we can evaluate the average <1/r3 > and obtain Hso = ξ l · s.
Here ξ is the spin-orbit coupling constant:
2 Z 4 e2 1
ξ= 2 2 3
(21)
2me c ao 4πεo n3 l l + 1/ (l + 1)
2
3 Anisotropy and Crystal Field 129
v2 1 1
me c 2 1 + = me c 2 + me α 2 c 2 − me α 4 c 4 (22)
c2 2 8
me 4 4 2 1
ξ= Z α c + (23)
2 1
n l l + /2 (l + 1)
3
This equation captures the relativistic nature of spin-orbit coupling and magnetic
anisotropy. In terms of powers of α, ξ is a small relativistic correction, similar to
the v4 term in Eqs. (18) and (22), but Z, which is largest for inner-shell electrons in
heavy elements, greatly enhances the effect in partially filled shells. Tables 7 and 8
show values of spin-orbit coupling constants ξ for 3d, 4d, 5d, 4f, and 5f elements,
obtained from Hartree-Fock calculations [32, 33]. A comparison of experimental
data and theoretical predictions indicates that these tables have an accuracy of the
order of 10% [32–34]. Furthermore, ξ somewhat increases with ionicity [34]: going
from T2+ to T3+ and T+ , respectively, changes the SOC constant of late 3d elements
by about ±10%.
There are two limits for many-electron spin-orbit coupling. Russell-Saunders
coupling means that the ion has well-defined values of L = i li and S = i si .
They are good quantum numbers, and the SOC is a weak perturbation. This limit
is realized when the intra-atomic interactions are stronger than ξ . In the opposite
limit of j-j coupling, the i-th electron first experiences a one-electron SOC so that
J = i (li + si ). Most solid-state magnetism involves Russell-Saunders coupling, but
j-j coupling is important in two limits: (a) low-lying levels of very heavy elements,
such actinides, and (b) excited levels of most elements, except very light ones. In (a),
the j-j coupling is imposed by the large λ in heavy atoms, whereas in (b), it reflects
the increased electron separation in excited states. In many cases, Russell-Saunders
coupling yields the correct multiplet structure but j-j coupling causes quantitative
deviations in the level spacing. For example, the j-j coupling effect on the 3 P2 -3 P0
splitting is negligible in C, about 20% in Si, and dominates in Ge, Sn, and Pb [26].
Magnetic anisotropy reflects low-lying excitations, and Russell-Saunders coupling
therefore applies to both transition metals and rare earths.
The Russell-Saunders coupling establishes the vector model, where J = L + S.
Using the Hund’s-rules ground-state terms to evaluate i ξ i li · si yields the ionic
spin-orbit coupling Λ L·S, where Λ = ± ξ /2S for less and more than half-filled
shells, respectively [17]. The change of sign at half filling yields Hund’s third rule:
for the early elements in each series, J = L – S, and for the late elements, J = L + S.
Each multiplet has 2 J + 1 Zeeman-like intramultiplet levels, Jz = − J, ...,
(J – 1), J, and the degeneracy of these levels is removed by a magnetic field or by the
crystal field. Due to the g-factor of the electron, a magnetic field couples to (L + 2S)
rather than to (L + S). This makes it necessary to project L + 2S onto J, so that
(L + 2S) · J = g J2 . The Landé g-factor of the ion g = 1 for pure orbital magnetism
(L = J) and g = 2 for pure spin magnetism (L = 0). For arbitrary L and S, less and
more than half-filled shells exhibit g = 1 – S/(J + 1) and g = 1 + S/J, respectively.
The exchange between magnetic ions involves spin only, which mandates the use of
the projection S · J = (g − 1) J2 and yields de Gennes factor G = (g – 1)2 J(J + 1).
This makes it possible to write the exchange interaction as J = G Jo , where Jo is a
J-independent Heisenberg exchange constant.
Spectroscopic and magnetic measurements indicate that Hund’s rules are well
satisfied in rare-earth ions (Sect. “Crystal-Field Theory”), but iron-series transition-
metal ions systematically violate them, especially the third rule. For example,
g ≈ 2 for iron-series atoms in almost all metallic and nonmetallic crystalline
environments. In other words, the magnetic moments of Fe, Co, and Ni originate
3 Anisotropy and Crystal Field 131
nearly exclusively from the spin of the 3d electrons, and the atoms look as if L = 0.
For example, iron has a magnetization of about 2.2 μB , but only about 5% of this
moment is of orbital origin. This effect is known as orbital-moment quenching.
Quenching was first recognized explicitly by van Vleck in 1937 [35].
Figure 10 illustrates the physics behind this effect, namely, the disruption of
the electron’s orbital motion by the crystal field. Mathematically, the difference
between quenched and unquenched wave functions is that between real and complex
spherical harmonics (Appendix A). Consider the two states |x2 –y2 >∼cos(4φ) and
|xy>∼ sin(4φ), which are shown in the top row of Fig. 7. Using lz = −i∂/∂φ
to calculate <lz > = − i ψ* lz ψ dφ yields <lz > = 0; it is completely
quenched. Pictorially, the electron “oscillates” in the valleys between the CF
potential mountains, as indicated by the dashed line in Fig. 10, and these oscillations
yield no net orbital motion. The respective electron densities <ψ|ψ> for |x2 –y2 > and
|xy>, namely, ρ = 1 + cos(8φ) and ρ = 1–2cos(8φ), exhibit complementary minima
and maxima, and the positioning of mountains decide which of the two densities
yields the lower energy.
Rather than asking why the orbital is quenched, we should therefore ask how
an orbital moment arises in a solid. Unquenched orbitals are described by wave
functions of the type exp (±imφ) = cos(mφ) ± i sin(mφ), or |±2>= |x2 –y2 >± |xy>.
These functions describe an uninhibited orbital motion and yield <lz > = ± 2 in units
of . However, the corresponding electron charge cloud is ringlike, ρ = const., so
that the electron occupies both valley and energetically costly hill regions, rather
than being confined to valleys. The competition between spin-orbit coupling (SOC)
and crystal field (CF) decides whether the orbital moment is quenched. In the 4f
case, the SOC is large, and the orbital motion of the electrons remains essentially
unquenched by the CF, as in Fig. 9. The opposite is true for 3d electrons, where the
SOC is a small perturbation to the CF, leading to nearly complete quenching.
132 R. Skomski et al.
Rare-Earth Anisotropy
Rare-Earth Ions
Rare-earth atoms tend to form tripositve ions in both metals and insulators. Since
spin-orbit coupling is very strong for inner-shell electrons in heavy elements, the
4f electrons experience a rigid coupling of their spin and orbital moments, with
unquenched orbitals and Hund’s-rules spin-orbit coupling. Magnetic anisotropy
is an intramultiplet effect, involving the 2 J + 1 magnetic quantum states Jz
of the ground-state multiplet. Excited multiplets have relatively high energies,
with the notable exceptions of Eu3+ and Sm3+ [33]. In the former, this energy
is only about 40 meV, but the ground-state moment of Eu2+ is zero, and the
element often adopts a Eu2+ configuration with half-filled shell and zero anisotropy.
Otherwise, the Eu3+ ion shows strong van Vleck susceptibility: the Eu3+ moment
is zero in its J = 0 ground-state multiplet, where the contributions from S = 3
and L=3 cancel, but the first-excited multiplet (7 F1 , J = 1) is only 330 K
above the 7 F0 ground-state multiplet. In the case of Sm3+ , the splitting between
the ground-state multiplet (6 H5/2 ) and the first-excited multiplet (6 H7/2 ) is about
100 meV (∼1000 K) [33], so that interatomic interactions and thermal excitations
yield some admixture of 6 H7/2 character (J-mixing). The focus of this section
is on ground-state multiplets, with a brief discussion of the excited Sm multi-
plet.
To determine the crystal-field energy, it is first necessary to specify the shape of
the 4f shells. Why is the Sm3+ ion in Fig. 1 prolate rather than oblate? Interchanging
oblate and prolate shapes changes the sign of K1 and has far-reaching implications.
A tentative answer is provided by the angular dependence of the (real) one-electron
4f wave functions, which are shown in Fig. 11. States with m = ±3, favored by
Hund’s second rule, are prolate, whereas the m = 0 state is oblate. The strong spin-
orbit coupling then creates axially symmetric superpositions exp.(±mφ) from states
with equal |m|, and Hund’s rules determine how the one-electron orbitals combine
to yield many-electron orbitals.
Like any electric charge distribution, the many-electron 4f shell can be expanded
in spherical harmonics. This multipole expansion provides a successively improved
description of angular features. In the zeroth order, the 4f shell is approximated by
a sphere of charge Q = Qo and does not support any anisotropy. The first-order
corresponds to an electric dipole moment Q1 , which is absent by wave-function
symmetry. The lowest-order electric moment is the second-order quadrupole
moment Q2 , which describes the prolaticity of a charge distribution. Table 10
lists some Hund’s-rules ground-state properties of the tripositive rare-earth ions,
including Q2 .
There is a systematic dependence of the ground-state ionic shape on the number
of 4f electrons. Gd3+ has a half-filled shell and a spherical charge distribution
because Hund’s rules mandate seven ↑ electrons having l = 3, 2, 1, 0, −1, −2,
−3, so that L = i li = 0 (S-state ion) and Q2 = 0. The other elements follow a
quarter-shell rule: the first and third quarters of the series have oblate ions, and the
second and fourth quarters have prolate ions. This rule is a consequence of particle-
134 R. Skomski et al.
hole symmetry in each half shell: 6 electrons are equivalent to a half-filled shell (7
electrons) with one hole. By Hund’s rules, the first electron(s) in a shell have a large
|m| and are oblate (Fig. 11), corresponding to a negative Q2 . Removing an electron
with a large |m| from a half-filled shell yields one oblate hole, which is the same as
a prolate electron distribution with a positive Q2 .
Table 10 is limited to the quadrupole moment Q2 . Higher-order multipole
moments provide a refined description of the angular dependence of the rare-earth 4f
electron cloud. The third-order octupole and fifth-order triakontadipole moments are
zero by symmetry, but the fourth-order hexadecapole moment (16-pole, Q4 ) and the
sixth-order hexacontatetrapole (64-pole, Q6 ) are generally nonzero. Figure 12 shows
the zoology of the angular dependence of the 4f charge distributions up to the fourth
order. For Hund’s-rules ions, the number of animals is limited by the symmetry of
the wave functions (Figs. 4 and 11), namely, n ≤ 4 for 3d ions and to n ≤ 6 for
4f ions [38]. Furthermore, since the rare-earth 4f electrons are unquenched, the 4f
charge distribution shows axial symmetry, and there are no multipole contributions
Ql m with m = 0. The anisotropy corresponding to the unquenched quadupole
3 Anisotropy and Crystal Field 135
Table 10 Hund’s-rules ground states of 4f ions. The orbitals listed from left to right, lz = 3, 2, 1,
0, −1,–2, −3.
moment of rare-earh ions can be very high, up to a few K per atom in temperature
units [36]. This temperature scale needs to be distinguished from that governing
the temperature dependence of anisotropy constants, which involves interatomic
exchange (Sect. 4.4.4).
136 R. Skomski et al.
Fig. 12 Cartoon illustrating the electrostatic R3+ multipole moments up to the fourth order (Q0 ,
Q2 , and Q4 ). The 4f charge distributions n(r) derive from Figs. 4 and 11 and are both axially and
inversion symmetric
Operator Equivalents
The next step is to quantitatively determine the interaction V (r) n (r) dV
(Sect. “One-Electron Crystal-Field Splitting”) between the crystal field and the
4f charge distribution. This can be done explicitly, in a straightforward but
cumbersome way, but a more elegant method is to use operator equivalents. Both
approaches assume that the crystal field, V (r) or Al m , and the 4f charge distribution,
n(r) or Qn , are known.
The straightforward method is best explained by considering
the lowest-order
uniaxial limit, where Eq. (16) reduces to V (r) = A2 0 3z2 –r 2 . Substituting this
expression into Eq. (12) yields
HCF = A02 3z2 − r 2 n(r)dV (24)
3 Anisotropy and Crystal Field 137
O2 0 (J ) = 3 Jz 2 –J (J + 1) (25)
1 2
O2 2 (J ) = J+ + J− 2 (26)
2
been tabulated in Refs. 33 and especially 38. It is also possible to define operator
equivalents Ol m (L, Lz ) and related spin Hamiltonians Hspin (S, Sz ) for 3d ions
(Sect. “Transition-Metal Anisotropy”), but the underlying physics is different from
the presently considered rare-earth limit, because L and S are only weakly coupled
(quenching).
The occurrence of Jz and of the ladder operators J± greatly simplifies the
calculation of matrix elements of magnetic ions in a crystal field or exchange field.
For Sm3+ , J = 5/2 yields Jz = ±5/2, ±3/2, and ± 1/2, corresponding to O2 0 = 10,
O2 0 = −2, and O2 0 = −8. The magnitude of the splitting is determined by A2 0 and
by the radial part of n(r), but the evaluation of the Ol m is sufficient to determine the
relative energies, namely, 5:–1:–4 in the present example.
The multipole moments are straightforward linear functions of the operator
equivalents:
Here Bm n = θ n < rn >4f Al m and g J·H describes the comparatively weak Zeeman
interaction and HJ is the exchange field. The quantities L, S, and λ enter this
equation only indirectly, via Hund’s rules and J = L ± S. However, O l m contains
intramultiplet excitations (−J < Jz < J), and the raising and lowering operators
J± in Eq. (26) indicate that off-diagonal crystal fields, such as A2 2 , can change
Jz . To exactly diagonalize Eq. (29), it is necessary to include matrix elements
<Jz | Ol m (J ) | Jz >, where Jz = J’z . These matrix elements are known [38] but
complicate the calculations and the evaluation of the results.
Major simplifications arise if the term involving the exchange energy is much
larger than the CF interaction. This is approximately the case in rare-earth transition-
metal (RE-TM) intermetallics such as Nd2 Fe14 B [39, 40], where the exchange field
is roughly proportional to the RE-TM intersublattice exchange JRT . This strong
exchange field stabilizes states with Jz = ±J, where the sign determines the net
magnetization but does not affect the anisotropy. Intramultiplet excitations, caused
by the operators J± , are effectively suppressed, and only the Ql = θl < r l >4f Ol 0
terms remain to be considered. Furthermore, putting Jz = ±J drastically simplifies
the operator equivalents:
O2 0 = 2 J · (J − 1/2) (30)
Single-Ion Anisotropy
The anisotropy constants are extracted by rotating the magnetization, that is, by
rotating the 4f charge distribution and calculating the energy. It is convenient to
choose a coordinate frame where J is fixed, that is, to actually rotate the crystal field
around the rare-earth ions. This can be done for each ligand separately, because
crystal fields obey the superposition principle. It starts conveniently from an axial
coordination, R || ez , and the corresponding crystal fields A 2 , A 4 , and A 6 are
referred to as intrinsic crystal fields [20]. In the point-charge model, A2 (R) =
–eq/4πεo R 3 . Due to the axial symmetry of the 4f charge distribution, the rotation
of R into the correct direction relative to the 4f moment involves a polar angle Θ.
For example
1
A2 0 = A2 3cos2 − 1 (33)
2
describes the rotation of a single ligand. By adding the contributions from all
ligands, one can create any crystal field and any relative orientation between crystal
and magnetic moment. This approach is not limited to uniaxial anisotropy. Equation
(16) is uniaxial, but it contains a z4 term, and by rotating different charges onto
the x- and y-axes, one can create crystal fields of the type x4 + y4 + z4 , which are
cubic. Figure 13 illustrates the rotation of the crystal around the rare-earth ion for a
fourth-order anisotropy contribution. Note that none of the rare-earth ions in Fig. 12
has the ghost shape, but quadrupole moments (Q2 ) do not interact with crystal fields
having fourfold symmetry, so that Fig. 13 actually applies to the UFOs (Ce, Tb) and
to the digesting snakes (Sm, Er, Tb).
Since crystal rotations, for example, Θ = 45◦ in Fig. 13(c), and magnetization
rotations are equivalent, Eq. (33) also describes the energy as a function of the
magnetization angle, that is, the anisotropy energy per rare-earth atom. Explicitly
140 R. Skomski et al.
1
Ea = Q2 A2 0 3 cos2 θ − 1 (34)
2
3
K1 = − A2 0 Q2 (35)
2VR
where VR is the crystal volume per rare-earth atom. This equation resolves the rare-
earth anisotropy problem by separating the properties of the 4f shell, described by
Q2 , from the crystal environment, described by A2 0 .
Crystal-field parameters such as A2 0 describe the surroundings of the rare-earth
ion and therefore change little across an isotructural series of compounds with
different rare earths. Examples are A2 0 values of 300 K/ao 2 for R2 Fe14 B, 34 K/ao 2
for R2 Fe17 , and – 358 K/ao 2 for R2 Fe17 N3 . In a given crystalline environment, the
sign of the rare-earth anisotropy depends on whether the ion is prolate or oblate.
A positive K1 is obtained by using oblate ions, such as Nd3+ , on sites where the
crystal-field parameter A2 0 is positive, and prolate ions, such as Sm3+ , in crystalline
environments where A2 0 is negative. This explains the use of neodymium in hard
R2 Fe14 B and RT12 N alloys, whereas samarium is preferred in RCo5 , R2 Fe17 N3 ,
and RT12 intermetallics. The rare-earth ions responsible for the anisotropy must
be magnetic, whereas both magnetic and nonmagnetic ligand atoms contribute to
the crystal field. An interesting example is interstitial nitrogen in Sm2 Fe17 , which
changes the anisotropy from easy-plane to easy-axis [41].
Using volume VR per rare-earth ion as a unit volume, the uniaxial anisotropy
constants are
3 21
K1 = − A2 0 Q2 − 5 A4 0 Q4 − A6 0 Q6 (36)
2 2
3 Anisotropy and Crystal Field 141
35 0 189
K2 = A4 Q4 + A6 0 Q6 (37)
8 8
231 0
K3 = − A6 Q6 (38)
16
1 5
K2 = A4 4 Q4 + A6 4 Q6 (39)
8 8
11
K3 = − A6 4 Q6 (40)
16
1
K3 = − A6 6 Q6 (41)
16
21 0
K1 c = −5 A4 0 Q4 − A6 Q6 (42)
2
231 0
K2 c = A6 Q6 (43)
2
A striking feature in the last two equations is the absence of independent in-
plane crystal-field parameters, such as A4 4 . While a separate consideration of O4 4 ,
as contrasted to O4 4 ∼ Q4 , is not necessary for rare earths due to the axial symmetry
of the 4f charge clouds, the non-uniaxial CF parameters are not independent but
obey A4 4 = 5A4 0 and A6 4 = − 21A6 0 in cubic symmetry.
Temperature Dependence
π
m JRT
< cos θ >= N exp cos θ cosm θ sin θ dθ (44)
kB T
0
JRT 2
K1 (T ) = K1 (0) (45)
15 kB T 2
Table 12 First and second-order anisotropy constants at low temperatures (LT) and at room
temperature
Element LT RT Structure Refs.
K2
K1 (MJ/m3 ) (MJ/m3 ) K1 (MJ/m3 ) K2 (MJ/m3 )
Fe 0.052 −0.018 0.048 −0.015 bcc [47]
Co 0.7 0.18 0.41 0.15 fcc [47]
Ni −0.012 0.03 −0.005 −0.002 hcp [47]
Nd2 Fe14 B −18 48 4.3 0.65 tetr. [48]
Pr2 Fe14 B 24 −7 5.6 ≈0 tetr. [48]
Sm2 Fe17 N3 12 3 8.6 1.9 rhomb. [48]
In other words, 2nd-, 4th-, and sixth-order anisotropy contributions are propor-
tional to the third, tenth and 21st powers of the magnetization, respectively. Equation
(46), which is valid up to about 0.65 Tc for Fe, means that higher-order anisotropy
contributions rapidly decrease with increasing temperature. A crude approximation,
based on Ms ∼ (1 – T/Tc )1/3 and used in Fig. 14(a), yields the linear dependence
K1 (T) ≈ K1 (0) (1 – T/Tc ) for the first anisotropy constant K1 of uniaxial magnets
(Table 12).
In summary, the temperature dependence of the anisotropy is a very com-
plex phenomenon. Each crystallographically nonequivalent site generally yields
a different anisotropy contribution with a different temperature dependence, and
the distinction is most pronounced between rare-earth (4f ) and transition-metal
(3d) sites. As a rule of thumb, the RE or TM contributions dominate at low
or high temperatures [40, 49], and their respective temperature dependences are
approximately given by Eqs. (44 and 45) and Eq. (46). In the latter case, K1 ∼ Ms 3
(uniaxial magnets) and K1 ∼ Ms 10 (cubic magnets). Actinide (5f ) anisotropy is
limited by the interatomic exchange, although the spin-orbit coupling is very large,
and its temperature dependence follows that of the magnetization, K1 ∼ Ms [50].
The anisotropy of 3d–5d (and 3d–4d) intermetallics, such as tetragonal PtCo, largely
originates from the heavy transition-metal atoms, but this anisotropy is realized via
spin polarization by the 3d sublattice, roughly corresponding to K1 ∼ Ms 2 [51, 52].
The same dependence is obtained for the two-ion (magnetostatic) contribution to the
magnetocrystalline anisotropy, Sect. “Two-Ion Anisotropies of Electronic Origin”,
because the magnetostatic energy scales as Ms 2 (Table 13).
3 Anisotropy and Crystal Field 145
Transition-Metal Anisotropy
Table 14 Anisotropy, magnetization, and Curie temperature of some oxides [9–11, 37, 63]
K1 μo Ms
Substance (RT) (RT) Tc Structure
MJ/m3 T K
α-Fe2 O3 −0.007 0.003 960 Rhombohedral (Al2 O3 )
γ-Fe2 O3 −0.0046 0.47 863 Cubic (disordered spinel)
Fe3 O4 −0.011 0.60 858 Cubic (ferrite)
MnFe2 O4 −0.003 0.52 573 Cubic (ferrite)
CoFe2 O4 0.270 0.50 793 Cubic (ferrite)
NiFe2 O4 −0.007 0.34 858 Cubic (ferrite)
CuFe2 O4 −0.0060 0.17 728 Cubic (ferrite)
MgFe2 O4 −0.0039 0.14 713 Cubic (ferrite)
BaFe12 O19 0.330 0.48 723 Hexagonal (M ferrite)
SrFe12 O19 0.35 0.46 733 Hexagonal (M ferrite)
PbFe12 O19 0.22 0.40 724 Hexagonal (M ferrite)
BaZnFe17 O27 0.021 0.48 703 Hexagonal (W ferrite)
Y3 Fe5 O12 −0.0007 0.16 560 Cubic (garnet)
Sm3 Fe5 O12 −0.0025 0.17 578 Cubic (garnet)
Dy3 Fe5 O12 −0.0005 0.05 563 Cubic (garnet)
CrO2 0.025 0.56 390 Tetragonal (rutile)
NiMnO3 −0.26 0.13 437 Hexagonal (FeTiO3 )
(La0.7 Sr0.3 )MnO3 −0.002 0.55 370 Rhombohedral (perovskite)
Sr2 FeMoO6 0.028 0.25 425 Orthorhombic
146 R. Skomski et al.
E1 (k) 0 0 i
H= +λ (47)
0 E2 (k) −i 0
where E1 (k) and E2 (k) are two 3d subbands connected by a spin-orbit matrix
elements ±iλ. The spin-orbit term favors a nonzero net orbital moment, as required
3 Anisotropy and Crystal Field 147
for magnetic anisotropy, but λ ≈ 50 meV is usually much smaller than |E1 (k) –
E2 (k)|, the latter being comparable to the bandwidth W of several eV. However,
even for |E1 (k) – E2 (k)| = W, perturbation theory leads to a small orbital moment
and some residual anisotropy. Furthermore, accidental degeneracies E1 (k) = E2 (k)
yield the eigenvalues ±λ and completely unquenched orbitals. The corresponding
anisotropy energy, about 50 meV per atom, is then huge compared to typical iron-
series anisotropies of 0.1 meV, or about 1 MJ/m3 .
The practical challenge is to add the spin-orbit couplings of all atoms (index i):
Hso = i λi l i · s i (48)
to the isotropic Hamiltonian and to determine the anisotropy contributions from all
bands and k-vectors. To quantitatively determine the anisotropy, this procedure must
be performed for different spin direction s, s || ez and s || ex .
Perturbation Theory
<μk σ |l · s|μ k σ ><μ k σ |l · s|μkσ >
Ek = λ2 (49)
μ,σ k Eμ k σ −Eμkσ
and σ z are Pauli’s spin matrices. Equation (50) is sometimes reformulated in form
of a statement that the anisotropy energy is proportional to the quantum average
of angular orbital moment. However, this equivalence is limited to small orbital
moments [55] – rare-earth orbital moments are fixed by Hund’s rules (Fig. 13) and
do not change as a function of magnetization direction.
The spin summation is greatly simplified by the factorization of the unperturbed
wave functions, |μ k σ >= |μ k>|σ >, but the k-space summations can only
be performed numerically for most systems. The factorization into |μk> and
|σ > makes it possible to formally perform a summation over |μ k>, |μ k >, and
|σ > only, leaving the spin s unaveraged. This leads to a spin Hamiltonian of the
general many-electron type:
λn
Kn/2 ∼ (53)
Vo (Eo − Eu )n−1
where Vo is the crystal volume per transition-metal atom. This important relation,
known as spin-orbit scaling, was first deduced for lowest-order cubic anisotropy,
where n = 4 and K1 c ∼ K2 ) [1]. In this case, the anisotropy constant scales as
λ4 /A3 , where A is the energy-level splitting in the absence of spin-orbit coupling
(crystal-field splitting or bandwidth). This scaling behavior explains the low cubic
anisotropy of bcc iron (0.05 MJ/m3 ) and Ni (−0.005 MJ/m3 ), as compared to that
of hexagonal Co (0.5 MJ/m3 ) and YCo5 (5 MJ/m3 ).
Equation (53) provides a semiquantitative understanding of transition-metal
anisotropies. In metallic systems, Eu – Eo ∼ W, where the bandwidth W is about
5 eV for iron-series (3d) magnets and somewhat larger for palladium -series (4d),
3 Anisotropy and Crystal Field 149
platinum-series (5d), and actinide (5f ) magnets. The spin-orbit coupling rapidly
increases as the atoms get heavier (Tables 7 and 8), so that heavy transition-
metal elements are able to support very high anisotropies so long as the induced
magnetic moments on the heavy atoms are appreciable. In particular, FePt magnets
are important in magnetic recording [58], but both the low Curie temperature and
the low intrinsic magnetic moment per heavy transition-metal atom make it very
difficult to exploit the high anisotropy of very heavy atoms, up to 1000 MJ/m3 for
actinide compounds such as uranium sulfide [59].
As outlined in Eqs. (49 and 50), quantitative anisotropy calculations require a
summation of all occupied and unoccupied states. This summation involves matrix
elements <o|l·s|u>, which couple wave functions of equal |Lz |, namely, Lz = ±1 and
Lz = ±2, where the quantization axis (z-axis) is parallel to the spin direction (see
below). These matrix elements affect the sign and magnitude of the anisotropy but
do not change its order of magnitude, because they are of order unity. The order of
magnitude of the anisotropy is given by the spin-orbit coupling, which is essentially
fixed for a given element (Tables 7 and 8) and by the denominator Eo – Eu , which
requires a detailed discussion.
In Eq. (50), the itinerant wave functions |o > and |u > are of the Bloch type and can
therefore be expanded into atomic wave functions. Including spin, there are 10 3d
orbitals per atom, which yield 100 matrix elements <l·s > for each spin direction.
However, the number of independent matrix elements is drastically reduced by
symmetry. First, for the highly symmetric point groups Cnv , Dn , Dnh , and Dnd
(Sect. “Anisotropy and Crystal Structure”), only three spin and orbital-moment
directions need to be considered, namely, x, y, and z. Second, the matrix elements
between ↑↑ and ↓↓ pairs are the same, whereas those for ↑↓ and ↓↑ are equal
and opposite in sign. Third, many of the remaining matrix elements are zero by
symmetry [60].
Explicit matrix elements are obtained by applying equations such as
lˆ z = i(y∂/∂x – x∂/∂y) or lˆ z = −i∂/∂φ to the real or quenched 3d wave functions
of Fig. 4. For example, |xy>∼ sin(4φ) and |x2 –y2 >∼ cos(4φ) yield:
2 2 ˆ
Fig. 15 The three “canonical” d electron orbital-momentum √ matrix elements: (a) <x –y |l z
|xy > = 2i, (b) <xz|lˆ z |yz>= i, and (c) <z2 | l̂x | yz>= 3 i. The dashed lines are out of
the paper plane and visualize the direction of l̂ , but the actual length of the lines is zero, because
all orbitals belong to the same atom
responsible for the small orbital contribution to the magnetic moment of itinerant
magnets, such as Fe, and for the corresponding magnetic anisotropy.
The five 3d orbitals yield a fairly large number of matrix elements such as
that in Eq. (54), but due to symmetry, many of them are zero, and only three
are nonequivalent. Figure 15 illustrates these three “canonical” matrix elements.
Figure 15(a) corresponds to Eq. (54) and is encountered only once, aside from the
conjugate complex value –2i created by interchanging xy and x2 –y2 . The matrix
element of Fig. 15(b) occurs five times, namely, in form of <xz|lˆ z |yz>, <xy|lˆ x |xz>,
<xy|lˆ y |yz>, <x2 –y2 |lˆ x |yz>, and <x2 –y2 |lˆ y |xz>, whereas that of Fig. 15(c) has two
realizations, namely, <z2 |lˆ x |yz> and <z2 |lˆ y |xz>. A physical interpretation of matrix
elements <ψ 1 |l̂ |ψ 2 > is that <ψ 1 |ψ 2 > = 0 but the angular momentum operator
rotates ψ 2 and thereby creates overlap with ψ 1 . The rotation angle is equal to π/m,
where m is the magnetic quantum number of the orbitals, so that π/4 in Fig. 15(a, c)
and π/2 in Fig. 15(b).
2 2
H=− ∇ + j Vo r − Rj + j Hso Rj (55)
2me
where the matrix elements of Hso are those of Fig. 15. The lattice periodicity is
accounted for by the ansatz
ψkμ (r) = N exp ik · Rj φμ r − Rj (56)
j
where the index μ labels the orbitals, such as |xy↑>. Putting Eq. (56) into Eq. (55)
yields, in matrix notation
Eμμ (k) = Eo δμμ + Aμ δμμ + m exp (ik · Rm ) tμμ (Rm ) + Eso,μμ (57)
Itinerant Anisotropy
the bands and creates an avoided crossing near k = π/a. The gap at this degenerate
Fermi-surface crossing (DFSC), 4λ, and the derived anisotropy energy K1 (k), shown
in Fig. 17(b), are finite, in contrast to the perturbative result of Eq. (50), where the
anisotropy contribution diverges at Eo (k) = Eu (k). To appreciate this peak, is useful
to recall that typical noncubic 3d anisotropies are of the order of 0.1 meV per atom,
as compared to SOC constants λ of about 50 meV and bandwidths W in excess of
1000 meV. In other words, the avoided crossings in Fig. 17(a) may look tiny on the
scale of the bandwidth but they are huge compared to anisotropies actually realized
in solids.
The bottom panel in Fig. 17(b) shows the k-space integrated density of states as
a function of the occupancy n of the spin-down |xy> and |x2 –y2 > bands. In analogy
to Eq. (50), it is sufficient to restrict the integration to the matrix elements between
occupied (o) and unoccupied (u) states, as schematically shown in Fig. 17(a). The
anisotropy, which favors a magnetization perpendicular to the chain, also exhibits a
DFSC peak for half filling, near k = π/a, although this peak is much less pronounced
than the k-space peak.
The simple model of Fig. 16 elucidates a major aspect of itinerant anisotropy,
namely, that different pairs of 3d subbands yield positive or negative anisotropy
contributions, depending on which of the three canonical matrix elements are
realized in each magnetization direction. Including spin, this creates 10 × 10 = 100
different contributions. Each of these contributions depends on the band filling and
may further split due to the involvement of different neighbors. As a consequence,
the anisotropies exhibit a complicated oscillatory dependence on d-band filling.
Figure 18 illustrates this point for a nanoparticle with a completely filled ↑ band.
Fig. 16 Monatomic spin-chain model (top) with two orbitals per site, |xy > (center) and
|x2 –y2 > (bottom)
3 Anisotropy and Crystal Field 153
Fig. 17 Magnetic anisotropy of the spin chain of Fig. 16: (a) band structure without CF and SOC
interactions (dashed lines) and with CF and SOC interaction (solid lines) and (b) anisotropy as a
function of the electron wave vector in units of 1/a (top) and band filling of the |xy> and |x2 –
y2 > orbitals (bottom). The gray area in (a) shows the occupied states used to define the electron
count 0 ≤ n ≤ 2 in the bottom part of (b). The peaks in (b) are caused by degenerate Fermi-surface
crossing near k = π/a
Fig. 18 First-order anisotropy constant of a hexagonal nanoparticle: (a) structure and (b) tight-
binding anisotropy as a function of the number of d electrons (after Ref. 66)
namely, in the diatomic pair model [60, 61], where the situation is reminiscent of a
quarter-shell rule.
It is instructive to compare the contributions of the nonperturbative DFSC
anisotropy peaks with the perturbative volume anisotropy due to Eu – Eo ∼ W. The
latter corresponds to the nearly homogeneous background in the top of Fig. 17(b)
and to the constant slopes near n = 0 and n = 2 in the bottom of Fig. 17(b).
In systems where the peak contribution is strong, a very dense k-point mesh is
necessary, or else the numerical error gets very big. The relative contribution of
the peaks depends on both the order of the anisotropy and the dimensionality of
the magnet. In one-dimensional magnets, the bulk and peak contributions to K1 are
comparable, as one may guess from the bottom of Fig. 17(b). More generally, Eq.
(53) means that perturbative anisotropy contributions scale as Km = W(λ/W)2m .
The peak contributions have a strength of λ but are restricted to a small k-
space volume of (l/W)d , so the corresponding anisotropy contribution scales as
λ(λ/W)d = W(λ/W)d + 1 . The peak contributions are therefore strongest in low-
dimensional magnets. They are of equal importance for d = 2 m – 1, that is for K1 in
one-dimensional magnets and K2 (K1 c ) in three-dimensional magnets. The latter is
fundamentally important, because it includes the anisotropy of cubic magnets such
as Fe and Ni. The former is important from a practical viewpoint, because quasi-one-
dimensional reflection from lattice planes creates pronounced peaks in the density
of states [77, 78].
First-Principle Calculations
[92, 93]. In this approach, the energy differences between two magnetization
directions are approximated by the difference of band-energy sums along different
magnetization directions, which can be achieved by a one-step diagonalization of
the full Hamiltonian. A better approach is to use total energy calculations, where
the energy is self-consistently calculated for each spin direction.
A specific problem is Hund’s second rule, which states that intra-atomic
electron-electron exchange favors states with large orbital momentum. The effect
is parameterized by the Racah parameter B and, in itinerant magnets, is known as
orbital polarization [89, 94]. The relative importance of this intra-atomic exchange
effect is reduced by band formation, but anisotropy calculations require a very high
accuracy, so that the corresponding orbital polarization effect cannot be ignored in
general. A simple but fairly accurate approach is to add an orbital polarization term
–½BL2 to the Hamiltonian, where B is of the order of 100 meV [94]. This term
lowers the energies of |xy> and |x2 – y2 > orbitals and enhances those of |z2 > orbitals.
The example of orbital polarization shows that correlation effects are important
in the determination of the anisotropy. In a strict sense, correlation effects involve
two or more Slater determinants [17], but sometimes their definition includes
Hund’s rule correlations. The latter are of the one-electron or independent-electron
type in the sense of a single Hartree-Fock-type Slater determinant [23]. Density
functional theory is, in principle, able to describe anisotropy, because anisotropy is
a ground-state property for any given spin direction. However, very little is known
about the density functional beyond the comfort zone of the free electron-inspired
local spin density approximation [95], including gradient corrections. For example,
rare-earth anisotropy, which is largely determined by the crystal-field interaction
of 4f charge distribution, can be cast in form of a density functional [96], but
this functional looks very different from the LSDA functional and its gradient
extensions.
One approach to approximately treat correlations is LSDA+U, where a Coulomb
repulsion parameter is added to the density functional [97]. The parameter U or, in
a somewhat more accurate interpretation, U ∗ = U –J is well-defined in the sense
that it should not be used to adjust theoretical results to achieve an agreement
with the experiment. Treating U as an adjustable parameter yields substantial
errors, of the order of 1 MJ/m3 for Ni [98]. However, similar to Hund’s-rules
correlations and LSDA, the LSDA+U approximation does not go beyond a single
Stater determinant. For example, it does not specifically address many-electron
phenomena such as spin-charge separation. The merit of the approach consists in
replacing local or quasilocal LSDA-type density functionals by density functionals
that are somewhat less inadequate for highly correlated systems. In particular, U
suppresses charge fluctuations and thereby improves the accuracy of the energy
levels connected by spin-orbit matrix elements [84]. Calculations going beyond a
single Slater determinant are still in their infancy. An analytic model calculation has
yielded Kondo-like corrections to the anisotropy [96], and dynamical mean-field
theory (DMFT) is being used to investigate the effect of charge fluctuations beyond
one-electron LSDA+U [99].
156 R. Skomski et al.
Case Studies
anisotropy contributions from different orbitals and k-space regions is nearly zero. It
is also known that LSDA+U-type one-electron correlations are important in Ni. An
LSDA+U or “static DMFT” calculation was performed for Fe and Ni [84]. Values
of U* = 0.4 eV and U* = 0.7 eV have been advocated for Fe and Ni, respectively,
leading to anisotropy constants of 0.02 MJ/m3 for Fe (experiment: 0.05 MJ/m3 )
and − 0.04 MJ/m3 for Ni (experiment −0.005 MJ/m3 ). The Ni anisotropy is
overestimated, but the sign is correct, and a major reason for the correct sign is
the absence of a pocket near the X point of the fcc Brillouin zone. Without U, the
Fermi level cuts the pocket and spin-orbit matrix elements between occupied and
unoccupied states, similar to Fig. 17(a), creating an unphysical positive anisotropy
contribution.
YCo5 . The intermetallic compound YCo5 , which crystallizes in the hexagonal
CaCu5 structure, has the largest anisotropy among all know iron-series transition-
metal intermetallics, about 8 MJ/m3 at low temperature and 5 MJ/m3 at room
temperature [101]. Nearly all this anisotropy arises from the Co sublattices, in spite
of Y being a relatively heavy atom. According to Table 7, the spin-orbit coupling
of Y (32 meV) is not much smaller than that of Co (68 meV), but according to Eq.
(50), the effect of atomic SOC on the anisotropy scales is λ2 s2 , and the magnitude
of the Y spin is only about 0.3 μB , as compared to about 1.4 μB for Co [89]. In
other words, the anisotropy of YCo5 is about ten times greater than that of hcp Co,
in spite of the magnetically largely inert Y.
There are two reasons for the high anisotropy of YCo5 . First, the structure of
the YCo5 consists of alternating Co and Y-Co layers, in contrast to the nearly cubic
atomic environment in hcp Co. In this framework, the Y acts as a nonmagnetic
crystal-field source with a contribution similar to a vacuum. This has been shown in
a computer experiment [101] where the Y atoms were replaced by fictitious empty
interstices without any changes to the Co positions. The replacement reduces the
anisotropy by only 13%, which confirms that the anisotropy of YCo5 is largely due
to the anisotropic distribution of the Co atoms.
A secondary reason for the high anisotropy is that the electronic structure of
YCo5 supports a fairly strong orbital moment, about 0.2 μB per Co atom [93],
as compared to about 0.1 μB per atom in hcp Co [82]. The less quenched orbital
moment in YCo5 , which translates into enhanced anisotropy, partially reflects the
presence of degenerate |xy> and |x2 – y2 > states near the Fermi level [89]. According
to Eq. (54), the mixing of these states yields an orbital moment of up to 2 μB
per atom and a disproportionally strong anisotropy contribution (Fig. 17). More
importantly, the bands are very narrow near the Fermi level, which reduces the
denominator Eo – Eu in Eq. (50).
Iron, steel, and Fe nitride. Purified iron is magnetically very soft, but steel
formation due to the addition of carbon (Fe100–x Cx , x ≈ 4) drastically enhances
the coercivity [70, 102, 103]. The underlying physics is that carbon causes a
martensitic phase transition in bcc Fe, leading to a tetragonally distorted phase [70].
Figure 19 illustrates this mechanism, which is responsible for both the mechanical
and magnetic hardnesses of steel. The carbon occupies the octahedral interstitial
sites in the middle of the faces of the bcc unit cell (a). These octahedra are strongly
158 R. Skomski et al.
Fig. 19 Martensitic distortion of bcc Fe: (a) undistorted unit cell and (b) unit cell distorted
along the c-axis (dashed line). The martensitic distortion involves spontaneous symmetry breaking
along the a-, b-, or c-axis and extends over many interatomic distances, typically over several
micrometers
√
distorted: perpendicular to the faces, the Fe-Fe distance is smaller by a factor 2
than along the face diagonals. In a hard-sphere model based on an Fe radius of
1.24 Å, the radius of the interstitial site is 0.78 Å along the face diagonals but
only 0.19 Å perpendicular to the face. The atomic radius of C is about 0.77 Å
[103], so that the interstitial occupancy requires a strong tetragonal distortion. This
distortion breaks the cubic symmetry locally and, via elastic interactions between C
atoms on different interstitial sites, macroscopically. For example, 4 at% C yields an
enhancement of the c/a ratio by 3.5% [103]. Figure 19(b) shows the C occupancy
for a tetragonal distortion along the c-axis.
The martensitic lattice strain and the chemical effect due to the presence of the
carbon atoms yield almost equal uniaxial anisotropy contributions [102], and K1
is negative for Fe1-x Cx , of the order of −0.2 MJ/m3 . Cobalt addition changes the
sign of the volume magnetoelastic constant (Sect. “Magnetoelastic Anisotropy”)
and therefore the sign of the strain effect [70]. The magnetization is as high as
2.43 T in Fe65 Co35 , and the corresponding Honda steel [104] has a coercivity of
μo Hc = 0.020 T, as compared to 0.004 T for ordinary carbon steel. Such steels
dominated permanent-magnet technology in the early twentieth century and have
recently attracted renewed attention. Substantial anisotropy, K1 = 9.5 MJ/m3 , and a
magnetization of μo Ms = 1.9 T have been predicted for tetragonally distorted Fe-
Co with c/a = 1.23 [105], although such a strong distortion is virtually impossible
to sustain metallurgically. Experimental room-temperature anisotropies reach about
2.1 MJ/m3 [106] and require a large amount of Pt (about 75 vol.%).
The behavior of interstitial N in Fe is similar to that of C [107], but nitrogen has
the additional advantage of improving the magnetization in tetragonal superlattices
of Fe8 N, or Fe16 N2 [108]. It is well-established that α -Fe16 N2 has a very high
magnetization [109, 110], about 2.8 ± 0.4 T, but the precise value has been a
subject of debate. An LSDA+U prediction of the magnetization is 2.6 T, which
3 Anisotropy and Crystal Field 159
Magnetostatic Anisotropy
μo 3m · R m · R − m · m R 2
EMS = (58)
4π R5
μo
Ksh = 1 − 3 N M2 (60)
4
Fig. 21 Micromagnetic nature of shape anisotropy in a slightly prolate but defect-free ellipsoid.
Imperfections, including nonellipsoidal edges, cause reduced nucleation fields (coercivities), which
is known as Brown’s paradox
coupling, which is separately realized in each atom and described by Eq. (21).
The single-ion mechanism does not exclude interactions between spins, such as
exchange, but the net anisotropy of a magnet is obtained by adding all single-ion
contributions. Examples of two-ion anisotropies are the magnetostatic anisotropy,
just discussed and epitomized by Eq. (58), and Néel’s phenomenological pair-
interaction model [119]. The latter uses an expansion of the anisotropy energy in
direction cosines. In the lowest order, the pair energy is equal to L (cos2 ψ – 1/3),
where L is a phenomenological parameter and ψ is the angle between bond axis and
magnetization direction. Néel’s expression is reproduced by putting m = m’ in Eq.
(58), that is, by assuming a uniform magnetization direction.
Single-ion and Néel two-ion anisotropies yield anisotropy-energy expressions of
the correct symmetry, but this does not mean that they are physically equivalent. For
example, both magnetic and nonmagnetic atoms contribute to the crystal field acting
on rare-earth ions, but the latter make no contribution in the Néel model, because is
based on pairs of magnetic atoms. Nonmagnetic ligands yield big anisotropy effects
in some materials, such as Sm2 Fe17 interstitially modified by N or C [41, 120]. The
alloy crystallizes in the rhombohedral Th2 Zn17 structure, where each Sm atom is
coordinated by three 9e interstitial sites, as shown in Fig. 22(a). The anisotropy of
Sm2 Fe17 is easy plane, that is, the Sm moment lies in the x-y-plane plane, which
also contains the 9e triangle. Heating powders of Sm2 Fe17 in N2 gas (gas-phase
interstitial modification) causes the nitrogen atoms to occupy the 9e interstices,
yielding the approximate composition Sm2 Fe17 N3 . The nitrogen addition changes
the anisotropy from easy-plane (K1 = −0.8 MJ/m3 ) to easy-axis (K1 = 8.6 MJ/m3 ),
because the virtually nonmagnetic N atoms act as strongly negative crystal-field
charges and repel the tips of the 4f charge distribution, Fig. 22(b).
One- and two-ion anisotropies are difficult to distinguish experimentally, partly
because interatomic exchange keeps neighboring spins parallel. The tempera-
ture dependence of the anisotropy is sometimes used as a criterion, scaling as
K1 (T) ∼ Ms (T)2 for magnetostatic anisotropy. However, a very similar behavior
is observed in L10 magnets such as FePt and CoPt, where the anisotropy is of the
single-ion type but requires proximity spin polarization of the 5d electrons by the
3d electrons [51, 52].
H = –Jxx Ŝx · Ŝx –Jyy Ŝy · Ŝy –Jzz Ŝz · Ŝz (61)
Fig. 22 Anisotropy of
Sm2 Fe17 N3 : (a) interstitial
sites surrounding the Sm3+
ion in Sm2 Fe17 (blue) and (b)
change of the easy-axis
direction due to interstitial
nitrogen (yellow). Since this
anisotropy mechanism
involves one magnetic atom
only, it cannot be cast in form
of a Néel interaction
J 2
Ea = − 3Sz − S (S + 1) (62)
2
Dzyaloshinski-Moriya Interactions
orbit coupling, the DM interaction is derived from the Dirac equation and is of the
same order relativistically. Phenomenologically, the interaction favors noncollinear
spin states, because HDM = 0 if the spins Si and Sj are parallel. Micromagnetically,
the DM interactions can be expressed in terms of magnetization gradients ∇S and
then assume the form of Lifshitz invariants. The corresponding energy contributions
depend on the point group of the crystal or film and are zero even for some crystals
without inversion symmetry [136].
DM interactions occur in some crystalline materials, such as α-Fe2 O3
(haematite), in amorphous magnets, in spin glasses, and in magnetic nanostructures
[37, 135, 137]. The resulting canting is small, because D competes against the
dominant Heisenberg exchange J, but the canting is easily observed in hematite
and other canted antiferromagnets where there is no ferromagnetic background.
The micromagnetism of the DM interactions [138] and its competition with single-
ion anisotropy is important in the context of magnetic vortices, for example, in
MnSi [139]. The spin angles between neighboring atoms are comparable to angles
encountered in domain walls, of the order of 1◦ for material ordered at room
temperature, which reflects the common relativistic origin of both phenomena
(D in the DM interactions and K1 determining the domain-wall width). DM
noncollinearities are not be confused with noncollinearities caused by competing
Heisenberg exchange interactions.
Antiferromagnetic Anisotropy
Magnetoelastic Anisotropy
HME λs E E
=− 3 cos2 θ − 1 ε + ε2 − ε σ (64)
V 2 2
where σ is the uniaxial stress, ε = l/l denotes the elongation along the stress axis,
E is Young’s modulus, and θ is the angle between the magnetization and strain
axis. The strength of the magnetoelastic coupling is described by the saturation
magnetostriction λs .
Putting σ = 0 and θ = 0 and minimizing the magnetoelastic energy with respect
to ε yields the elongation ε = λs . A magnet which has a spherical shape in the
paramagnetic state becomes a prolate ferromagnet when λs > 0 but an oblate
ferromagnet when λs < 0. Physically, the spin alignment creates, via spin-orbit
coupling, an alignment of the atomic electron distributions and a change in lattice
parameters. Since λs is only 10–100 ppm in most ferromagnetic compounds, a
moderate stress σ = Eε can outweigh the spontaneous magnetostriction. This then
produces a magnetoelastic anisotropy energy density:
HME λs σ
=− 3 cos2 θ − 1 (65)
V 2
3 Anisotropy and Crystal Field 167
and the magnetoelastic contribution to K1 KME = 3λs σ /2, which may be fairly
large.
For cubic crystallites, there are two independent magnetostriction coefficients in
the lowest order, and the polycrystalline average over all possible orientations is
[141]
2 3
λs = λ100 + λ111 (66)
5 5
where the quantities λ100 and λ111 are the spontaneous magnetostriction along
the cube edge and the cube diagonal, respectively. Experimental room-temperature
values of λs , measured in parts per million (10−6 ), are −7 for Fe, −33 for Ni,
+75 for FeCo, +40 for Fe3 O4 , −1560 for SmFe2 , and + 1800 for TbFe2 , and
practically zero for Py (permalloy, Fe20 Ni80 ) [11, 70, 115]. For example, high-
carbon steel (Fe94 C6 ) has E = 200 GPa and is strained by about 5% [103], so that
KME ≈ −0.1 MJ/m3 (see the discussion of steel magnets in Sect. “Case Studies”).
Surface Anisotropy
Surface and interface anisotropies, which are closely related, play an important role
in magnetic thin films and nanostructures. Surface anisotropies easily dominate the
bulk anisotropy in nanostructures with cubic or amorphous crystal structures, but
surface and interface contributions are also of interest in noncubic systems. For
example, L10 -ordered magnets such as FePt and CoPt can be considered as naturally
occurring multilayers. In line with other 3d anisotropies, the sign and magnitude of
surface anisotropies are difficult to predict, but some crude rules of thumb exist for
168 R. Skomski et al.
Fig. 24 Anisotropic
nanostructures: (a) thin films
(L10 -FePt/MgO), (b)
free-standing Pd zigzag
nanowire, (c) monatomic Fe
nanowire on Pt(001), and (d)
Co adatom on an insulating
substrate. First-principle
calculations often use
periodic arrays of supercells
with sufficiently big
airgaps (a)
the anisotropy as a function of band filling [60, 61]. For example, anisotropy often
changes sign between Fe and Co, the Fe preferring an easy axis perpendicular to the
Fe-Fe bonds (perpendicular to the plane).
Surface anisotropy tends to dominate when the thin-film thickness is in the range
of a few atomic layers. Phenomenologically [88, 147]
K1 = KS /t + KV (67)
where t is the film thickness, KS is the surface anisotropy, and KV includes the bulk
magnetocrystalline and shape anisotropies. Typical iron-series surface anisotropies
are of the order of 0.1–1 mJ/m2 [147], or 0.03–0.3 meV per surface transition-
metal atom, which corresponds to bulk equivalents of 0.5–5 MJ/m3 . When KV and
KS favor in-plane and perpendicular anisotropy, respectively, then there is a spin-
reorientation transition from perpendicular to in-plane as the thickness exceeds
KS /|KV |. Note that Eq. (67) does not mean that the anisotropy is limited to the
surface: the equation is asymptotic, with small contributions from subsurface atoms
and from atoms deeper in the bulk.
Thin-film, multilayer, surface, and interface anisotropies have the same physical
origin as bulk anisotropies, mostly single-ion anisotropy with magnetostatic correc-
3 Anisotropy and Crystal Field 169
tions. The anisotropic distribution of exchange bonds at the surface does not create
magnetic anisotropy. The Heisenberg Hamiltonian is isotropic, even if the exchange
bonds Jij = J(ri – rj ) are anisotropic. Only relative angles between neighboring spins
matter, and the Heisenberg model is silent about the easy magnetization directions.
Both the easy axes and the strength of the anisotropy depend on the index of the
surface, and there is no reason to expect that the anisotropy axis should necessarily
be normal to the surface. For example, the (100) surface of bcc Fe, Fig. 25(a), has
fourfold in-plane symmetry and yields a fourth-order anisotropy contribution. By
comparison, the (011) surface, Fig. 25(b), has a twofold in-plane symmetry, which
yields two nonzero lowest-order anisotropy constants , K1 and K1 [148]. Surface
defects often yield substantial anisotropy contributions [88, 144]. Stepped surfaces
are an example, which can also be considered as high-index surfaces [144, 149].
Many magnetic materials are characterized by random easy axes n(r), so that the
uniaxial anisotropy-energy expression K1 sin2 θ must be replaced by
Ha = – K1 (n · s)2 dV (68)
where s = M(r)/Ms . Atomically, K1 in Eq. (68) is the same as the K1 in Sect. “Low-
est-Order Anisotropies”, the only difference being the randomness of the local
c-axis. Random anisotropy is important in a variety of materials, including hard
and soft-magnetic polycrystalline solids [150–155], amorphous magnets [124, 137,
156], spin glasses [135], and nanoparticles [143, 157]. One example is the approach
to saturation in polycrystalline materials (Sect. “Anisotropy Measurements”).
Nanoparticles and nanoclusters are defined very similarly, but in a strict sense,
the former are random objects, whereas the latter are characterized by well-defined
atomic positions. Typical nanoparticles contain surface patches with many different
indexes, and the corresponding anisotropy contributions add.
The net anisotropy of nanoparticles is generally biaxial, involving both K1 and
K1 , and there is generally no physical justification for considering nanoparticles as
170 R. Skomski et al.
uniaxial magnets. This can be seen from Eq. (3): aside from accidental degeneracies,
there is always one axis of lowest energy. However, uniaxiality goes beyond
having an axis of lowest energy (easy axis), because it also requires the absence
of “secondary” anisotropy axes perpendicular to the easy axis. The secondary
anisotropy is important, because it causes hysteresis loops to deviate from the
uniaxial predictions.
Consider a nanoparticle with a highly disordered surface, so that each of the
NS surface atoms yields an anisotropy contribution ±Ko , where Ko is 0.03–0.3 meV
(Sect. “Surface Anisotropy”) and ± refers to orthogonal easy axes. For NS = ∞, the
surface anisotropy would average to zero, but in patches of finite NS , the averaging
is incomplete. The addition of NS random contributions √ ±Ko creates a Gaussian
distribution√of net anisotropies of the order of ±Ko / NS per surface atom [9], or
Keff = Ko NS /N averaged over all N atoms in the particle. Here the negative sign
means that the easiest axis switches into a direction perpendicular to the reference
axis (z-axis). Since Ns ∼ R2 and N ∼ R3 , Keff scales as 1/R.
Atomic-scale random-anisotropy effects in bulk solids were first discussed in
the context of amorphous magnets, which exhibit random-field [158], random-
anisotropy [159], and random-exchange spin glasses [135, 137]. In less than four
dimensions, the ground state of random-anisotropy magnets does not exhibit long-
range ferromagnetic order [135]. However, this does not preclude the use of
random-anisotropy magnets as nanostructured magnetic materials, where hysteretic
properties are important [155, 160] and true equilibrium is rarely reached. The
coercivity and remanence of atomic-scale random-anisotropy magnets were first
investigated in the late 1970s [151, 156], but a very similar situation is encountered
in nanocrystalline magnets [161, 162].
The random anisotropy in Eq. (68) creates magnetic hysteresis. In the case
of noninteracting random-anisotropy grains, which also includes noninteracting
nanoparticles,
the M(H) loops are obtained by adding the Zeeman interaction –μo
Ms H·s dV to Eq. (68), finding the M(H) loop for each direction n, and then
averaging over all n. In terms of Ha = 2 K1 /μo Ms , the behavior near remanence is
M(H) = Ms (1/2 + 2H/3Ha ). In particular, the remanence ratio Mr /Ms = M(0)/Ms
is equal to 1/2. Performing the same analysis for cubic magnets with iron-type
(K1 > 0) and nickel-type (K1 < 0) anisotropy yields the remanence ratios 0.832 and
0.866, respectively. Replacing the easy-axis anisotropy by easy-plane anisotropy
yields a very similar curve for H > 0, namely, M(H) = Ms (π/4 + H/3Ha ), and
the same asymptotic behavior (Sect. “Anisotropy Measurements”). However, the
coercive behavior is very different: random easy-axis anisotropy yields Hc = 0.479
Ha , whereas easy-plane anisotropy leads to Hc = 0.
Intergranular exchange modifies the hysteresis loops, creating some coercivity
in the easy-plane ensembles but reducing the coercivity in the case of easy-
axis anisotropy. The exchange energy density, A(∇σ m )2 , is largest for rapidly
varying magnetization directions σ m , so that exchange effects are most pronounced
grain with small radius R. In the weak-coupling limit, A/R2 K1 , there are
quantitative corrections to the hysteresis loop [9], but the strong-coupling behavior
is qualitatively different.
3 Anisotropy and Crystal Field 171
A 1
η= 2
− K1 √ (69)
L N
where L is the magnetic correlation length, that is, the radius of the correlated
regions. In d dimensions, it is given by N = (L/R)d . Putting this expression into
Eq. (69) and minimization with respect to L yields the scaling relation
Very high anisotropies per atom are possible in small-scale nanostructures such
as adatoms on surfaces or monatomic wires. These high anisotropies indicate
unquenched orbital moments , due to either high spin-orbit coupling or high crystal-
field symmetry. The former is realized for Co atoms on Pt(111) [163], where
a giant magnetic anisotropy of about 9 meV per Co atom has been measured.
Platinum is predisposed toward strong anisotropy, because it is close to the onset
of ferromagnetism and possesses a spin-orbit coupling of about 550 meV. A single
atom of Fe or Co easily spin-polarizes several Pt atoms, which then make large
contributions to the anisotropy. Atomically thin nanowires, such as the zigzag wire
172 R. Skomski et al.
in Fig. 24(b), may support very high anisotropy, partly due to pronounced van-Hove
peaks in the density of states. In terms of Eq. (53), van-Hove singularities near
the Fermi level correspond to small energy differences Eu – Eo . For example, an
anisotropy of 5.36 meV per atom has been predicted for free-standing ladders of Pd
atoms [164].
An upper limit to the anisotropy per atom is given by the spin-orbit coupling
constant, λ ≈ 50 meV for the late iron-series transition metals. This huge value
corresponds to 140 MJ/m3 for dense-packed atoms. It is unlikely that this anisotropy
could be exploited in nanotechnology, because anisotropy is defined as anisotropy
energy per unit volume and the requirement of isolated or freestanding wires leads to
a dilution of the anisotropy. Densification is incompatible with such huge anisotropy,
because crystal formation involves interactions of the order 1000 meV, which tend
to quench the orbital moment.
Quenching is ineffective in free-standing monatomic nanowire however, and
anisotropy energies of 20–60 meV have been predicted or experimentally inferred
for these structures. In 3d systems, anisotropies as high 6–20 meV/atom have been
calculated for free-standing linear monatomic Co wires [165]. Some monatomic
4d and 5d wires exhibit larger anisotropies, up to 60 meV per atom in stretched
Rh and Pd, respectively [166]. The high anisotropy of freestanding monatomic
nanowires indicates that some levels undergo little or no quenching. The wires
have C∞ symmetry, which leaves the states with nonzero Lz , namely, |xz> and
|yz> (Lz = ± 1) and |xy> and |x– y2 > (Lz = ± 2), completely unquenched so long
as the spin is parallel to the symmetry axis of the wire (z-axis). Figure 26 compares
the corresponding level splitting with the tetragonal one in Fig. 6. Physically, the
electrons freely orbit around the wires, because there are no in-plane crystal-field
charges that could perturb this motion. The corresponding wave functions, |xz > ± i
|yz > and |xy > ± i |x– y2 >, yield anisotropy energies of up to λ and 2λ, respectively,
depending on the number of electrons in the system.
Configurations similar to Fig. 6 also exist in a few crystalline environments.
Recent experiments have indicated that a Co ad-atom deposited on MgO shows
the giant magnetic anisotropy of 58 meV [167]. This huge anisotropy requires a
degeneracy between two levels of equal |Lz |. Co adatoms on MgO(001) have C4
symmetry. Due to Hund’s rules, the Co2+ ion (3d7 ) has one electron in the xy-xz
doublet, and this degeneracy yields a large orbital moment, <Lz > ≈ 1, and a huge
anisotropy.
The example of Co on MgO shows high anisotropy energies can also be obtained
in some crystalline environments. The C4 argument can be extended to vertically
embedded but laterally isolated wires. Such configurations might conceivably be
used for magnetic recording. In terms of thermal stability, 50 meV corresponds to
580 K, or about 2kB T per atom. For magnetic recording, one would need about 50
kB T, or chain lengths of 25 strongly exchange-coupled 3d atoms. Heavier elements
have stronger spin-orbit couplings but cannot be used for this purpose, because
3 Anisotropy and Crystal Field 173
Fig. 26 Crystal-field
splitting in an insulating
free-standing nanowire. Since
states with the same quantum
number |Lz | > 0 form
degenerate states (doublets),
there is no quenching, and
large magnetocrystalline
anisotropies K1 Vo ∼ λ are
possible
Acknowledgments This chapter has benefited from discussions with B. Balamurugan, C. Binek,
R. Choudhary, J. Cui, P. A. Dowben, A. Enders, O. Gutfleisch, G. C. Hadjipanayis, H. Herper,
X. Hong, S. S. Jaswal, P. Kharel, M. J. Kramer, P. Kumar, A. Laraoui, L. H. Lewis, S.-H. Liou,
J.-P. Liu, R. W. McCallum, O. N. Mryasov, D. Paudyal, R. Sabirianov, S. S. Sankar, T. Schrefl,
D. J. Sellmyer, J. E. Shield, A. K. Solanki, and A. Ullah. The underlying work was or has been
supported by ARO (W911NF-10-2-0099), DOE (DE-FG02-04ER46152), NSF EQUATE (OIA-
2044049), partially NSF-DMREF (1729288), HCC, and NCMN.
174 R. Skomski et al.
Appendices
m
Yl m (θ, φ) = Nl exp (imφ) Pl m (cos θ ) (72)
where the Pl m are the the associated Legendre polynomials. Concerning sign and
magnitude of the normalization factor N l m , we use the convention
(2l + 1) (l − m)!
Nl m = (73)
4π (l + m)!
1 5
Y2 0 = 3 cos2 θ –1 (74a)
2 4π
or
1 5 3z2 − r 2
Y2 0
= (74b)
2 4π r2
Note that the Cartesian coordinates require a factor 1/rl , which ensures that the
m
Yl are dimensionless and that the expansion is in terms of direction cosines x/r,
y/r, and z/r. Up to the sixth order, there are Table 16 lists real and complex spherical
harmonics up to the sixth order.
3 Anisotropy and Crystal Field 175
Table A.16 Spherical harmonics √ in several representations. For m = 0, the real representation
requires an additional factor 1/ 2, because the normalization behavior of cos(mφ) ± sin(mφ)
differs from that of exp.(imφ). Furthermore, the minus sign in N l m is not used for m = 0.
The following formulae can be used to extract the full spherical harmonics from the table:
Yl m = π-1/2 fN fP exp.(imφ), Yl m = π-1/2 fN fR /rl (m = 0), and Yl m = (2π)-1/2 fN fR /rl (m = 0).
Anisotropy energies involve even-order spherical harmonics only (gray rows)
Y6 3 – 1/32 · 1365
3 3
sin T cos T – 3 cosT xz (x2 – 3 y2)(11 z2 – 3 r2)
Y6 2 1/64 · 1365 sin2T 33 cos4T – 18 cos2T + 1) (x2 – y2)(33 z4 – 18 z2r2 + r4)
Y6 1 5
– 1/16 · 273/2 sinT (33 cos T – 70 cos T + 5 cosT )
3
xz (33 z4 – 30 z2r2 + 5 r4)
Y6 0 1/32 · 13 231 cos 6
T – 315 cos 4
T + 105 cos2
T – 5 231 z6 – 315 z4r2 + 105 z2r2 – 5 r6
Y6 – 1 1/16 · 273/2
5
sinT (33 cos T – 70 cos T + 5 cosT )3
yz (33z4 – 30z2r2 + 5r4)
Y6 – 2 1/64 · 1365
2 4
sin T 33 cos T – 18 cos T + 1) 2
2 xy (33 z4 – 18 z2r2 + r4)
Y6 – 3 1/32 · 1365 sin3T cos3T – 3 cosT 3 yz (3 x2 – y2)(11 z2 – 3r2)
Y6 – 4 3/32 · 91/2 sin4T cos2T – 1 4 xy (x2 – y2)(11 z2 – r2)
Y6 – 5 3/32 · 1001 sin5T cosT zy (5 x4 – 10 x2y2 + y4)
Y6 – 6 1/64 · 3003 sin T 6
xy (6 x4 – 20 x2y2 – 6 y4)
176 R. Skomski et al.
Table A.17 Less common space and point groups. The space groups in bold characters are
frequently encountered in magnetism and separately considered in the main text of the chapter
(Table 1)
Crystal system Point group Space group
Triclinic C1 (1) P1
Triclinic Ci (1) P1
Monoclinic C2 (2) P2, P21 , C2
Monoclinic Cs (m) Pm, Pc, Cm, Cc
Monoclinic C2h (2/m) C2/m, C2/c, P2/m, P21 /m, P2/c, P21 /c
Orthorhombic D2 (222) P222, P2221 , P21 21 2, P21 21 21 , C2221 , C222, F222, I222,
I21 21 21
Orthorhombic C2v (mm2) Pmm2, Pmc21 , Pcc2, Pma2, Pca21 , Pnc2, Pmn21 , Pba2,
Pna21 , Pnn2, Cmm2, Cmc21 , Ccc2, Amm2, Aem2, Ama2,
Aea2, Fmm2, Fdd2, Imm2, Iba2, Ima2
Orthorhombic D2h (mmm) Pnma, Pmmm, Pnnn, Pccm, Pban, Pmma, Pnna, Pmna,
Pcca, Pbam, Pccn, Pbcm, Pnnm, Pmmn, Pbcn, Pbca, Cmcm,
Cmce, Cmmm, Cccm, Cmme, Ccce, Fmmm, Fddd, Immm,
Ibam, Ibca, Imma
Tetragonal C4 (4) P4, P41 , P42 , P43 , I4, I41
Tetragonal S4 (4) P4, I4
Tetragonal C4h (4/m) P4/m, P42 /m, P4/n, P42 /n, I4/m, I41 /a
Tetragonal D4 (422) P422, P421 2, P41 22, P41 21 2, P42 22, P42 21 2, P43 22,
P43 21 2, I422, I41 22
Tetragonal C4v (4 mm) P4mm, P4bm, P42 cm, P42 nm, P4cc, P4nc, P42 mc, P42 bc,
I4mm, I4cm, I41 md, I41 cd
Tetragonal D2d (42m) P42m, P42c, P421 m, P421 c, P4m2, P4c2, P4b2, P4n2, I4m2,
I4c2, I42m, I42d
Tetragonal D4h (4/mmm) P4/mmm, P42 /mnm, I4/mmm, P4/mcc, P4/nbm, P4/nnc,
P4/mbm, P4/mnc, P4/nmm, P4/ncc, P42 /mmc, P42 /mcm,
P42 /nbc, P42 /nnm, P42 /mbc, P42 /nmc, P42 /ncm, I4/mcm,
I41 /amd, I41 /acd
Trigonal C3 (3) P3, P31 , P32 , R3
Trigonal S6 (3) P3, R3
Trigonal D3 (32) P32 12, P312, P321, P31 12, P31 21, P32 21, R32
Trigonal C3v (3 m) P3m1, P31m, P3c1, P31c, R3m, R3c
Trigonal D3d (3m) R3m, R3c, P31m, P31c, P3m1, P3c1
Hexagonal C6 (6) P6, P61 , P65 , P62 , P64 , P63
Hexagonal C3h (6) P6
Hexagonal C6h (6/m) P63 /mmc, P6/m, P63 /m
Hexagonal D6 (622) P622, P61 22, P65 22, P62 22, P64 22, P63 22
Hexagonal C6v (6 mm) P63 mc, P6mm, P6cc, P63 cm
Hexagonal D3h (6m2) P6m2, P6c2, P62m, P62c
Hexagonal D6h (6/mmm) P6/mcc, P63 /mcm
Cubic T (23) P21 3, P23, F23, I23, I21 3
(continued)
3 Anisotropy and Crystal Field 177
|z2 > = R3d (r) 3 sin2 θ − 1 (78)
√
where N = 15/16π, ao = 0.529 Å, and
4Z 5/2 r 2 Zr
R3d (r) = exp − (80)
81ao2 30ao3 ao
Aside from the real set of wave functions, there exist complex wave functions of
the type exp.(±imφ). The two sets of wave functions are linear combinations of
each other, and both are solutions of the Schrödinger equation. However, they are
nonequivalent with respect to orbital moment and magnetic anisotropy.
More generally, Ψ (r, φ, θ ) = Rn l (r) Yl m (φ, θ ), where it is convenient to express
the radial wave functions in terms of the parameter ro = ao /Z:
2 r
R1s = exp −
ro 3 ro
178 R. Skomski et al.
1 r r
R2s = 2− exp −
2 2ro 3 ro 2ro
1 r r
R2p = exp −
2 6ro 3 ro 2ro
2 r r2 r
R3s = 27 − 18 + 2 2 exp −
81 3ro 3 ro ro 3ro
4 r r2 r
R3p = 6 − 2 exp −
81 6ro 3 ro ro 3ro
4 r2 r
R3d = exp −
81 30ro 3 ro 2 3ro
1 r3 r
R4f = exp −
768 35ro 3 ro 3 4ro
From the radial wave functions, the following averages are obtained:
n2 ro 2 2
<r 2 > = 5n + 1 − 3l (l + 1)
2
ro 2
<r> = 3 n − l (l + 1)
2
1
<1/r> =
n2 r o
2
<1/r 2 > =
n3 ro 2 (2l + 1)
2
<1/r 3 > =
n3 ro 3 l (l + 1) (l + 2)
3 Anisotropy and Crystal Field 179
These formulae have numerous applications. For example, <r> and the square
root of <r2 > are used to estimate shell radii, <1/r> gives the electronic energy,
and <1/r3 > determines the strength of the spin-orbit coupling on which magne-
tocrystalline anisotropy relies.
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Electronic Structure: Metals and Insulators
4
Hubert Ebert, Sergiy Mankovsky , and Sebastian Wimmer
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
Electronic Structure Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
Spin Density Functional Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
Band Structure Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Relativistic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
Adiabatic Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
Itinerant Magnetism of Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
Stoner Model of Itinerant Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
Slater-Pauling Curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
Heusler Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
Total Electronic Energy and Magnetic Configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
Total Electronic Energy and Magnetic Ground State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
Exchange Coupling Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
Magneto-Crystalline Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
Excitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
Magnon Dispersion Relations Based on the Rigid Spin Approximation . . . . . . . . . . . . . . . 231
Spin Spiral Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
Excitation Spectra Based on the Dynamical Susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . 237
Finite-Temperature Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
Methods Relying on the Rigid Spin Approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
Methods Accounting for Longitudinal Spin Fluctuations . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
Coherent Treatment of Electronic Structure and Spin Statistics . . . . . . . . . . . . . . . . . . . . . . 244
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
Abstract
This chapter gives an overview on the various methods used to deal with
the electronic properties of magnetic solids. This covers the treatment of
noncollinear magnetism, structural and spin disorder, as well as relativistic and
many-body effects. An introduction to the Stoner theory for itinerant or band
magnetism is followed by a number of examples with an emphasis on transition
metal-based systems. The direct connection of the total electronic energy in the
ground state and its magnetic configuration is considered next. This includes
mapping the dependence of the energy on the spin configuration on a simplified
spin Hamiltonian as provided, for example, by the Heisenberg model. Another
important issue in this context is magnetic anisotropy. As it is shown, considering
excitations from a suitable reference state provides a powerful tool to search
for stable phases, while calculating the wave vector- and frequency-dependent
susceptibility gives a sound basis to understand the dynamical properties of
magnetic solids. Finally, magnetism at finite temperature is dealt with starting
from a pure classical treatment of the problem and ending with schemes that deal
with quantum mechanics and statistics in a coherent way.
Introduction
Theory and modeling always played an important role for the understanding and
development of magnetism [1, 2, 3, 4]. An early example for this is the presence of
ring currents suggested by Ampère to explain the properties of permanent magnetic
materials. Another example is the introduction of the molecular field by Weiss when
discussing magnetism at finite temperature. Another important milestone in the the-
ory of magnetism is the Bohr-van Leeuwen theorem [3] that unambiguously made
clear that magnetism is a quantum mechanical phenomenon and for that reason
requires a corresponding description. In line with this, Heisenberg’s investigation on
the relation between the energy and the spin configuration clearly demonstrated that
spontaneous spin-magnetic ordering is connected with the exchange interaction and
is not due to the much weaker dipole-dipole interaction. Interestingly, the existence
of the electronic spin follows directly from the Dirac equation that is the proper
relativistic counterpart of Schrödinger’s equation [5]. Another important direct
consequence of Dirac’s equation is the presence of spin-orbit coupling [5] that
gives rise to many technologically important phenomena as the magnetocrystalline
anisotropy, magnetostriction [6, 7], anomalous Hall [8], and magneto-optical Kerr-
effect [9]. Although these phenomena were discovered already in the nineteenth
century, a proper explanation could be given only much later on the basis of quantum
mechanics. Spin-orbit coupling is also the origin of many other important new
effects that are exploited in the field of spintronics as, for example, the spin Hall
effect [10] and spin-orbit torque [11]. In addition, one has to mention the spin-orbit-
induced anisotropy in the magnetic exchange interaction. Apart from adding to the
magnetocrystalline anisotropy, this includes the so-called Dzyaloshinskii-Moriya
4 Electronic Structure: Metals and Insulators 189
Dealing with the electronic structure of magnetic solids requires to account for
exchange and correlation and to solve the resulting electronic structure problem.
Spin density functional theory provides a powerful and flexible platform to tackle
the first issue while still allowing for extensions aiming at an improved treatment
of correlation effects. Concerning the second issue, there are many band structure
schemes now available that provide the necessary accuracy. In particular, they allow
dealing with two important aspects that are often of crucial importance for magnetic
properties, namely, disorder and relativistic effects.
1. The total ground state energy E of any many-body system is a functional of the
density n(r)
E[n] = F [n] + d 3 r n(r) Vext (r), (1)
where Vext (r) is an arbitrary external potential, in general the Coulomb potential
of the nuclei, and F [n] itself is a functional of the density n(r) but does not
depend on Vext (r).
2. For any many-electron system, the functional E[n] for the total energy has a
minimum equal to the ground-state energy E0 = E[n0 ] at the ground-state
density n0 (r).
Applying the variational principle to the minimal property of the energy functional
Kohn and Sham [22] derived Schrödinger-like single-particle equations whose
solution allows calculating any property of the system. For this purpose, the
functional F [n] is split into three parts:
n(r) n(r )
F [n] = T [n] + 3
d r d 3r + Exc [n], (2)
|r − r |
with the two first terms representing the kinetic and Coulomb or Hartree energy
of the electrons. The last term is a universal functional Exc [n] that represents all
4 Electronic Structure: Metals and Insulators 191
Here φiσ (r) and iσ are the wave function and energy of the single-particle state i
with spin character σ (up or down). While these quantities have a priori no physical
meaning, they can nevertheless be used to determine the central properties of the
system. This applies in particular for the spin densities
Nσ
nσ (r) = |φiσ (r)|2 , (4)
i=1
as the basic variables of the system. In Eq. (4), the summation runs over all Nσ states
with their energy iσ below the Fermi energy EF that in turn is determined by the
requirement
N= d 3 r n↑ (r) + n↓ (r) , (5)
a functional of the spin densities takes a minimum. This leads finally to the
expression:
n(r )
Vσeff (r) = Vσext (r) + 2 d 3r + Vσxc (r), (8)
|r − r |
with
δExc [n↑ , n↓ ]
Vσxc (r) = . (9)
δnσ (r)
Equations (3), (8), and (9) constitute the coupled Kohn-Sham equations that
obviously have to be solved self-consistently. With this accomplished, the total
energy of the system can be obtained from:
Nσ
n(r) n(r )
E[n↑ , n↓ ] = iσ − d 3r d 3r
|r − r |
σ =↑,↓ i=1
− d 3 r Vσxc (r) nσ (r) + Exc [n↑ , n↓ ]. (10)
σ =↑,↓
When the impact of spin-orbit coupling is included into the formalism (see
section “Relativistic Effects”), the corresponding expression for E[n↑ , n↓ ] is very
convenient for investigations on the magnetic anisotropy. In this case, one can in
general neglect the change of nσ (r) with the orientation of the magnetization, and
one has to consider only the first term in Eq. (10) representing the single-particle
energies of the system.
The collinear formulation given above is adequate for most situations. In case of
noncollinear magnetic configurations with the orientation of the spin magnetization
changing with position, one has in principle to use the spin-matrix formulation
of SDFT [23]. This implies that the wave functions φiσ (r) in Eq. (3) have to be
replaced by spinors φi (r), i.e., two component wave functions, that in general will
have no pure spin character. However, very often one can still assume a uniform
orientation of the magnetization within an atomic cell. In this case the potential is
also spin-diagonal in a local frame of reference with the spin-quantization axis along
the orientation m̂ of the local spin moment m. Accordingly, one can represent the
spin-dependent part of the effective 2 × 2 potential matrix function by:
where σ is the vector of 2 × 2 Pauli spin matrices [5] and the effective field
B(r) = (V ↑ (r) − V ↓ (r))/2 is given by the difference of the spin-up and spin-down
potentials in the local frame. Alternatively, the spin-diagonal potential in the local
frame may be related to the 2 × 2 potential matrix function in the global frame by
4 Electronic Structure: Metals and Insulators 193
Here (n↑ (r), n↓ (r)) is the exchange-correlation energy per electron for the
homogeneous free electron gas with uniform spin densities n↑ (r) and n↓ (r) that can
be determined with high accuracy [25]. A fit to numerical results for (n↑ (r), n↓ (r))
allows giving explicit expressions for the corresponding spin-dependent exchange-
correlation potential Vσxc (r) = Vσxc [n↑ (r), n↓ (r)].
As an example for a spin-polarized solid, Fig. 1 gives the band structure or
dispersion relation Ej kσ and the density of states (DOS) nσ (E) of bcc-Fe as cal-
culated within LSDA (see section “Band Structure Methods”). These curves clearly
show the exchange splitting due to the spin dependency of the exchange-correlation
potential when compared with results for the corresponding paramagnetic state.
Integrating nσ (E) up to the Fermi energy EF obviously gives the number of
electrons Nσ with spin character σ . The corresponding spin-magnetic moment
M = N↑ − N↓ is given in Table 1 for bcc-Fe, fcc-Ni, and hcp-Co [27]. Obviously,
2 2
0 0
Ejkσ (eV)
-2 -2
E (eV)
-4 -4
-6 -6
-8 -8
Γ Δ X 3 2 1 0 1 2 3
wave vector k n↓(E) (sts./eV) n↑(E) (sts./eV)
Fig. 1 Dispersion relation Ej kσ (left) and density of states nσ (E) (right) of ferromagnetic bcc-Fe
as calculated within LSDA. Results for the majority (↑) and minority (↓) spin states are given in
red and blue, respectively. In addition, results for the corresponding paramagnetic state are given
in black [26]
194 H. Ebert et al.
Table 1 Spin-magnetic moment of bcc-Fe, fcc-Ni, and hcp-Co calculated on the basis of the
LSDA and the GGA, compared with experimental values. The calculated magnetic moments given
in the last two columns have been obtained for the theoretical equilibrium and experimental lattice
parameter, respectively. (All data taken from [27])
Magnetic moment (μB )
Wigner-Seitz- Bulk modulus Cohesive energy
radius (a.u.) (Mbar) (eV) (atheo ) (aexpt )
Fe LSDA 2.59 2.64 7.32 2.08 2.14
GGA 2.68 1.74 6.31 2.20 2.17
Expt. 2.67 1.68 4.28 – 2.22
Co LSDA 2.54 2.68 5.98 1.50 1.62
GGA 2.63 2.14 4.52 1.63 1.63
Expt. 2.62 1.91 4.39 – 1.72
Ni LSDA 2.53 2.50 5.45 0.59 0.61
GGA 2.63 2.08 4.18 0.65 0.63
Expt. 2.60 2.86 4.44 – 0.61
the results depend to some extent on the chosen functional for Vσxc (r) (LSDA or
GGA) and the lattice parameter. Nevertheless, the calculated moments are in fairly
good agreement with experiment.
Although LSDA turned out to be astonishingly successful for many situations,
it nevertheless shows severe limitations. For example, LSDA leads in general to an
over-binding as can be seen from the Wigner-Seitz radius given in Table 1 that is too
small when compared to experiment. Furthermore, calculations on ferromagnetic Fe
led to a lower total energy for the fcc instead of the bcc structure (see section “Total
Electronic Energy and Magnetic Ground State”). These deficits could be removed
when the generalized gradient approximation (GGA) was introduced that expresses
ExcGGA [n , n ] not only in terms of the spin densities n (r) but also of their
↑ ↓ σ
gradients ∇nσ (r). A more systematic route to derive accurate exchange-correlation
energies and corresponding potentials is supplied by the optimized potential method
that leads to a functional expressed in terms of the Kohn-Sham orbitals [15].
Unfortunately, this approach is numerically much more demanding than the very
efficient LSDA or GGA schemes in particular when a reliable representation of
correlation is incorporated. Accordingly, the development of parametrizations for
the exchange-correlation potential that are at the same time efficient and sufficiently
accurate is a field of ongoing research.
A major problem of LSDA and comparable SDFT schemes is the accurate
treatment of correlation effects in case of moderate or strong correlations as they
occur in systems with narrow energy bands. A way to cure this problem is the
use of the GW method [28] that is applicable to moderately correlated systems.
Application to Ni, for example, showed in particular a narrowing of the d-band
when compared to LSDA-based results [29] as expected from photoemission [30].
A scheme that is applicable also to strongly correlated materials at a much lower
4 Electronic Structure: Metals and Insulators 195
numerical cost is the LDA+U [31] that accounts for static correlations by adding
corrections to the LDA or LSDA Hamiltonian that depend on the Hubbard Coulomb
parameter U . In case that U is much larger than the band width W , a situation
typically met in oxides, the correction term leads in particular to a splitting into
an upper and lower Hubbard band. Dynamical correlations, on the other hand, are
accounted for by the dynamical mean field theory (DMFT) that when merged with
the LSDA leads to the combined Hamiltonian [32, 33]:
1 σσ
H = HLSDA + Umm n̂ilmσ n̂ilm σ
2
il mσ m σ
1 † †
− Jmm ĉilmσ ĉilm σ̄ ĉilm σ̄ ĉilmσ
2
il mσ m
− Δl n̂ilmσ . (13)
il mσ i=id ,l=d
Here, ĉ, ĉ† , and n̂ are creation, annihilation, and particle density operators that refer
to atomic orbitals labeled by the quantum numbers l, m, and σ and site index i, with
σ σ and J
Umm mm corresponding to Coulomb and exchange integrals, respectively.
The quantity Δl represents the so-called double counting term that takes care that
static correlations are not accounted for twice – by the LSDA Hamiltonian HLSDA
and by its complementary DMFT counterpart HDMFT . As Eq. (13) indicates, the
DMFT correction is usually restricted to the correlated subsystem of the system as,
for example, d-states in case of transition metals (i = id , l = d). Furthermore,
the Coulomb and exchange integrals are assumed to be site diagonal (single-
site approximation) leading for the many-body problem to the same situation as
for the Anderson impurity model (AIM). Accordingly, all the various many-body
techniques available to deal with the AIM can also be used when dealing with
the combined LSDA+DMFT Hamiltonian. In most cases, Eq. (13) is dealt with
by calculating in a first step the one-electron Green function (see section “Band
Structure Methods”) associated with HLSDA . In a next step, the single-site problem
is solved by a so-called impurity solver that allows representing the impact of
HDMFT in terms of a corresponding complex and energy-dependent self-energy
ΣDMFT (E). Finally, making use of the Dyson equation (see Eq. (21) below), the
one-electron Green function of the system is updated.
Figure 2 shows typical results for the spin-dependent self-energy ΣDMFT (E) of
ferromagnetic Ni. The characteristics of these curves lead to the various correlation-
induced features expected from photoemission [30]: the real part gives rise to a
renormalization of the energy bands leading to band narrowing, reduction of the
exchange splitting, and the occurrence of a satellite structure at 6 eV binding energy.
The imaginary part, on the other hand, implies a finite lifetime of the electronic state
that increases for the d-states with distance from the Fermi energy. This is reflected
in the DOS curves by a smearing-out of its structure when compared to the LSDA
result.
196 H. Ebert et al.
Fig. 2 Left: real (red) and imaginary (blue) parts of the spin-resolved self-energy ΣDMFT (E)
of ferromagnetic Ni. Right: corresponding DOS obtained on the basis of plain LSDA and
LSDA+DMFT [26]
Most methods for calculating the electronic structure of solids on the basis of the
Kohn-Sham equation (3) assume three-dimensional periodicity for the potential
Vσeff (r). This implies that the corresponding solutions ψj k (r) are Bloch states that
transform under a lattice translation as:
and accordingly can be labeled by the wave vector k and an additional band index
j . A direct consequence of this is that Bloch states for different wave vectors k
are orthogonal. This property simplifies the solution of the band structure problem
tremendously when using the variational principle to solve Eq. (3) and transforming
that way the problem to solving an algebraic eigenvalue problem. Constructing in
this case the basis functions such that they obey Eq. (14), one is led to a secular
equation with finite dimension for each k-vector
H k − Ej k S k α j k = 0 (15)
with the Hamilton and overlap matrices, H k and S k , referring to the basis functions
and Ej k and α j k the associated eigenvalues and eigenvectors, respectively.
Obviously one still has great freedom to construct a suitable basis set, and
accordingly there is a large number of methods and corresponding computer
codes available [34]. One route to set up an electronic structure method is to
take the tightly bound core states as frozen. This allows introducing effective
pseudo-potentials that do not show the singularity of the Coulomb potential when
4 Electronic Structure: Metals and Insulators 197
approaching the atomic nucleus. As a consequence, one may use even plane
waves as basis functions. Higher accuracy and flexibility, however, can be achieved
by using a technique called projector-augmented wave method (PAW) [35] that
mediates between pseudo-potential and so-called all-electron methods, with the
latter aiming to solve the Kohn-Sham equations directly. Again one may distinguish
between methods using analytical or numerical basis functions. Within the LMTO
method [36], for example, the Kohn-Sham equation is solved numerically at a fixed
energy Eν and angular momentum l for a spherical potential inside an atomic cell
that is approximated by a sphere. A linear combination of these solutions φlν (r)
and their energy derivatives φ̇lν (r) are augmented outside the atomic cell in a way
that leads to a decaying muffin-tin orbital that solves the Kohn-Sham equation also
within all neighboring atomic cells. The Bloch sum of such muffin-tin orbitals
is obviously a suitable basis function. By construction, it is energy independent,
but with an appropriate choice of Eν it will account, within the energy regime of
interest, for the energy dependence of the exact solution up to first order. This is a
common feature of all so-called linear methods [36] like the LAPW [36, 37]. The
special choice of the basis function of the LMTO method has the additional feature
that it is minimal: this means that one can restrict the angular momentum expansion
of the basis function in line with chemical intuition, i.e., for transition metals, one
should go at least up to d-states with l = 2. Solving the resulting secular equation
or algebraic eigenvalue problem, one gets finally the energy eigenvalue Ej k of the
Bloch states together with a corresponding representation of their wave functions
ψj k (r) in terms of the radial functions φlν (r) and their energy derivatives φ̇lν (r):
jk jk
ψj k (r) = Alm φlν (r) Ylm (r̂) + Blm φ̇lν (r) Ylm (r̂), (16)
lm
jk jk
where the expansion coefficients Alm and Blm are given by the eigenvectors α j k
and Ylm (r̂) are spherical harmonics. A similar representation of the Bloch wave
functions is obtained for most other all-electron band structure methods.
Although most band structure methods are formulated as k-space methods
assuming three-dimensional periodicity, they can nevertheless be applied to situ-
ations with lower dimensionality or symmetry by means of the super-cell technique.
This is illustrated for the case of a random substitutionally disordered binary alloy
Ax B1−x in Fig. 3. Instead of dealing with an, in principle, infinitely large unit cell
that represents the random distribution of the A- and B-atoms on the geometric
lattice, periodic boundary conditions are imposed implying the use of a finite size
super-cell that is enlarged when compared to the unit cell of the underlying lattice.
To achieve a reliable representation of the configurational average of a disordered
alloy, obviously the unit cell has to be large enough and a representative average has
to be taken concerning the atomic configuration within the super-cell [38] using,
for example, the concept of a special quasi-random structure [39]. As indicated by
the lower panel of Fig. 3, the same type of reasoning can be applied when dealing
with the problem of a disordered spin configuration of a solid that may occur due to
thermal spin fluctuations [40]. The super-cell technique is also frequently applied
198 H. Ebert et al.
Fig. 3 Top row: representation of a random substitutionally disordered binary alloy Ax B1−x (left)
by means of the super-cell technique (middle) and by means of an effective medium theory (right).
Bottom row: corresponding application of these schemes to the problem of a disordered spin
configuration
in case of reduced dimensionality of the system as, for example, when dealing with
surfaces or impurities in a host system. In the latter case obviously the size of the
super-cell has to be chosen large enough to avoid an interaction of impurities in
neighboring super-cells.
Instead of representing the electronic structure of a solid in terms of Bloch
states with associated wave functions ψj k (r) and energy eigenvalues Ej k , this can
be done by means of the corresponding retarded single-particle Green function
G+ (r, r , E). With the solutions to the band structure problem available, the
Green function G+ (r, r , E) can be given via the so-called Lehmann spectral
representation [41]
ψj k (r) ψj†k (r )
+
G (r, r , E) = lim , (17)
→0 E − Ej k + i
jk
that allows straightforwardly to derive convenient expressions, for example, for the
density of states n(E) and electron density n(r), respectively:
1
n(E) = − d 3 r G+ (r, r, E) (18)
π
4 Electronic Structure: Metals and Insulators 199
EF
1
n(r) = − dE G+ (r, r, E). (19)
π
Although Eq. (17) is frequently used, it is not very convenient as one needs in
principle the whole spectrum connected with the underlying electronic Hamiltonian
to get the Green function for a given energy E. An alternative to this is offered
by the multiple scattering theory-based KKR (Korringa-Kohn-Rostoker) formalism
that leads to the following expression for G+ (r, r , E) [42]:
i×
G+ (r, r , E) = ZLi (r, E) τLL
ii
(E) ZL (r , E)
L,L
−δii ZLi (r < , E) JLi× (r > , E) (20)
L
that in particular does not require Bloch translational symmetry for the system
considered. The functions ZLi (r, E) and JLi (r, E) in Eq. (20) are regular and
irregular solutions, respectively, to the Kohn-Sham equation with angular character
L = (l, m) for r in the atomic cell at site i and a specific normalization [42]. The
quantity τLLii (E) is the so-called scattering path operator that transfers a wave with
character L coming in at site i into a wave going out from site i with character L
with all intermediate scattering events accounted for. From Eq. (18), it is obvious
that the site-diagonal quantity τLL ii (E) determines in particular the variation of the
density of states ni (E) at site i with energy E.
The use of the Green function offers many advantages when dealing with
embedded subsystems, response functions, spectroscopy, disorder, or the many-
body problem. To a large extent, this is due to the Dyson equation that allows to
express the Green function G+ (r, r , E) of a complex system on the basis of that of
a simpler reference system (G+
0 (r, r , E)) and the arbitrary perturbing Hamiltonian
Hpert (r) that connects the two systems:
G+ (r, r , E) = G+
0 (r, r , E) + d3 r G+
0 (r, r , E)
Ω
with Ω the region for which Hpert (r) has to be accounted for. For a substitutional
impurity, this would include the atomic cell of the impurity and the region of the
neighboring host atoms that are distorted by the impurity.
The Green function formalism is particularly useful when dealing with the
electronic structure of disordered systems. By using the concept of the molecular
field, Soven [43] introduced the Coherent Potential Approximation (CPA) approach
when dealing with disordered substitutional alloys. The corresponding hypothetical
effective CPA medium plays the role of the molecular field and is constructed such
that it represents the configurational average for the alloy as accurate as possible
200 H. Ebert et al.
(see Fig. 3). The standard CPA is a so-called single-site theory implying that the
occupation of neighboring lattice sites is uncorrelated, i.e., short-range order is
excluded. Within the KKR approach, the CPA medium is therefore determined by
requiring that for an Ax B1−x alloy, the embedding of an A- or B-atom into the CPA
medium should on the average lead to no additional scattering:
A + (1 − x) τ B = τ CPA .
x τ ii ii ii
(22)
2 2 2
0 0 0
-2 -2 -2
E (eV)
E (eV)
E (eV)
-4 -4 -4
-6 -6 -6
-8 -8 Ni Pd -8
Γ Δ X 0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2
wave vector k n↑(E) (sts./eV) n↑(E) (sts./eV)
2 2 2
0 0 0
-2 -2 -2
E (eV)
E (eV)
E (eV)
-4 -4 -4
-6 -6 -6
-8 -8 Ni Pd -8
Γ Δ X 0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2
wave vector k n↓(E) (sts./eV) n↓(E) (sts./eV)
Fig. 4 Left: spin-resolved Bloch spectral function AB σ (k, E) of the disordered ferromagnetic alloy
fcc-Ni0.8 Pd0.2 calculated on the basis of the CPA. Middle and right column: corresponding spin-
resolved partial density of states nασ (E) for α = Ni or Pd, respectively. The top and bottom row
give results for spin up and down, respectively. As a reference, the dispersion relation Ej kσ of pure
Ni is superimposed as a black line to AB Ni
σ (k, E) (left). In addition, nσ (E) for pure ferromagnetic
Pd
Ni (middle) and of nσ (E) for pure paramagnetic Pd (right) are included in the figures as dashed
lines [26]
4 Electronic Structure: Metals and Insulators 201
middle and right columns give the spin-resolved partial density of states nασ (E) for
α = Ni or Pd, respectively. Comparison of AB σ (k, E) with the dispersion relation
Ej kσ of fcc-Ni and of nNiσ (E) for the alloy with that for pure Ni clearly shows the
smearing-out of these curves for the alloy in particular in the regime of the d-states.
This reflects the fact that for the alloy the wave vector k is not a good quantum
number. In fact the width of the AB σ (k, E) functions can be interpreted as a measure
for the electronic lifetime to be used in the calculation of the residual resistivity on
the basis of the Boltzmann formalism [44]. The right column of Fig. 4 gives results
for the partial DOS nPd σ (E) of Pd in fcc-Ni0.8 Pd0.2 and for pure paramagnetic Pd
that clearly shows that Pd gets spin-polarized due to hybridization leading to an
induced spin-magnetic moment of about 0.21 μB .
It is important to note that the concept of the CPA is not restricted to alloys but
can be applied to any type of disorder. Making use of the alloy analogy, the CPA is
used, for example, within the disordered local moment (DLM) model [45] to per-
form an average over spin configurations connected with thermal spin fluctuations
(see section “Coherent Treatment of Electronic Structure and Spin Statistics”).
Relativistic Effects
A most coherent way to account for the influence of relativistic effects is to work on
the basis of the Dirac Hamiltonian [5]:
1 2
ĤD = −icα · ∇ + c (β − 1) + V̄ (r) + β σ · B(r) + eα · A(r). (23)
2
Here c is the speed of light, αi and β are the standard 4 × 4 Dirac matrices, cα
is the electronic velocity operator, σi are the 4 × 4 spin matrices, and the local
potential may involve a spin-independent part V̄ (r), an effective magnetic field
(B(r)) coupling only to the spin [46] and the vector potential (A(r)) coupling
to the electronic current, where the effective fields B(r) and A(r) combine
exchange-correlation and possible external contributions. This approach implies a
four-component electronic wave function ψ(r, E) or bi-spinor, respectively, with a
large and small component [5]. Corresponding versions based on this framework
have been worked out for several band structure methods [47, 48] assuming in
general a spin-dependent potential only (A(r) = 0). The appealing feature of these
schemes is that they treat all relativistic effects and magnetic ordering on the same
footing.
Alternatively, one may apply a Foldy-Wouthuysen transformation [5] to the Dirac
equation. Considering only a spherical scalar potential V (r) in Eq. (23) and keeping
only terms up to the order of 1/c2 , this leads to three relativistic corrections when
compared to the Schrödinger Hamiltonian [49]:
1 4
Hmass = −β p (24)
c2
202 H. Ebert et al.
1 2
HDarwin = ∇ V (r) (25)
2c2
1 1 ∂V (r)
HSOC = 2 σ · l. (26)
c r ∂r
The first two corrections, mass enhancement (Hmass ) and Darwin (HDarwin ) terms,
do not involve the spin operator σ , and for that reason, they are called scalar
relativistic. In general, these corrections give rise to a downward shift in energy
for s- and p-states and, in response to this, to an upward shift in energy for d-states
[50]. For a paramagnetic metal, this influences the density of states at the Fermi
level and this way the tendency toward spontaneous formation of spin magnetism
via the Stoner mechanism (see section “Stoner Model of Itinerant Magnetism”).
The third correction term is the spin-orbit coupling (HSOC ), which is given in its
commonly simplified form, that holds in case of a spherically symmetric scalar
potential V (r). As HSOC couples the electronic orbital and spin degrees of freedom,
this term will lead to the removal of degeneracies for any material. For a spin-
polarized material, it leads furthermore to a reduction in symmetry as reflected by
many important properties as, for example, the magnetocrystalline anisotropy [51,6]
or galvanomagnetic [8] and magneto-optical [9] properties.
In practice, most electronic structure calculations are based on relativistic
correction schemes that first of all aim to eliminate the small component from
the Dirac equation leading to a two-component formalism [52, 53]. Within so-
called scalar relativistic calculations, spin-orbit coupling is ignored leading to no
technical changes when compared to a nonrelativistic calculation on the basis of
the LSDA that treat spin-up and spin-down states separately. However, including
HSOC does not allow this simplification any more requiring higher computational
effort. While HSOC can still be accounted for when setting up the basis functions of
a band structure scheme [52, 54], it is in most cases seen as a correction to a scalar
relativistic Hamiltonian and therefore accounted for only in the variational step of a
standard band structure scheme [36, 37].
As an illustration, Fig. 5 gives the dispersion relation Ej k of ferromagnetic Ni
calculated in a non-, scalar, and fully relativistic way. The left panel of the figure
shows the impact of the scalar relativistic corrections Hmass and HDarwin . The
middle panel shows results that account in addition for the spin-diagonal part of
HSOC proportional to lz σz [55]. Although this term leaves spin as a good quantum
number, it obviously removes many degeneracies and band crossings giving rise, for
example, to spin-orbit-induced orbital magnetic moments [55]. Accounting finally
for the full spin-orbit coupling HSOC (right panel), one finds further removals of
band crossings and a coupling of the two spin systems. This spin mixing gives rise
to so-called hot spots in the band structure [56] that are important, for example, for
spin-flip relaxation processes.
The relativistic corrections mentioned so far concern only the kinetic part of
the electronic Hamiltonian, but not the effective potential. Starting from a fully
relativistic framework in fact corresponding corrections have to be expected when
4 Electronic Structure: Metals and Insulators 203
-0.5 -0.5
-1 -1
Ejkσ (eV)
-1.5 -1.5
-2 -2
NREL SOC zz FREL
-2.5 -2.5
Γ Δ X Γ Δ X Γ Δ X
wave vector k
Fig. 5 Dispersion relation Ej k of ferromagnetic Ni. Left: spin-resolved curves Ej kσ for non-
(black lines) and scalar (up and down triangles) relativistic mode. Middle: relativistic mode that
accounts only of the spin-diagonal part of HSOC proportional to lz σz (black lines) and scalar
relativistic mode (up and down triangles). Right: fully (black lines) and scalar (up and down
triangles) relativistic mode [26]
considering the free electron gas as a reference system [15]. The impact of such
corrections to the exchange-correlation potential has been monitored in particular
for paramagnetic materials [57]. For magnetic materials, a coherent derivation
of nonrelativistic spin-density functional theory could be given by starting from
a relativistic formalism [24]. Later on, a relativistic formulation of spin-density
functional theory assuming a spin-dependent exchange-correlation potential that
couples only to the spin degree of freedom was worked out [58, 46] leading
to Eq. (23) with A(r) = 0. This simplification seems to be acceptable for
many magnetically ordered transition metal systems. On the other hand, spin-orbit
coupling gives for spin-polarized materials automatically rise to orbital magnetism
[59] that can be associated with a corresponding orbital current. Accordingly,
relativistic spin-density functional theory should in principle be replaced by a
current density formalism with the four current as a basic system variable [15],
i.e., one has B(r) = 0 and A(r) = 0 in Eq. (23). While various developments have
been made in this direction [60], there are no functionals for the corresponding
exchange-correlation available at the moment. As a consequence, the feedback of
orbital magnetism or polarization on the electronic Hamiltonian has been accounted
for primarily by means of hybrid schemes like the OP- [61], the LSDA+U- [62], or
the LSDA+DMFT-formalism [63].
Another consequence of a fully relativistic formalism is a modification of the
Coulomb potential and the occurrence of the Breit interaction [13]. The latter one
can be seen as a current-current interaction and accordingly can be represented
by a corresponding vector potential A(r) in Eq. (23). For magnetic materials, the
Breit interaction contributes not only to the total energy but also to its magnetic
anisotropy. In fact it has been pointed out that the Breit interaction is the quantum
204 H. Ebert et al.
mechanical source for the classical dipole-dipole interaction giving rise to the
magnetic shape anisotropy [14].
Adiabatic Dynamics
The features of the electronic band structure determine not only the ground-state
properties of a material but also the dynamical properties of electrons in the presence
of external time-dependent perturbations. When a perturbation varies slowly in time,
the dynamics of the electronic subsystem can be efficiently described using the
concept of the Berry phase [64] arising during the adiabatic evolution of electronic
quantum states. According to its definition, the Berry phase is connected to a
parameter-dependent Hamiltonian [65,66,67]. For systems with a periodic effective
potential Veff (r + R n ) = Veff (r) with R n a lattice translation vector, leading to a
Bloch-like solution of the eigenvalue problem (see Eq. (14)):
2
p̂
the unitary transformation of the Hamiltonian H = 2m + Veff (r) leads to a
momentum-dependent Hamiltonian (for details see [67])
(p̂ + h̄k)2
H(k) = e−ik·r Heik·r = + Veff (r). (28)
2m
This allows treating the Brillouin zone as the parameter space of the transformed
Hamiltonian H(k) with cell-periodic eigenfunctions uj k (r). The Berry phase is
expressed as an integral over the path C in the parameter space of the electronic
momentum k,
γj (k) = dk · Aj (k). (29)
C
The integral is gauge-invariant for a closed path, while the Berry vector potential,
or the Berry connection
∂
Aj (k) = i uj k
uj k ,
(30)
∂k
or, alternatively,
4 Electronic Structure: Metals and Insulators 205
∂j (k) e
v j (k) = − E × Ω j (k), (34)
h̄∂k h̄
with the Berry curvature Eq. (32) given in the form [69, 67]:
Ω j (k) = i ∇ k uj k | × |∇ k uj k
. (35)
with D the dimensionality of the system and αβγ the Levi-Civita tensor. As one
can see, this contribution is determined by all occupied states, and it is the only term
206 H. Ebert et al.
Fig. 6 (a) Fermi surface in the (010) plane (solid lines) and integrated Berry curvature −Ω z (k)
in atomic units (color map) of fcc Fe. (From Yao et al. [70]); (b) Berry curvature projected onto
the (k3 , k1 ) plane for Mn3 Ge, where k3 and k1 are aligned with the kz and kx axes, respectively.
It is calculated by integrating along the k2 direction. (From Ref. [71]); (c) Energy dispersion of
Mn3 Ge along k2 with (k3 , k1 ) fixed at the point with the largest Berry curvature, indicated by a
black dashed circle in (b). (From Ref. [71]). (Figure are printed with permission from [70] by
the American Physical Society; Figure (b) and (c) reprinted with permission from [71] by the
American Physical Society.)
contributing to the AHC for insulating systems. It is independent on the nature of the
impurities and their concentration and therefore is called intrinsic contribution to the
AHE. Note, however, that this contribution is not the only intrinsic contribution in
metals. The so-called side-jump mechanism suggested by Berger [74] is contributed
by the electrons at the Fermi surface and also yields a Hall conductivity that is
independent of the impurity concentration [69].
Note that the anomalous thermoelectric transport driven by statistical forces due
to a temperature gradient ∇T (the same concerns also the transport driven by
chemical potential gradients ∇μ) cannot rely on the anomalous velocity term as
it vanishes in the absence of an electric field. A corresponding theory giving the
intrinsic contribution to transverse thermoelectric transport has been reported by
Xiao et al. [75]. It is based on the generalization to finite temperatures of a theory
giving a Berry-phase correction to the orbital magnetization [76, 77, 17]:
4 Electronic Structure: Metals and Insulators 207
dDk
M(r) = f (j (k))mn (k)
BZ (2π )D
j
1 dDk e
+ D
Ω j (k)log 1 + e−β(j (k)−μ) , (37)
β BZ (2π ) h̄
j
dDk 1
Mz (r) = D
f (j (k))mn,z (k) + df ()σxy (). (38)
BZ (2π ) e
j
It has two different contributions associated with the self-rotation of the wave packet
representing an electron and with the center-of-mass motion, respectively. The first
term, obviously, occurs by treating the carrier as a wave packet having finite spread
in the phase space. The second term comes from the Berry-phase correction to the
electron density of states [67].
A crucial point for thermoelectric transport is that the conventional expression
used for the current density is incomplete as it is derived for the carrier treated as a
point particle. Having a corresponding expression for the local current J obtained by
treating the carrier as a wave packet, introducing the concept of a transport current
j = J − ∇ × M(r), (39)
and using the expression Eq. (37) for the orbital magnetization density M(r), one
obtains the transport current as given by:
dDk
j = −e D
g(r, k)ṙ (40)
BZ (2π )
1 dDk e
−∇ × Ω(k)log(1 + e−β((k)−μ) ). (41)
β BZ (2π )D h̄
Talking about the AHE in antiferromagnets (AFM), one has to distinguish the
systems according to their symmetry. The AHE does not occur in collinear AFMs
symmetric with respect to time-reversal symmetry T combined with a half-magnetic
208 H. Ebert et al.
Historically there was for a long time a heated discussion whether the model of
itinerant or band magnetism is a suitable platform to discuss the magnetic properties
of a specific solid or whether the assumption of local magnetic moments is more
appropriate. With the advances in electronic structure theory to provide schemes
that allow treating the electronic structure of solids from wide-band metallic solids
up to narrow-band oxides, including localized systems showing the formation of
electronic multiplets, the competition between these extreme models gets more
or less obsolete. Accordingly, this section gives only a brief introduction to the
theory of itinerant or band magnetism on the basis of the Stoner model followed
by discussing the main electronic features of two prototype class of materials:
disordered alloys of transition metals and the Heusler alloys.
E E E
EF EF EF
2 μBBext
n↓(E) n↑(E) n↓(E) n↑(E) n↓(E) n↑(E)
Fig. 7 Left: spin-dependent DOS n(EF ) at the Fermi energy EF for a paramagnetic metal. Middle:
Zeeman splitting ΔEZ = 2 μB Bext due to an external magnetic field Bext . Right: spin flip leads to
a common Fermi energy EF and a finite spin-magnetic moment M = (N↑ − N↓ )
energy for both spin systems leading to a net spin-magnetic moment M = (N↑ −
N↓ ). For small magnetic fields Bext , the resulting Pauli spin susceptibility χ =
M μB /Bext is determined by the density of states n(EF ) at the Fermi energy EF :
An imbalance of N↑ and N↓ also changes the total energy due to the exchange
interaction. The corresponding spin-dependent correction for the electron energies
Ej kσ for spin σ (with σ = ±1/2) may be written as [82]:
Ej kσ = Ej k + sign (σ ) M I (44)
with the Stoner exchange integral I originally seen as a parameter. Accounting for
this correction, in addition one is led to the enhanced spin susceptibility
χ = S χ0 , (45)
The paramagnetic state remains stable as long as I n(EF ) < 1 holds. However, when
I n(EF ) approaches the value 1, the enhancement factor S and with this the induced
magnetic moment diverge indicating an instability. In fact, I n(EF ) > 1 for the
paramagnetic reference state implies that the increase of kinetic energy associated
with the flip of the spin for electrons at the Fermi energy is more than compensated
by the resulting change in the exchange-correlation energy even without an external
field leading to a stabilization of the ferromagnetic state [83]. Accordingly, the
Stoner criterion I n(EF ) > 1 indicates the spontaneous formation of ferromagnetic
spin order for a solid.
210 H. Ebert et al.
Linear response theory allows deriving explicit expressions for the static [84,
85, 86] and dynamic [87, 88] spin susceptibility of arbitrary systems that confirm
Eqs. (43) and (45) even for inhomogeneous, i.e., non-bulk, systems. Working within
the framework of SDFT provides in particular a clear prescription for the calculation
of the Stoner exchange integral [89, 84]:
I= d 3 r γ (r)2 K(r), (47)
with the induced spin polarization γ (r) and the exchange-correlation kernel K(r):
γ (r) = |ψj k (r)|2 δ(EF − Ej k )/n(EF ) (48)
jk
1 δ 2 Exc
K(r) = − . (49)
2 δm2 m(r)=0
1
3d 2 3d
4d 4d
0.9 5d 5d
n(EF) (1/eV)
1.5
0.8
I (eV)
0.7 1
0.6
0.5
0.5
0.4 0
Ti V Cr Mn Fe Co Ni Cu Ti V Cr Mn Fe Co Ni Cu
Zr Nb Mo Tc Ru Rh Pd Ag Zr Nb Mo Tc Ru Rh Pd Ag
Hf Ta W Re Os Ir Pt Au Hf Ta W Re Os Ir Pt Au
Fig. 8 Stoner exchange-correlation integral I (left) and density of states n(EF ) (right) at the Fermi
energy EF for the 3d, 4d, and 5d transition metal rows [26]
4 Electronic Structure: Metals and Insulators 211
As the Stoner integral I in general does not change much with the atomic
environment, the Stoner factor is primarily determined by the DOS n(EF ) at the
Fermi energy EF . As the d-band width W of the transition metals decreases with
coordination number, this leads usually to an increase of n(EF ). This implies
a corresponding increase of the tendency toward ferromagnetic ordering with
reduced dimensionality. Accordingly, magnetically ordered surface layers have been
predicted by theory for the paramagnetic metals V and Pd while the experimental
situation is unclear. For free and deposited transition metal clusters, many SDFT-
based calculations led to finite spin-magnetic moments as, for example, for free
Ru13 , Rh13 , and Pd13 clusters [90]. Additional calculations for the paramagnetic
state gave a large peak for the DOS near the top of the valence band with the Fermi
energy located at its maximum, i.e., the magnetic ordering could be explained on
the basis of the Stoner criterion. These results are fully in line with experimental
data for RuN and PdN clusters; for example, mRh ≈ 0.8 μB /atom in Rh9 , mPd <
0.4 μB /atom in Pd13 and mRu < 0.32 μB /atom in Ru10 clusters [91]. In accordance
with the Stoner criterion, an increase of cluster size led to a decrease of magnetic
moments as, for example, mRh ≈ 0.16 μB /atom in Rh34 and mRu < 0.09 μB /atom
in Ru1115 clusters.
The Stoner criterion was also applied successfully to deposited atoms. For exam-
ple, in line with experiment, self-consistent LSDA-based calculations predicted a
finite and vanishing spin-magnetic moment for Fe and Ni atoms, respectively, on a
chalcogenide topological insulator surface [92].
Slater-Pauling Curve
The substitutional magnetic alloys of 3d transition metals are often seen as prototype
materials for itinerant metallic magnetism. The experimental data on the average
magnetic moment M per atom of these systems is summarized by the well-known
Slater-Pauling curve shown in Fig. 9 (top). There are two main branches to be seen:
one leading from Fe to Cu with a slope of −45◦ and another one from Fe to Cr
with a slope of +45◦ . M is obviously given by M = N↑ − N↓ , where Nσ is the
average number of valence electrons with spin character σ . With the total number
of valence electrons Z = N↑ + N↓ , one gets the simple relation M = 2 N↑ − Z. On
the basis of the outdated rigid-band model that postulates a common electronic band
structure for both components of a binary alloy, all Ni and Co alloys are considered
to be strong ferromagnets with their spin-up band filled. Accordingly, N↑ is constant
and M decreases with Z explaining the right main branch of the Slater-Pauling
curve. For Z = 8.25, one may assume that the Fermi energy is at the top of the
spin-up band. Decreasing Z, one can now expect that N↓ stays constant leading to
M = Z − 2 N↓ . This obviously gives a simple explanation for the second branch
including in particular the Fe-Cr and Fe-V alloys.
Using the tight-binding version of the CPA combined with the Hartree-Fock
approximation, Hasegawa and Kanamori [94] could already give an alternative qual-
itative explanation for the Slater-Pauling curve avoiding the unrealistic assumptions
212 H. Ebert et al.
2.5 FeCo
Experiment FeTi
FeNi
2
magnetic moment (µ B)
CoFe
NiCr
0
NiV
24 25 26 27 28
electron number / atom
2.5
FeCo
Theory
2 FeNi
magnetic moment (µ B)
FeCu
NiFe CoFe
FeSc
1.5 CoMn(2)
NiCo
CoCr
1
FeTi CoMn (1) NiMn
0.5 NiTi NiCu
FeV FeCr
NiCr
0 NiV
24 25 26 27 28
electron number / atom
Fig. 9 Top: experimental Slater-Pauling curve, i.e., the average magnetic moment corresponding
to the saturation magnetization of Fe-, Ni-, and Co-based alloys vs. average number of electrons
per atom. Bottom: corresponding theoretical results obtained by means of the KKR-CPA. The fcc,
instead of hcp, structure is assumed for Co-based alloys. For Co-Mn, two solutions, CoMn(1) with
a Mn local moment parallel to the bulk magnetization and CoMn(2) with an antiparallel moment,
are obtained. (All data taken from [93])
of the rigid-band model. This approach could be improved a lot by Akai using
the KKR-CPA within the framework of SDFT leading for most alloy systems to
a quantitative agreement between theory and experiment [93] (see bottom panel of
Fig. 9). Most importantly, this implies that the average moments are well described
by the effective CPA medium.
As found by experiment, the curves on the left-hand side, connected with Fe-
based bcc alloys, have a slope of about +45◦ although there is some spread. The
common feature of the alloys belonging to these subbranches is that the solute
atoms (Sc, Ti, V, and Cr) have negative local magnetic moments; i.e., they are
aligned antiparallel to the moments of the host (Fe, Co, and Ni). These negative
4 Electronic Structure: Metals and Insulators 213
moments can be associated with the appearance of hole states above or at the top
of the majority-spin d-bands. These hole states have a large amplitude at the solute
atoms causing a negative local moment there, as well as the rapid decrease of the
average moment with the solute concentration. The existence of the hole states in
the majority-spin band also affects the concentration dependence of the average
moment. In the case that no holes exist in the majority-spin band, the main origin
of the concentration dependence of the average moment is the reduced number of
available d-electrons as determined by the average number of valence electrons. In
fact, the straight line with a slope of −45◦ in the right half of the Slater-Pauling
curve, that is mainly associated with Ni-based fcc alloys, is explained this way.
Contrarily, in the case that holes exist in the majority-spin band, it is mainly the
missing number of majority d-states that causes the concentration dependence.
Thus, the slope of the average moment against the total number of electrons varies
depending on the solute atoms; the smaller the difference in the number of the
valence electrons, the steeper the slope. The above discussion, however, is useful
only for simple cases where the magnetic state is rather stable, typically in the
region of the strong ferromagnetism of Ni. More delicate situations as, for example,
the Ni-Fe, Ni-Mn, and Fe-Mn alloys in the vicinity where ferromagnetism becomes
instable, however, need a more detailed and specific discussion [93].
An important feature of the CPA calculations is that the alloy components
essentially keep their intrinsic properties. Fe, Co, and Ni, for example, have in
general in the various alloys a spin moment close to that of the pure elements (2.2,
1.7, and 0.6 μB , respectively; see Table 1). This is fully in line with results of neutron
scattering experiments or XMCD (X-ray magnetic circular dichroism) experiments
that give access to the spin and orbital moment in an element-specific way via the
XMCD sum rules [9]. Figure 10 shows corresponding results for the average spin-
and orbital magnetic moment per atom in fcc-Fex Ni1−x together with component-
specific data as calculated via the relativistic KKR-CPA on the basis of the LSDA
and LSDA+DMFT, respectively, in comparison with experiment [95]. As one notes,
the individual spin-magnetic moments of Fe and Ni in fcc-Fex Ni1−x show only a
rather weak concentration dependence. This also applies for the spin-orbit-induced
orbital moments that are defined by the expectation value of the angular momentum
operator lz (see, e.g., the discussion in [17]). These findings are in full agreement
with the individual moments determined via XMCD at the L2,3 -edges of Fe and Ni
[95]. Here, it is interesting to note that the theoretical results for the spin moment
hardly depend on the computational mode, i.e., whether the calculations are based
on the LSDA or the LSDA+DMFT. The orbital moment, on the other hand, depends
strongly on the computational mode. In particular it is found that inclusion of
correlation effects via the DMFT improves agreement with experiment.
Heusler Alloys
LSDA
2 0.12 LSDA+DMFT
Expt
1.5
mspin (μB)
morb (μB)
0.08
1
LSDA
LSDA+DMFT 0.04
0.5 Expt
0 0
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
xFe xFe
3
0.2 LSDA
Fe Fe LSDA+DMFT
Expt
2.5 0.15
mspin (μB)
morb (μB)
2 0.1
morb (μB)
0.6 0.15
0.4 0.1
LSDA
0.2 LSDA+DMFT 0.05
Expt
0 0
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
xFe xFe
Fig. 10 Top row: average spin- (left) and orbital (right) magnetic moment per atom in fcc-
Fex Ni1−x as calculated on the basis of the LSDA and LSDA+DMFT, respectively, in comparison
with experiment. In addition, the individual moments calculated for Fe (middle row) and Ni (bot-
tom row) are given. The experimental component-specific data stem from XMCD measurements.
(All data taken from [95])
Fig. 11 Left: spin-resolved DOS for Co2 MnSi showing a bandgap for the minority states. Right:
comparison of the spin polarization obtained by in situ SRUPS on a Co2 MnSi thin film with
the calculated DOS-derived spin polarization, the calculated UPS spin polarization including
broadening effects and considering only bulk states, and the calculated total UPS spin polarization
including broadening effects with additional surface state contributions [99]
n↑ (E) − n↓ (E)
p= (50)
n↑ (E) + n↓ (E)
one has for half-metallic materials 100% spin polarization at the Fermi energy that
should lead to a fully spin-polarized electric current.
For real materials, however, the spin polarization may be influenced in various
ways. Mavropoulos et al. [100], for example, demonstrated the impact of spin
mixing caused by spin-orbit coupling for the Heusler alloys of the type XMnSb.
As expected, this influence increased with increasing atomic number of the element
X, as reflected by the ratio n↓ (EF )/n↑ (EF ) = 0.25, 0.30, 0.35, 0.75, and 2.70 found
for the series X = Co, Fe, Ni, Pd, and Pt. As a consequence, one can expect a spin
polarization well below 100% for compounds with heavier elements.
The influence of the surface on the spin polarization has been studied by
Galanakis [101] investigating the (001) surfaces of the semi-Heusler alloys
NiMnSb, CoMnSb, and PtMnSb and for the full-Heusler alloys Co2 MnGe,
Co2 MnSi, and Co2 CrAl. In general, a rather strong modification of electronic
and magnetic properties has been found for the surface region. In the case of semi-
Heuslers, the Ni-, Co-, or Pt-terminated surface has a rather large DOS at the Fermi
level for minority-spin states, while for the MnSb-terminated surfaces the calculated
properties are close to those of the bulk. Nevertheless, half-metallicity disappears
also in this case due to surface states, resulting in a spin polarization at the Fermi
216 H. Ebert et al.
level of 38%, 46%, and 46% for NiMnSb, CoMnSb, and PtMnSb, respectively. A
similar behavior was found for the Co-terminated surfaces of the full-Heusler alloys
Co2 MnGe, Co2 MnSi, and Co2 CrAl. In the case of the MnGe-terminated (001)-
surface of Co2 MnGe, the spin polarization vanishes also due to the surface states,
although the CrAl termination of Co2 CrAl leads to a very high spin polarization of
around 84%.
In experiment, the spin polarization of a material can be determined among
others by tunneling experiments or by spin-resolved photoemission [102, 103, 104].
Figure 11 shows corresponding experimental and theoretical spin-polarization
curves of Co2 MnSi [99] for the UPS-regime (hν = 21.2 eV) that showed for the
surface regime a value of 93% at the Fermi level, the largest observed so far.
NiMnSb was among the first semi-Heusler compounds predicted to be half-
metallic [105] and was intensively investigated since then by experiment as well
as theory [106, 107, 108]. The Sb atoms with the atomic configuration 5s2 5p3 lead
to the formation of a deep lying narrow s- and a p-band at around 12 and 3 − 5 eV,
respectively, below the Fermi energy EF . Accordingly, these states are not involved
in the formation of the bandgap near EF . The Ni and Mn d-states hybridize with
each other as well as with the sp-states of Sb leading to the formation of bonding
and antibonding bands. For the paramagnetic state of NiMnSb, the Fermi level
lies in the middle of an antibonding band mainly associated with the d-states of
Mn. Accordingly, exchange splitting of the antibonding band leads to a gain in
energy accompanied by formation of a strong magnetic moment for the Mn atom.
As a result, the Fermi energy moves to the energy gap separating bonding and
antibonding minority-spin states. Due to this, there are nine minority-spin states per
unit cell below EF , one due to the Sb-like s-band, three due to the Sb-like p-bands,
and five due to the Ni-like d-bands, that are all occupied. As atoms forming the alloy
contribute 22 electrons per unit cell, the majority-spin band contains 22 − 9 = 13
electrons, resulting in a moment of 4 μB per unit cell.
Plotting the total spin-magnetic moment per unit cell, M, of NiMnSb together
with that of other semi-Heusler half-metallic compounds as a function of the total
number of valence electrons Z, one can see that M – in analogy to the Slater-Pauling
curve for the binary transition metal alloys – follows the relation: M = Z −18 [107]
(see Fig. 12 (left)). This relation is a consequence of the complete occupation of the
nine minority-spin bands and follows directly from the definitions Z = N↑ + N↓
and M = N↑ − N↓ that lead to mt = Z − N↓ [98].
The occurrence of half-metallicity in the case of the prototype full-Heusler
compounds Co2 MnSi and Co2 MnGe was also predicted by electronic structure
calculations [109, 110]. Similar to the case of semi-Heusler alloys, the sp-bands
of Si and Ge are located well below EF . For that reason, they do not participate in
the formation of the energy gap that is caused by the hybridization of Mn and Co d-
states. As a result, for the spin-polarized state of the material, the Fermi level is again
located within the minority-spin energy gap, so that the minority band contains 1 s-
band and 3 p-bands derived from the sp-element and 8 Co-related d-bands, which
are fully occupied by 12 electrons [98]. As shown by Galanakis et al. [111], the
spin-magnetic moment of the full-Heusler alloys accordingly follows the relation
M = Z − 24. Corresponding theoretical and experimental data are summarized in
4 Electronic Structure: Metals and Insulators 217
6 6
Co2MnSi
Co2MnAs
Co2MnGe Co2MnSb
Co2CrAl Co2MnSn Co2FeSi
NiMnSe
NiMnSb Fe2MnSi Co2FeAl
NiMnTe Ru2MnSi Rh2MnIn
PdMnSb
4 PtMnSb
4 Ru2MnGe Rh2MnTl
Ni2MnAl
CoFeSb Ru2MnSn
RhMnSb NiFeSb Rh2MnGe
Co2VAl Rh2MnSn
M
M
CoMnSb 2 Fe2MnAl Rh2MnPb
IrMnSb Co2TiSn
2 FeMnSb
NiCrSb Fe2CrAl Co2MnAl
CoCrSb Co2TiAl Co2MnGa
0
24
CoVSb NiVSb Fe2VAl Rh2MnAl
Z-
18
Mn2VGe Rh2MnGa
=
Z-
Ru2MnSb
M
0 CoTiSb
=
-2 Mn2VAl
M
16 18 20 22 24 20 22 24 26 28 30 32
Z Z
Fig. 12 Left: calculated total spin moments per unit cell for several semi-Heusler alloys.
Experimental values are given for NiMnSb (3.85 μB ), PdMnSb (3.95 μB ), PtMnSb (4.14 μB ), and
CoTiSb (nonmagnetic) [107]. Right: calculated total spin moments for several full-Heusler alloys.
Experimental values are given for Co2 MnAl (4.01 μB ), Co2 MnSi (5.07 μB ), Co2 MnGa (4.05 μB ),
Co2 MnGe (5.11 μB ), Co2 MnSn (5.08 μB ), Co2 FeSi (5.9 μB ), Mn2 VAl (1.82 μB ), and Fe2 VAl
(nonmagnetic) [111]. In both figures the dashed line represents the corresponding Slater-Pauling
curve. The open circles represent the compounds deviating from this curve
the Slater-Pauling plot in Fig. 12 (right). The difference to the Slater-Pauling curve
of the binary transition metal alloys in Fig. 9 is due to the fixed number of minority-
spin electrons in the half-metallic Heusler compounds. In this case, increasing Z
leads to a filling of the majority band, while for the ferromagnetic transition metal
alloys, the relation M = 10 − Z for the right branch is a result of the full occupation
of five majority-spin d-states and charge neutrality achieved by filling the minority-
spin d-states.
Within the family of Heusler compounds, there are furthermore the so-called
inverse full-Heusler compounds that have a similar chemical formula X2 YZ but
crystallize in the so-called Xα structure [98]. The prototype of the inverse full-
Heusler compounds is Hg2 TiCu [112]. As Fig. 13 demonstrates, the magnetic
moments per unit cell as a function of valence electrons also follow in this case
corresponding Slater-Pauling rules.
The calculation of the electronic total energy allows to seek for the magnetic ground
state of a solid. This applies to the crystal structure as well as to the specific magnetic
ordering or spin configuration, respectively. For many purposes, it is helpful to
represent the neighborhood of the ground state or a suitable magnetic reference
state by mapping the complex configuration dependence of the total energy of the
system on an approximate spin Hamiltonian. An issue in this context is spin-orbit
coupling that removes energetic degeneracies of competing spin configurations, may
218 H. Ebert et al.
Mn2NiAs
M = Z-18 M = Z-24 Mn2CoAs
4 Ti2NiAl Ti2CuAl
4 Mn2NiSi
Cr2CoAs
Ti2CoAl Ti2CoSi Mn2FeSi Mn2FeAs
Sc2NiAl Ti2FeSi Ti2FeAs Mn2CoSi
Mn2MnAs
2 Sc2CoSi V2MnAl V2CrSi 2 Cr2NiSi
Ti2FeAl Mn2CoAl
Sc2NiSi V2CoSi
V2CrAl V2FeAs Cr2NiAl
Ti2MnAs V2NiAs Cr2CoSi
Cr2CrAs
M
M
0 Ti2CrAl Ti2MnAl 0 Cr2FeAl Cr2CoAl Cr2FeAs
Sc2MnAl Ti2VAs Cr2MnAs Mn2FeAl
Sc2CrSi Ti TiSi Sc2FeAl Mn2CrAl V2NiAl Mn2MnSi
V2VAl Mn MnAl
Sc2VAs 2 Sc2MnSi Cr2MnSi Mn2CrAs
Cr2CrSi 2
Mn2CrSi
-2 Ti2VAl Sc 2
CrAs -2 V2MnSi V2CoAl
Ti2VSi V2FeSi
Sc2VSi V2FeAl
Sc2VAl Sc2CrAl V2MnAs
Cr2MnAl
-4 -4 Cr2CrAl
13 15 17 19 21 23 20 22 24 26 28 30
Z Z
Fig. 13 Total spin-magnetic moments per unit cell (in μB ) as a function of the total number
of valence electrons Z in the unit cell for several compounds. The lines represent the two of the
various forms of the Slater-Pauling rule [98]. The compounds within the frames follow one of these
rules and are perfect half-metals, while the rest of the alloys slightly deviate. For this reason, their
total spin-magnetic moment is represented by an open red circle. The sign of the spin-magnetic
moments has been chosen so that the half-metallic gap is in the spin-down band
Access to the electronic total energy Etot (see Eq. (10)) in principle allows to
determine the magnetic ground state of any solid. As a corresponding example
for this, results of LSDA-based calculations for Fe in the para- (PM), ferro- (FM),
as well as antiferromagnetic (AFM) state with bcc and fcc structure are shown in
Fig. 14 [27]. Obviously, the use of the LSDA led to an over-binding, i.e., to a lattice
parameter that is too small and a bulk modulus that is too large when compared
with experiment (see Table 1). Most importantly, however, the paramagnetic fcc-
phase was found as the ground state instead of the ferromagnetic bcc-phase. Use of
the GGA on the other hand improved the situation very much giving in particular
the ferromagnetic bcc-phase as the ground state.
Another example for a search for the magnetic ground state configuration is given
by Fig. 15. In this case, the so-called fixed spin moment method was used to explore
the dependency of the total energy Etot on the lattice parameter and average atomic
moment of disordered fcc-Fex Ni1−x alloys. As one notes, a double minimum occurs
in the vicinity of the concentration x = 0.65 indicating the competition between a
low-volume, low-spin moment phase and a high-volume, high-spin moment phase.
In fact, this has been seen as a possible explanation for the occurrence of the invar
effect for that composition. Another study on the invar effect, however, stressed the
importance of a noncollinear spin configuration [114].
4 Electronic Structure: Metals and Insulators 219
400 600
PM bcc
PM bcc
200 400
E (meV)
E (meV)
FM bcc
0 200 PM fcc
PM fcc AFM fcc
FM bcc
-200 0
60 65 70 75 80 70 75 80 85 90
Volume (a.u.) Volume (a.u.)
Fig. 14 Total energy Etot of paramagnetic (PM) bcc and fcc, ferromagnetic (FM) bcc, and
antiferromagnetic (AFM) fcc-Fe as a function of the volume as obtained within the LSDA (left)
and GGA (right), respectively. The curves are shifted in energy so that the minima of the FM-bcc
curves, corresponding to Etot = 0, coincide. (All data taken from [27])
2.5 2.5
2.0 2.0
M avg ( μ Β/atom )
M avg ( μ Β/atom )
1.5 1.5
1.0 1.0
0.5 0.5
Fe 60 Ni 40 Fe 65 Ni 35
0.0 0.0
6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.3 6.4 6.5 6.6 6.7 6.8 6.9
a (a.u.) a (a.u.)
Fig. 15 Total energy or binding surfaces for the disordered ferromagnetic alloys Fe60 Ni40 and
Fe65 Ni35 . (All data taken from [113])
Mn Sn
z=1/4
z=3/4
1 1 1 1
2 3 2 2 2
3 3 3
Fig. 16 Crystal and magnetic structure of Mn3 Sn. Rotations of the magnetic moments leading
to weak ferromagnetism in the structure in (c) and (d) are shown only for atoms in the z = 0.25
plane (thin arrows). Moments of the atoms in the z = 0.75 plane are parallel to the moments of the
corresponding atoms of the z = 0.25 plane. (All data taken from [115])
H=− Jij m̂i · m̂j , (51)
i=j
with m̂i(j ) the orientation of the magnetic moment on the lattice site i(j ), for
corresponding simulations. The isotropic exchange coupling parameters Jij , on
the other hand, are calculated in an ab initio way. This can be done by applying
a corresponding version of the so-called Connolly-Williams method [122]. This
implies to calculate the total energy for many different magnetic configurations
within a super-cell and to determine the exchange coupling parameters by fitting
the energy on the basis of Eq. (51). This way one obviously achieves a mapping
of the complicated energy landscape E({m̂i }) on the rather simple expression in
Eq. (51) involving only pair interactions that is easy to handle. Accordingly, a more
accurate representation of the energy as a function of the magnetic configuration
can therefore be expected by a cluster expansion as suggested by various authors
[123, 124].
Another approach to determine the exchange coupling parameters Jij in Eq. (51)
is to consider the change of the single-particle energy ΔEij if two magnetic
moments on sites i and j change their relative orientation. The necessary formal
developments started with the work of Oguchi et al. who expressed the difference
in energy between the ferro- and antiferromagnetic state of a solid making use of
multiple scattering theory and Lloyd’s formula [125]. Lichtenstein et al. [126]
extended this approach dealing with the coupling energy ΔEij associated with an
individual pair (i, j ) of atoms. If ΔEij is expressed to lowest order with respect to
the orientation angle of the moments m̂i and m̂j , one gets a one-to-one mapping of
the exchange coupling energy ΔEij to the Heisenberg Hamiltonian in Eq. (51), with
the exchange coupling constants Jij given by [126]:
EF
1 −1 −1
τ↑ tj−1 −1
ij ji
Jij = dE Trace ti↑ − ti↓ ↑ − tj ↓ τ↓ , (52)
4π
ij
where ti↑(↓) is the spin-dependent single site scattering matrix for site i and τ↑(↓) is
the spin-dependent scattering path operator matrix connecting sites i and j . Results
for the isotropic exchange coupling parameter Jij of Fe and Co as a function of
the distance Rij between sites i and j that have been obtained using an analogous
expression derived within the LMTO-GF formalism [127] are shown in Fig. 17. The
big advantage of this approach is that it can be applied with comparable effort to
more complex systems like disordered substitutional alloys [128], Heusler alloys
[129, 130, 131], diluted magnetic semiconductors [132, 133, 134, 135, 136, 137],
magnetic surface films [127,138], or finite deposited clusters [139,140]. In addition,
it should be mentioned that an approach similar to that leading to Eq. (52) was
worked out by Katsnelson and Lichtenstein [141] that allows for an improved
treatment of correlated systems.
If spin-orbit coupling is accounted for, the exchange coupling parameter in the
Heisenberg Hamiltonian has to be replaced by a corresponding tensor:
222 H. Ebert et al.
20 20
16 Fe 16 Co
12 12
Jij (meV)
Jij (meV)
8 8
4 4
0 0
-4 -4
1 1.5 2 2.5 1 1.5 2 2.5
Rij (units of lattice parameter) Rij (units of lattice parameter)
Fig. 17 Isotropic exchange coupling constants Jij of Fe and Co as a function of the distance Rij
between sites i and j . (All data taken from [127])
H=− m̂i J m̂j + K(m̂i ) (53)
ij
i=j i
=− Jij m̂i · m̂j − m̂i J S m̂j
ij
i=j i=j
− D ij · m̂i × m̂j + Ki (m̂i ), (54)
i=j i
θ2
E(q, θ ) = E0 (θ ) − J (q). (55)
2
Accordingly, performing an inverse Fourier transformation, one can determine the
real-space interatomic exchange coupling parameters J0j . In the case of a simple
Bravais lattice, this is given by the expression
1 −iqR 0j
J0j = e J (q). (56)
N q
Uhl et al. [147] applied this scheme among others for a study of the invar system
Fe3 Pt. From their numerical results for ΔE(q, θ ), they evaluated the spin-wave
stiffness constant A and the exchange parameter J0 that allows to give an estimate
for the Curie temperature on the basis of the mean field approximation (MFA) (see
section “Finite-Temperature Magnetism”). Similar work was also done for two-
dimensional systems as for example magnetic surface films. Within their study on
an Fe film on W(110), Heide et al. also accounted for the spin-orbit coupling [148].
This way they could determine not only the spin-wave stiffness constant A but also
the Dzyaloshinsky-Moriya interaction vectors D.
As discussed in section “Spin Density Functional Theory”, dealing with systems
with narrow electronic energy bands, in order to go beyond the local spin-density
approximation, the LDA+U or +DMFT methods can be used to properly account
for strong electronic correlation in these materials. In order to adapt the method for
the treatment of exchange interactions formulated within the LSDA [126, 18, 142],
a corresponding theory was developed by Katsnelson and Lichtenstein [141] that
employs an analog of the local force theorem to derive expressions for effective
exchange parameters, Dzyaloshinsky-Moriya interaction, and magnetic anisotropy
in highly correlated systems. The authors demonstrated for the particular case of
ferromagnetic Fe that treating correlation effects beyond the LSDA (within the
LDA+Σ approach) in the exchange interactions results in a spin-wave spectrum
and spin-wave stiffness which are in better agreement with experiment than those
obtained within plain LSDA. The important role of additional contributions to the
exchange coupling of the correlation interactions has been demonstrated, e.g., for
half-metallic ferromagnetism in CrO2 [149], magnetic properties of CaMnO3 [150],
and magnetic properties of transition metal oxides [151]. Another important
feature of the exchange interactions observed in various materials are their strong
224 H. Ebert et al.
orientation dependence that would require to go beyond the Heisenberg model when
considering the finite-temperature or spin-wave properties of these materials. This
problem was recently discussed by different groups [151, 152, 153, 154].
Magneto-Crystalline Anisotropy
Considering the difference in energy ΔEX (m̂, m̂ ), with X=A, MCA or shape,
respectively, for the magnetization oriented along directions m̂ and m̂ , respectively,
one has accordingly ΔEX (m̂, m̂ ) = EX (m̂) − EX (m̂ ).
A convenient phenomenological representation of the magnetocrystalline
anisotropy energy can be given by an expansion in terms of spherical harmonics
Ylm (m̂)
m=l
EMCA (m̂) = κlm Ylm (m̂) (58)
l even m=−l
Assuming degeneracy of the energy upon time-reversal, i.e., flip of the magnetiza-
tion, only terms that are even with respect to the orientation m̂ of the magnetization
can occur in these equations. Further restrictions on the expansions are imposed by
the crystal symmetry of the investigated material [7]. Considering, for example,
a hexagonal system with the expansion up to sixth order, the corresponding
hex (m̂) are given by:
expressions for EMCA
hex
EMCA (m̂) = K̃0 + K̃1 Y20 (θ, φ) + K̃2 Y40 (θ, φ)
+K̃3 Y60 (θ, φ) + K̃4 Y64 (θ, φ) (60)
= K0 + K1 (α12 + α22 ) + K2 (α12 + α22 )2 + K3 (α12 + α22 )3
+K4 (α12 − α22 ) (α14 − 14α12 α22 + α24 ), (61)
4 Electronic Structure: Metals and Insulators 225
The shape anisotropy energy Eshape (m̂) is usually associated with the classical
dipole-dipole interaction of the individual magnetic moments mν on the lattice sites
[6, 155]. Accordingly, it can be determined straightforwardly by a corresponding
lattice summation:
mν mν
1 [R nνν · m̂]2
Edip (m̂) = 1−3 , (62)
c2 |R nνν |3 |R nνν |2
νν Rn
EFm̂
ΔESOC (m̂, m̂ ) = − dE N m̂ (E) − N m̂ (E)
1
− nm̂ (EFm̂ ) (EFm̂ − EFm̂ )2 + O(EFm̂ − EFm̂ )3 . (63)
2
Here EFm̂ is the Fermi energy for the magnetization along m̂ while nm̂ (E) and
E
N m̂ (E) = dE nm̂ (E ) are the corresponding DOS and integrated DOS,
respectively.
This approach is used extensively for compounds and layered systems and leads
typically to anisotropy energies that deviate less than 10% from results obtained
from full SCF calculations. By using, in the case of layered systems, layer-resolved
data for the DOS in Eq. (63), a corresponding layer decomposition of the anisotropy
energy ΔESOC (m̂, m̂ ) could be achieved [157]. Application of this scheme for the
spatial decomposition of ΔESOC (m̂, m̂ ) shows that the dominating contributions
originate in general from the interface or surface layers, respectively.
Equation (63) implies that spin-orbit coupling is accounted for within the
underlying electronic structure calculations. Instead one can start from a scalar
relativistic calculation and treat HSOC as a perturbation. Solovyev et al. [158] used
this approach on the basis of the Green function method in combination with the
Dyson equation Eq. (21). This allowed to write the spin-orbit-induced correction
226 H. Ebert et al.
with
EF
1 ij j ji
Eij (m̂) = − dE Trace G0 (m̂) HSOC G0 (m̂) HSOC
i
, (65)
2π
ij
where G0 (m̂) are real space structural Green function matrices corresponding to the
scattering path operator in Eq. (20) [42]. In contrast to Eq. (63), Eq. (65) provides
a unique spatial or component-wise decomposition of the magnetocrystalline
energy. Solovyev et al. [158] used this approach for a detailed study of the
ordered compounds TX with T = Fe, Co and X = Pd, Pt having CuAu structure.
This way they could in particular show that the hybridization between the T
and X sublattices essentially determines their magnetocrystalline anisotropy. In
addition, an expression analogous to Eq. (65) allowed to demonstrate and discuss
the interconnection between the energy correction E(m̂) and the spin-orbit-induced
orbital magnetic moment μorb represented by the expectation value of the angular
momentum operator l. Using a similar approach as sketched here, this relation
was already investigated before by Bruno [159] and also by van der Laan [160].
Assuming a strong ferromagnet with the majority band filled, the relation:
1
ESOC (m̂) = − C ζ σ · l
, (66)
4
was derived, where C is a constant and ζ represents the strength of the spin-orbit
coupling. This equation was used in numerous experimental studies that exploited
the XMCD (X-ray magnetic circular dichroism) and the associated sum rules [9]
to determine in an element specific way the change of the angular momentum Δl
when changing the orientation of the magnetization from m̂ to m̂ to get a component
resolved estimate for the corresponding anisotropy energy ΔESOC (m̂, m̂ ).
A further approach to calculate the spin-orbit-induced anisotropy energy is to
consider the torque T (θ ) exerted on a magnetic moment m when the magnetization
is tilted by the angle θ away from its equilibrium orientation (easy axis). The
corresponding expression for T (θ ),
∂HSOC
T (θ ) =
ψj k
ψj k , (67)
∂θ
j k occ
was given first by Wang et al. [161] for the case that the electronic structure is
represented in terms of Bloch states. A more general expression was obtained on
the basis of multiple scattering theory [162]:
4 Electronic Structure: Metals and Insulators 227
1 EF ∂
−1
Tαm̂û = − dE ln det t( m̂) − G0
, (68)
π ∂α û
where the torque component with respect to a rotation of the magnetization around
an axis û is considered and where t(m̂) is the single-site t-matrix for an orientation
of the moments along m̂ and G0 is the corresponding free electron Green function
matrix.
On the basis of Eq. (67) or (68), respectively, the anisotropy energy
ΔESOC (m̂, m̂ ) is obtained from the torque by integrating along a path connecting
m̂ and m̂ . This approach is especially suited when dealing with systems with
uniaxial anisotropy. Neglecting in this case the dependence on φ, the anisotropy
energy can be represented as ESOC (θ ) = K0 + K1 sin2 (θ ) + K2 sin4 (θ ) with the
torque given by:
dESOC (θ )
T (θ ) = = K1 sin(2θ ) + 2K2 sin(2θ ) sin2 θ. (69)
dθ
Co1Pd2
2 0.68
Co1Pd5 0.4
ΔE (meV/unit cell)
Kt (mJ/m )
Co2Pd4
ΔE (meV)
2
1 0.34 0
Co4Pd2
-0.4
0 0
-0.8
Co3Pd3
-1 -0.34 -1.2
2 4 6 8 10 12 14 1 2 3 4 5 6
t (Å) Number of Fe layers
Fig. 18 Left: calculated total anisotropy energy ΔE of Con Pdm multilayers with (111)-oriented
fcc structure as a function of the thickness t of the magnetic Co layers. Corresponding experimental
data for the product of the anisotropy energy density K and Co thickness t are shown for
polycrystalline films deposited at two different temperatures (triangles up and down). (All data
taken from [163]) Right: SOC-induced (ΔESOC ; circles) and dipole-dipole (ΔEdip ; triangles)
contributions to the total anisotropy energy (ΔE; squares) for the magnetic surface layer system
Fen /Au(001) as a function of the number n of Fe layers. (All data taken from [155])
cases that the classical treatment on the basis of the dipole-dipole interaction leads
to results for ΔEdip (m̂, m̂ ) that are very close to those of a coherent quantum-
mechanical calculation that accounts also for the Breit interaction.
Starting from the 1950s, compounds of rare-earth (RE) with 3d transition metal
(TM) elements, as, for example SmCo5 , or Nd2 Fe14 B, attracted much attention
because of their strong magnetic anisotropy. In these materials, the MCA is
primarily determined by the RE sublattice, while the TM sublattice is responsible
for the magnetic ordering [167]. For that reason, the simplified two-sublattice
Hamiltonian
H = Hd + HCEF
f
+ Hex
d-f
(71)
is often used to discuss their properties, where Hd and HCEF f characterize the TM
and RE, respectively, sublattices while Hex describes the exchange interactions
d-f
between the two. Within the single-ion model, HCEF f accounts for the interaction
of the aspherical 4f-charge with the crystalline electric field (CEF). Due to strong
spin-orbit interaction for the 4f-electrons, rotation of the magnetization leads to a
rotation of their aspherical charge cloud. This in turn results in a dependency of the
electrostatic energy on the orientation of the 4f-magnetic moment as described by
the Hamiltonian [168, 169, 170]
HCEF
f
= n θJ n r
4f On
4f .
Am n m
(72)
n,m
4 Electronic Structure: Metals and Insulators 229
Here Am n are crystal field parameters for the angular momentum quantum numbers
n and m determined by the charge contribution in the system excluding the 4f-
electrons, θJ n are Stevens’ factors depending on the total angular momentum
quantum number J , Onm
4f are the expectation values of the Stevens’ operators, and
r n
4f are the expectation values of r n calculated for the 4f-states of the RE atom.
As the quantities θJ n and Onm
4f are all tabulated, calculation of the crystal field
n together with r
4f allows to fix HCEF and with this to determine
parameters Am n f
0 0
-100
-10
A2 < r >4f (K)
-200
-20
2
-300
-30
0
-400
-500 -40
Ce Nd Sm Gd Dy Er Yb Ce Nd Sm Gd Dy Er Yb
Pr Pm Eu Tb Ho Tm Pr Pm Eu Tb Ho Tm
A02 r 2
have been done, for example, for the Nd sites of the (001)-surface of
Nd2 Fe14 B [175]. It turned out that the sign of A02 r 2
depends on the positions of
the Nd atoms in the unit cell supplying this way an explanation for the different
coercivity of crystalline and sintered Nd2 Fe14 B. Similar calculations have been
performed also to investigate the impact of Dy impurities on the coercivity of
Nd2 Fe14 B [176]. From these, it was found that the parameter A02 r 2
for Dy
atoms in the surface region of Nd2 Fe14 B also may have a positive or negative sign
depending on its position, leading finally to a decrease of the coercivity of sintered
samples.
P. Novák et al. introduced a scheme for the calculation of the crystal field
parameters that avoids the assumption of an inert 4f-charge cloud and allows for
the hybridization of the 4f-states with the surrounding electronic states [177].
The approach is based on a local Hamiltonian represented in the basis of Wannier
functions and expanded in a series of spherical tensor operators. Applications to RE
impurities in yttrium aluminate showed that the calculated crystal field decreases
continuously as the number of 4f-electrons increases and that the hybridization of
4f-states with the states of the oxygen ligands is important. This method has been
successfully applied also to calculate crystal field parameters for RE impurities in
LaF3 [178].
Dealing with ferrimagnetic materials composed of several, inequivalent mag-
netic sublattices, calculating the magnetic anisotropy may become more compli-
cated as an additional canting between the sublattices introduced by an external
field may play a significant role and should be taken into account to get a
reasonable agreement with experiment. This was demonstrated for the RE-TM
ferrimagnet GdCo5 [179], where the authors report a first-principles magnetization-
versus-field (FPMVB) approach giving temperature-dependent magnetization as
a function of an externally applied magnetic field in excellent agreement with
experiment.
Excitations
When considering the magnetization dynamics of solids, one usually assumes the
magnetization to be collinear inside an atomic cell i oriented along the common
direction m̂i implying a coherent rotation of the magnetization within the cell during
progress of time (rigid spin approximation (RSA)) [144]. As a consequence, the
equation of motion for the magnetization can be replaced by the equation of motion
for the local magnetic moments mi = mi m̂i that can be written as [144, 180, 181]:
d 2μB 1 ∂E
m̂i = − × m̂i , (73)
dt h̄ mi ∂ m̂i
where the right-hand side represents the torque acting on the magnetic moment mi .
Making use of the harmonic approximation for the energy, Eq. (73) yields for the
spin waves uλν (q) = uλν eiqR n with wave vector q the following eigenvalue problem
[181]:
2μB νν
h̄ ωλ (q) uλν = J (q) uλν , (74)
mν
ν
for solids with translational symmetry. Here the eigenvectors uλν numbered by the
index λ represent small deviations of magnetic moments from the direction of the
ground state and the J νν (q) are the Fourier transforms of the interatomic exchange
coupling parameters with ν labeling the basis atoms within a unit cell.
Solution of the eigenvalue problem in Eq. (74) obviously yields the frequencies
ωλ (q) of the various collective spin-wave eigenmodes that can be compared with
magnon excitation energies as deduced, for example, from neutron scattering.
Corresponding results obtained for Fe and Ni are given in Fig. 20 in comparison
with experiment. Although good agreement between theory and experiment is
achieved, one has to stress that the theoretical results depend on the method used to
calculate the J νν (q) parameters. The data shown by a solid line were obtained using
the exchange coupling parameters Jij calculated on the basis of the Lichtenstein
formula Eq. (52) [182]. In the case of a lattice with one atom per unit cell, the
magnon energy spectra E(q) possess only a single branch. Therefore, the bcc-
Fe and fcc-Ni magnon spectra in Fig. 20 could be obtained by a simple Fourier
transformation [182]
4μB
E(q) = J0j (1 − eiq·R j ). (75)
m
j
E(q) (meV)
E(q) (meV)
400
300
300
200
200 Expt
Halilov et al.
100 Pajda et al.
100
0 0
Γ N P Γ H N L Γ X W K Γ
Fig. 20 Magnon dispersion relations for bcc-Fe (left) and fcc-Ni (right) along high-symmetry
directions in the Brillouin zone, in comparison with experiment (open symbols [182]). Solid lines
represent the results by Pajda et al. [182], while full circles show the results by Halilov et al. [180]
700
Co 30 Gd Expt
600 Theory
25
500
E(q) (meV)
E(q) (meV)
400 20
300 15
200 10
100 5
0 0
Γ M K Γ A L Γ M K Γ A
Fig. 21 Left: magnon dispersion relation for hcp-Co along high-symmetry lines in the Brillouin
zone [180]. Right: magnon dispersion relation for hcp-Gd (full lines) in comparison with
experimental data. (All data taken from [183])
is performed over a sufficiently large number of atom shells around the central
atomic site with index 0.
As an example for a lattice with a multiatom basis, Fig. 21 (left) displays the
magnon spectrum calculated for hcp-Co [180]. As there are two atomic sites in the
unit cell, solving the eigenvalue problem Eq. (74) leads to two magnon branches.
A similar approach was applied to hcp-Gd [183]. The corresponding experimental
data shown in Fig. 21 (right) were obtained at T = 78 K. This was accounted for
in the calculations within the RPA (see section “Methods Relying on the Rigid Spin
Approximation”) leading to a simple rescaling of the magnon energies proportional
to the temperature-dependent average magnetization.
4 Electronic Structure: Metals and Insulators 233
Usually calculations of the electronic structure for magnetic systems are performed
assuming a collinear spin-magnetic structure and using the smallest unit cell
corresponding to the space group of the system. However, this configuration does
not have to correspond to the ground state of the system. A possible way to
search for the proper magnetic ground state is to consider incommensurate spin-
spiral configurations. Furthermore, within the adiabatic approximation, spin spirals
can be seen as a representation of transverse spin fluctuations. Therefore, self-
consistent calculations on static spin spirals or so-called frozen magnons give
access to the energies of spin-wave excitations that can be used in particular to
investigate the finite-temperature magnetism. Considering a corresponding spin
spiral characterized by the wave vector q and the tilt angles θν and φν , the variation
of the spin-magnetic moment mnν from site to site may be expressed via:
where ν labels the atomic site in the unit cell located at lattice vector R n .
Because of broken translational and rotational symmetry, the presence of a spin
spiral in principle implies an increased unit cell compared to a collinear spin
configuration. However, as shown by Brinkman and Elliot [184, 185] as well as
Herring [186], one can make use of the fact that a spin-spiral structure characterized
by the wave vector q is invariant with respect to a so-called generalized translation:
Tn = {α(φ)|αR |t n }, (77)
that specifies the behavior under a generalized translation for the two-component
eigenfunctions ψj k of a Hamiltonian with a noncollinear spin-dependent potential
of the form (see also Eq. (11)):
q†
↑
Vnν (r) 0 q
V (r) = Unν (θν , φν ) ↓ Unν (θν , φν ). (79)
nν
0 Vnν (r)
Here n specifies the Bravais lattice vector R n , ν gives the position ρ ν of an atom
q
in the unit cell, and Unν is a spin-transformation matrix that connects the global
frame of reference of the crystal to the local frame of the atom site at R n + ρ ν
that has its magnetic moment mnν tilted away from the global z-direction. The
234 H. Ebert et al.
x ϕ=qR
m
θ
z
y
Fig. 22 Geometry of a spin spiral with the wave vector q along the z-direction
q
transformation Unν is characterized by the Euler angles θnν and φnν as it is shown
in Fig. 22. Assuming a collinear alignment of the spin density within the atomic cell
at (n, ν), it is natural to use a local frame of reference with its z-axis oriented along
q
mnν . The corresponding transformation matrices Unν occurring in Eq. (79) can be
q
written as a product of two independent rotation matrices Unν = Un (θν , φν , q) =
Uν (θν , φν ) UqR n , where the matrix UqR n depends only on the translation vector R n
[187]:
i
i
q cos θ2ν sin θ2ν e 2 φν 0 e 2 q·Rn 0
Unν = . (80)
− sin θ2ν cos θ2ν 0e − 2i φν
0e − 2i q·Rn
Results for the wave vector-dependent energy and spin-magnetic moments per
atom obtained by Uhl et al. [188] from corresponding spin-spiral calculations
for γ -Fe are shown in Fig. 23. This work was based on the LSDA and used the
augmented spherical wave (ASW) band structure method in combination with the
atomic sphere approximation (ASA). In addition, noncollinearity within an atomic
cell was neglected. The investigations on γ -Fe by Kurz et al. [189], on the other
hand, avoided these simplifications by the use of the LAPW band structure method.
The noncollinear magnetic structure was imposed by a constraining magnetic field
applied to the magnetic moments of the atoms. Furthermore, the GGA was used
for the exchange-correlation potential. In spite of the various technical differences
between the two studies, the results shown in Fig. 23 agree fairly well and justify
the approach used by Uhl et al. as well as many others.
The implementation of the spin-spiral method within the KKR band structure
method allows dealing not only with ordered materials but also with random alloys
[190]. Figure 24 gives as an example the energy (left) and individual spin moments
(right) for a spin-spiral magnetic structure in Fe0.5 Mn0.5 as a function of the wave
vector q directed along the [001] direction. One can see a transition from the
antiparallel alignment of the Fe and Mn magnetic moments at small q to a parallel
alignment when q approaches the boundary of the Brillouin zone at |q| = 2π/a.
As it is seen from the left part of Fig. 24, the latter magnetic configuration is
energetically more stable.
Apart from exploring the magnetic phase space by performing self-consistent
spin-spiral calculations, the technique can also be used to get access to magnon
4 Electronic Structure: Metals and Insulators 235
0 2
mspin (μB)
-30 1
-60 0
Γ X W Γ X W
Fig. 23 The energies of the spin-spiral structure with respect to the energy of the FM state (left)
and spin-magnetic moments per atom (right) calculated for γ -Fe for the wave vector q varying
along Γ − X − W in the Brillouin zone. Open diamonds represent the results obtained by Uhl et al.
[188] while full circles represent the results obtained by Kurz et al. [189]. (All data taken from
[188] and [189])
3
0.2 MFe
Mn and Fe parallel 2.5 MMn
2 Mtotal
Espin spiral (eV)
1.5
Mspin (μB)
0.1
1
0.5
Mn and Fe
antiparallel 0
0
-0.5
-1
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
qz qz
Fig. 24 Left: energy of a spin spiral in a Fe0.5 Mn0.5 alloy calculated for the wave vectors q =
2π
a (0, 0, qz ) along the [001] direction. Right: local magnetic moments on Fe and Mn atoms as a
function of the wave vector q. (All data taken from [190])
excitation energies h̄ω(q). In the case of simple lattices, the energy ΔE(q, θ ) of a
spin spiral with wave vector q and tilt angle θ can be used directly to get h̄ω(q)
from the expression [191]:
4 ΔE(q, θ )
h̄ω(q) = lim . (81)
θ→0 m sin2 θ
This approach was used, for example, by Halilov et al. [180] to calculate the magnon
energy spectra for Fe and Ni represented in Fig. 20. Obviously, the results are in a
reasonably good agreement with those of Pajda et al. [182] that are based on a
236 H. Ebert et al.
calculation of the real space exchange coupling parameters Jij via the Lichtenstein
formula Eq. (52). As one notes, the minima for Fe along the Γ − H and H − N
directions are given by both approaches. However, the magnons obtained by the
spin-spiral calculations are softer, because of the self-consistent relaxation within
the electronic structure calculations.
As another example, Fig. 25 represents spin-wave dispersion curves obtained for
the full-Heusler alloys Cu2 MnAl, Pd2 MnSn, Ni2 MnSn, and the L12 -type ferromag-
net MnPt3 [192]. The simplified approach used in this work did not fully account for
the magnetic sublattices of the investigated systems providing for that reason only
the first magnon branch. Nevertheless, this already led to values for the Curie tem-
perature calculated within the RPA approach (see section “Methods Relying on the
Rigid Spin Approximation”) in reasonable agreement with experiment. As a general
trend, one can see in Fig. 25 that the calculated magnon energies h̄ω(q) are too high
when compared with experiment. The authors attribute this to the treatment of elec-
tronic correlations on the basis of the GGA. In fact, previous work on the series of
Heusler alloys Co2 Mn1−x Fex Si [62] clearly demonstrated the impact of correlation
effects by comparison of results based on the LSDA, LSDA+U, and LSDA+DMFT.
40
100
20
50
E(q) (meV)
40 100
20 50
Fig. 25 Calculated (solid lines) spin-wave dispersion curves h̄ω(q) in the first Brillouin zone
along high-symmetry directions for the L21 -type full-Heusler and L12 -type ferromagnets. As indi-
cated, the experimental data stem from neutron diffraction measurements at various temperatures.
(All data taken from [192])
4 Electronic Structure: Metals and Insulators 237
The use of the spin-spiral technique for the calculation of the full magnon energy
spectrum in case of complex compounds was demonstrated by Şaşıoğlu et al. [193].
In this case, a set of spin-spiral calculations is required to obtain all exchange
coupling parameters J νν (q) that enter the eigenvalue problem Eq. (74).
Despite the many successful applications of the adiabatic approach for the investi-
gation of spin-wave excitations, one has to stress that it has severe limitations. In
particular it can be applied only to systems for which single-particle or the so-called
Stoner excitations can be neglected [194, 195]. Figure 26 gives a simplified picture
of the exchange-split band structure of an itinerant ferromagnet in the vicinity of its
Fermi level. Excitation of an electron from an occupied majority-spin state below
the Fermi level to an empty minority state may not only be associated with a spin
flip but also with a change of the electronic wave vector. As it is visualized in the
right panel of Fig. 26, these Stoner excitations lead to a broad continuum that in
general overlaps and hybridizes with the discrete magnon dispersion spectrum. For
this and other reasons, a more sophisticated description of spin-wave excitations was
worked out making use of the linear response formalism within the framework of
time-dependent density functional theory [196,197,87,198]. This allows expressing
the magnetization Δmi (r, q, ω) induced by a magnetic field B(r, q, ω), with its
time and spatial dependency expressed by the wave vector q and frequency ω,
respectively, in terms of a corresponding susceptibility tensor [2]:
Δmi (r, q, ω) = d 3 r χ ij (r, r , q, ω) B j (r , q, ω). (82)
j Ω
Δk = q Minority-spin
Excitation energy, ε
Electron energy, E
EF
ΔE = ε δ Stoner continuum
U
U
Magnons
Majority-spin
0 δ
Electron wave vector, k Excitation wave vector, q
Within spin-density functional theory and making use of circular coordinates, one
may write in particular for the transverse susceptibility tensor element χ ± a Dyson-
like equation [87]:
Aλ (q)
χλ+ (q, ω) ≈ , (84)
(ω − ω0λ (q))2 + βλ (q)2
with the amplitude Aλ (q), the spin-wave energy ω0λ (q), and inverse lifetime βλ (q).
As an example, Fig. 27 shows the magnon dispersion curves ω0 (q) together with
the corresponding broadening for the magnon states as deduced from the dynamical
susceptibility as calculated for bcc-Fe and fcc-Co [203]. As one can clearly see
from the given width, Stoner excitations have only a very small influence on the
long-period magnons.
Results for ω0λ (q) and βλ (q) for the Heusler alloy Co2 MnSi that has three
magnetic sublattices are shown in Fig. 28. The corresponding eigenvectors (EV)
Fig. 27 Spin waves of bcc-Fe (left) and fcc-Co (right). Solid circles correspond to ω0 (q), while
the error bars denote full width at half maximum of the peak. Solid line denote spin-wave energies
obtained using the magnetic force theorem [203]
4 Electronic Structure: Metals and Insulators 239
800 150 EV 2
EV 3
600
ω(q) (meV)
β(q) (meV)
EV 1 100
400 EV 2
EV 3
200 50
0
Γ [ξ00] X K [ξξ0] Γ [ξξξ] L Γ [ξ00] X K [ξξ0] Γ [ξξξ] L
Fig. 28 Energies ω0λ (left) and inverse lifetimes βλ (middle) of three spin-wave modes in
Co2 MnSi together with the corresponding eigenvectors (right); arrows indicate the orientations
of the magnetic moments. The basis atoms are Co at (1/4, 1/4, 1/4)a and (3/4, 3/4, 3/4)a and Mn
at (1/2, 1/2, 1/2)a. The parameter β1 of EV 1 does not exceed 5 meV and is not shown. (All data
taken from [87])
of the resulting spin-wave modes are given on the right-hand side of the fig-
ure. The acoustic mode that is lowest in energy has a vanishing energy for
q = 0, and its value for βλ is very small (therefore not shown in Fig. 28).
The optical modes, on the other hand, appear at higher energies where the
continuum density is appreciable. Accordingly, their inverse lifetime βλ is quite
large and depends strongly and non-monotonously on the wave vector q. For
the Heusler alloy Cu2 MnAl, only one magnetic sublattice has to be consid-
ered, and accordingly, there is only one acoustic spin-wave mode. In contrast
to Co2 MnSi, a more pronounced damping is found in this case. The influence
of the Stoner excitations can also be seen for the spin-wave energies. Calcu-
lating these by use of the so-called adiabatic approach [202] that neglects the
hybridization, the spin-wave energies are higher and in less good agreement with
experiment [202].
Comparable studies based on the dynamical susceptibility were done (i) to
investigate the Landau damping in Fe(100) and Fe(110) films and the effect of
the substrate on this [201], (ii) to study the Landau damping of spin waves
and large Rh moments induced by the AFM magnons in FeRh [203], and
(iii) on acoustic magnons in the long-wavelength limit in order to analyze the
Goldstone violation in many-body perturbation theory [204]. The concept of
the dynamic spin susceptibility has been applied also to paramagnetic systems
at finite temperatures by Staunton et al. [205, 206]. Due to the use of the
multiple scattering formalism, investigations on alloys could be made, for exam-
ple, on paramagnetic Cr0.95 V0.05 and antiferromagnetic Cr0.95 Re0.05 above the
Néel temperature TN . While the work sketched here was primarily based on
the linear response formalism applied within the framework of time-dependent
density functional theory, similar work on quasiparticle and collective electronic
excitations in solids was done using techniques from many-body perturbation
theory [207].
240 H. Ebert et al.
Finite-Temperature Magnetism
3kB TC
w= , (85)
m20
e−β hW n̂·ê
P n̂ (ê) = , (86)
d ê e−β hW n̂·ê
constant from the calculated exchange coupling parameters Jij . Within this mean
field approach (MFA), application of classical spin statistics leads to:
2 2
TCMFA = J0j = J0 , (87)
3kB 3kB
j =0
1 1
Gm (z) = , (88)
N q z − E(q)
with E(q) the magnon energies that allows expressing the critical, i.e., Curie or
Néel, respectively, temperature TcRPA as [182]:
1 6
RPA
= − lim
Gm (z), (89)
k B Tc z→0 m
that is applicable to systems with several atoms per unit cell. Here Lν is the so-
called local moment of atom ν that should be found in a self-consistent way [191].
However, in the case of well-localized magnetic moments, values of mν at T = 0
K can be used as a reasonable approximation [216]. Finally, jn (q) in Eq. (90)
is the exchange function after diagonalization of jνν (q) [191]. This expression
accounts in particular for the fact that different atomic types have in general different
moments, while the expressions in Eqs. (88) and (89) that are often applied to
multicomponent systems are based on the assumption that Lν = m0 with m0 , the
average saturation moment. As is demonstrated by the results in Table 2, Eq. (90)
gives in general results for the critical temperature that are in good agreement with
experiment.
An important alternative to the RPA-GF scheme for dealing with magnetic
properties at finite temperatures is provided by the Monte Carlo method that is
used to deal with the statistical aspect of the problem. Corresponding work again
is in general based on the Heisenberg Hamiltonian (see Eq. (51)) with the exchange
parameters calculated in an ab initio way. Numerous successful applications have
been done, both for ordered compounds [218] and for disordered alloys such as
diluted magnetic semiconductors like Ga1−x Mnx As [135, 219, 220] or Heusler
alloys [129, 221]. In most cases, good agreement with RPA-based results as well as
with corresponding experimental data for the critical temperature could be achieved.
Despite the good results often obtained via the RPA and MC methods, one has
to stress that they are based on a classical spin Hamiltonian and therefore are
4 Electronic Structure: Metals and Insulators 243
Table 2 Structure, magnetic moments on M1 and M2 sublattices, as well as critical Curie or Néel
temperature calculated via the MC (TcMC ), RPA (TcRPA ), or MFA (TcMFA ) approaches in comparison
with experiment. (All data taken from [191] and [217])
Exp
System Structure M1 (μB ) M2 (μB ) TcMC/RPA (K) TcMFA (K) Tc (K)
Fe bcc 2.330 – 1060MC 1460 1043
Co fcc 1.410 – 1080MC 1770 1388
Ni fcc 0.630 – 510MC 660 633
FeNi CuAu 2.551 0.600 972RPA 1130 790
CoNi CuAu 1.643 0.673 1149RPA 1538 1140
FeNi3 AuCu3 2.822 0.588 986RPA 1290 870
CoNi3 AuCu3 1.640 0.629 733RPA 925 920
NiMnSb C1b 3.697 0.303 968RPA 1281 730
Mn2 VAl L21 −0.769 1.374 580RPA 663 760
Co2 FeSi L21 2.698 1.149 1058RPA 1267 1100
Mn3 Al L21 −2.258 1.128 196RPA 342 –
Mn3 Ga L21 −2.744 1.363 314RPA 482 –
Mn3 Ga DO22 −2.829 2.273 762RPA 1176 –
RhMn3 AuCu3 3.066 – 1059RPA – 855
suitable only for systems with their magnetic moments depending only weakly on
the temperature. As the latter assumption is not always fulfilled, an extension of
the Heisenberg Hamiltonian was suggested that is meant to account for longitudinal
fluctuations [222, 217] that express the total energy by an expansion in even powers
of the magnetic moments per atom m:
E(M, q, θ ) = An m2n + Jn (q, θ ) m2n . (91)
n n
Here the functions Jn (q, θ ) are proportional to the energy difference between the
ferromagnetic and the spin-spiral states specified by wave vector q and tilt angle θ .
Monte Carlo simulations for bcc-Fe, fcc-Co and fcc-Ni performed on this basis
[217] led to a rather good agreement with experiment as one can see from Table 2.
Another model to account for temperature-induced longitudinal spin fluctuations
was suggested by Ruban et al. [223] that also led for Fe and Ni to a rather realistic
description of the magnetic properties at finite temperatures.
An important class of materials, for which longitudinal spin fluctuations are
of great importance, are alloys and compounds composed of magnetic and other-
wise nonmagnetic elements. Such systems exhibit so-called covalent magnetism
[224, 225], i.e., the magnetization of the nonmagnetic component is caused by
the spontaneously magnetized atoms via a spin-dependent hybridization of the
electronic states. Ležaić et al. [129, 221], for example, emphasized the need
to account for longitudinal fluctuations of the magnetic moment induced on the
Ni atoms for a proper description of the temperature dependence of the spin
polarization at the Fermi energy EF when performing Monte Carlo investigations
244 H. Ebert et al.
on the half-metallic Heusler alloy NiMnSb. For that purpose, they used an extended
Heisenberg Hamiltonian:
1
Hext = Jij mi · mi + (a m2i + b m4i ), (92)
2
ij i∈N i
that allows accounting for transverse and longitudinal magnetic fluctuations con-
nected with the temperature-dependent induced magnetic moment on the Ni atom.
The Heusler alloy NiMnSb was also investigated by Sandratskii et al. [212] using
the spin-spiral approach and treating the magnetic moment of Ni atom as being
induced.
Mryasov et al. [226] found that the induced magnetic moment of Pt plays a
crucial role for the magnetic anisotropy of FePt at finite temperatures. To account
for this, a renomalization of the Fe-Fe exchange interactions according to:
2
χPt
J˜ij = Jij + I Pt
Jiν Jνj (93)
m0Pt ν∈Pt
The methods sketched above that are based on the Heisenberg model obviously
have problems to account for longitudinal spin fluctuations. In addition, they consist
in an incoherent combination of electronic structure calculations and classical
4 Electronic Structure: Metals and Insulators 245
T (K)
T (K)
300
200
200
100
0 0
0 0.05 0.1 0.15 0.2 0 0.2 0.4 0.6 0.8 1
xFe xNi
Fig. 29 Calculated Curie temperature TC of disordered alloys for fcc-Fex Pd1−x (left) using the
Monte Carlo method and fcc-Nix Pd1−x (right) using the MFA, RPA, and renormalized RPA (rRPA)
approaches, in comparison with experiment. (All data taken from [128] and [228])
statistics. These problems can be avoided by the use of the disordered local moment
(DLM) method [230] that deals with the temperature-dependent magnetization
within self-consistent electronic structure calculations. The slow dynamics of the
magnetic moments spatially localized on the atoms when compared to the fast
electron propagation and relaxation time scale allows to make use of the adiabatic
approximation. Assuming ergodicity for the system of local magnetic moments, the
time average required to calculate the average magnetization at a given temperature
can be replaced by the average over the ensemble of all orientational configurations
characterized by a set of unit vectors {êi }. Within the DLM theory, this is determined
by the corresponding single-site probabilities P n̂ (êi ) obtained from Eq. (86) for
the Weiss field hW = hn̂ . Following Györffy et al. [230], hn̂ is determined by
approximating the free energy F corresponding to the microscopic Hamiltonian
H of the considered system by the free energy F0 based on the trial Hamiltonian
H0n̂ = j hn̂ · êj with hn̂ = hn̂ n̂ and using the Feynman-Peierls inequality [231]:
F ≤ F0 + H − H0
, (94)
where the canonical distribution Eq. (86) is used to calculate the average. Using the
Weiss field hn̂ as a variational parameter to minimize the right-hand side of Eq. (94)
one is led to [162]:
n̂ 3
h = d êi êi Hn̂
êi , (95)
4π
where Hn̂
êi denotes the average of Hn̂ with the restriction that the orientation
of the moment on site i is fixed to êi [230]. Self-consistent electronic structure
calculations for a given temperature result in a temperature-dependent magnetic
moment that automatically accounts for longitudinal fluctuations. The resulting
246 H. Ebert et al.
0.8
ΔESOC (meV)
-0.5
0.6
M(T)
-1
0.4
-1.5
0.2
0 -2
200 400 600 800 0.2 0.4 0.6 0.8
2
Temperature T (K) (M(T))
Fig. 30 RDLM calculations on FePt. Left: the magnetization M(T ) versus T for the magnetiza-
tion along the easy [001] axis (filled squares). The full line shows the mean field approximation
to a classical Heisenberg model for comparison. Right: the magnetic anisotropy energy ΔESOC
as a function of the square of the magnetization M(T ). The filled circles show the RDLM-based
results, the full line give K(T ) ∼ [M(T )/M(0)]2 , and the dashed line is based on the single-ion
model function. (All data taken from [232])
4 Electronic Structure: Metals and Insulators 247
m2eff
χCW (T ) = . (97)
3(T − TC )
Using the atomic exchange coupling parameter J , the values J = 0.9, 0.94, and
0.9 eV for Fe, Co, and Ni and the Curie temperatures TC = 1930, 2250, and 620 K,
respectively, are found. The corresponding effective magnetic moments meff = 3.0,
expt
3.0, and 1.93 μB are in reasonable agreement with experiment (meff = 3.2 , 3.15,
and 1.6 μB , respectively)
The importance of correlation effects for finite-temperature magnetism has been
investigated within the framework of the dynamical mean field theory (DMFT) (see
section “Spin Density Functional Theory”) [16,32]. As demonstrated by Kakehashi
248 H. Ebert et al.
1 1
1000
Fe
M(T)/M(0)
χ meff 3TC
TCW (K)
2
Ni
-1
500
CPA+DMFT
Peschard 1925
Chechernikov 1962
0 0
0 0.5 1 1.5 2 0.2 0.4 0.6 0.8 1
T/TC xNi
Fig. 31 Left: temperature dependence of the magnetization M(T )/M(0) and the inverse ferro-
magnetic susceptibility for Fe (open squares) and Ni (open circles) compared with experimental
results for Fe (squares) and Ni (circles). Right: CPA+DMFT-based and experimental values for
the Curie-Weiss temperature of Fe1−x Nix alloys as a function of Ni concentration. (All data taken
from [16, 32] (left) and [239] (right))
Acknowledgments Financial support by the DFG through the SFB 689 and 1277 is gratefully
acknowledged.
4 Electronic Structure: Metals and Insulators 249
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Hubert Ebert studied physics and received his Ph.D. from the
Ludwig-Maximilians-University Munich in 1986. After a post-
doc stay at the University of Bristol (UK), he worked for several
years at the central laboratory for research and development of
Siemens Company in Erlangen. Since 1993 he is professor for
theoretical physical chemistry at the university of Munich.
Contents
Spin Paths and Spin Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
The Importance of Decoherence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Quantum Relaxation in Dipolar Nets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
Large-Scale Coherence and Entanglement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
Future Directions and Open Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
Abstract
Macroscopic quantum effects have been familiar since the discovery of super-
fluids and superconductors over 100 years ago. In the last few decades, it
has been understood how large-scale quantum effects can also show up in
“spin space.” The collective tunneling of many spins was observed in magnetic
nanomolecules and in insulating dipolar-coupled spin arrays, and the tunneling
of ferromagnetic domain walls has also been cleanly identified. To see large-
scale coherence or entanglement effects, the decoherence caused by interactions
with the environment (particularly with nuclear spins) must be controlled.
Theory indicates ways of doing this, and systems ranging from classic magnetic
compounds to deterministically doped silicon will make the job easier. Coherent
G. Aeppli ()
Physics Department (ETHZ), Institut de Physique (EPFL) and Photon Science Division (PSI),
ETHZ, EPFL and PSI, Zürich, Lausanne and Villigen, Switzerland
e-mail: [email protected]
P. Stamp ()
Pacific Institute of Theoretical Physics, University of British Columbia, Vancouver, BC, Canada
e-mail: [email protected]
Ho (τ̂ ) = o τ̂ x + o τ̂ z (1)
We see the tunneling term o tries to drive quantum transitions between | ↑ and
| ↓, but is hindered by the longitudinal field bias o , which pushes the states | ↑,
| ↓ out of resonance. Notice that we can manipulate both o and o with external
fields.
Quantum Ising Spin Networks: Now imagine an interacting “spin net” of two-
level systems τ̂i , with i = 1, 2, ..N, and each with its own tunneling amplitude i
and bias i . Adding interspin interactions between them generalizes (1) to:
HoQI = i τ̂ix + i τ̂iz + Vij τ̂iz τ̂jz (2)
i ij
264 G. Aeppli and P. Stamp
a b
flux
ω n(t)
c 1E+1
1E+0
1E-1
1E-2
o
1E-3 90
1E-4 o
50
Δ(K)
1E-5
o
20
1E-6
o
1E-7 7
o
1E-8 0
1E-9
1E-10
0 1 2 3 4 5
H (T)
Fig. 1 (Continued)
5 Quantum Magnetism 265
Decoherence arises when a quantum system interacts with its environment, and their
Feynman paths and quantum phases become entangled. Even if they later decouple,
averaging over the unknown environmental states then “smears” over states of
the system, destroying phase coherence over some timescale τφ (the “decoherence
time”). Decoherence in many-particle systems is usually much larger than expected,
Fig. 1 Path integrals on the spin sphere. In (a), we show a spin S as a unit charge, moving on the
unit sphere around a magnetic monopole of strength q = h̄S, along a path which has coordinate
n̂(t) = S(t)/S, and encloses a solid angle . The kinetic phase φB = q/h̄ A · dn, where A
is the monopole vector potential (compare the “Aharonov-Bohm” phase [8] accumulated by a
charged particle moving through an ordinary magnetic vector potential A(r) in real space). For
a closed path, Gauss’s theorem then shows that the enclosed flux from the fake monopole is just
φB = S. In (b), a biaxial (easy ẑ-axis, hard x̂-axis) potential field Ho (S) is added (dark areas
are regions of higher potential). The spin moves preferentially between the two minimum energy
states at the poles by tunneling along the pair of minimum action paths (shown as dashed lines),
with amplitudes 12 μ eiϕμ respectively, where μ = 1, 2 labels the paths, and the μ are real.
An external field H⊥ o , applied along the hard x̂-axis, pulls the two states, and the paths between
them, toward x̂, thereby reducing the enclosed area on the unit sphere. In this “symmetric”
case, ϕ1 = −ϕ2 = ϕ(H⊥ ˜
o ) and 1 = 2 = o . The total tunneling amplitude is then just the
sum 12 o (eiϕ + e−iϕ ), i.e., ˜ o (H⊥
o ) = o (H ⊥ ) cos ϕ(H⊥ ). (c) shows the resulting oscillations in
o o
˜ o (H⊥o ), for a typical biaxial potential (easy axis ẑ, hard axis x̂), as a function of transverse field
H⊥ ⊥
o . If Ho is rotated away from x̂ by an angle φ (shown here in degrees), then |ϕ1 | = |ϕ2 |, and
1 = 2 , i.e., one path is favored over the other, and the oscillations are lost
266 G. Aeppli and P. Stamp
a b
+ E(t)
ε(t)
t=0
γk
γk
- E(t)
c Vo Dipolar-Dominated
Regime
Li Ho x Y1-x F4
0.2 K
Mn-12 Quantum
0.1 K
ξ o Relaxation
Regime
Fe-8
1K
Δo Quantum
Coherence
Regime
Fig. 2 (Continued)
5 Quantum Magnetism 267
and still somewhat mysterious (witness the debate over the saturation of dephasing
times in mesoscopic conductors [17, 18]). Moreover, superpositions and entangled
states are extraordinarily sensitive to even very small environmental interactions.
To get a feeling for decoherence, let us go back to our toy tunneling spin, and now
couple it to a bath of “satellite” spins. In the real world, these satellite spins describe
localized modes (defects, nuclear and paramagnetic spins, etc.) which couple to the
central spin [19]. There are also delocalized environmental modes like electrons,
photons, phonons, etc., which also cause decoherence [21, 22], and which can be
described as a bath of oscillators [20]).
How do the satellite spins and oscillators dephase the “central” tunneling spin?
We explain this again using path integral language (Fig. 2). There are three main
decoherence mechanisms:
(i) Typically the environmental modes have their own dynamics, creating an
extra fluctuating “noise” field on the central system. This adds random phases
to each path, eventually destroying phase coherence between them (“noise
decoherence”). The noise can even push the central spin in and out of resonance
(Fig. 2a).
(ii) When the central spin tunnels, it causes a sudden “kick” perturbation on
the satellite spins, giving them an extra phase which is entangled with the
central spin phase – thence dephasing the central spin dynamics (“topological
decoherence” [23]).
(iii) The field on the k-th satellite, from the central spin, flips with the central
spin between two (in general noncollinear) orientations (Fig. 2b). Between
flips, the satellite precesses in these fields. Summing over all central spin
paths, each involving a different accumulated satellite precessional phase,
Fig. 2 The role of decoherence: In (a), we see the effect of a randomly fluctuating environmental
noise bias ε(t) (black curve) on a tunneling two-level qubit with tunneling matrix element o .
The two levels having adiabatic energies ±E(t), with E 2 (t) = 2o + ε2 (t), are shown as red
and blue curves. The system can only make transitions when near “resonance” (i.e., when |ε(t)|
is ∼ o or less, the regions shown in green). In (b), we show schematically the motion of a
satellite spin, in the presence of a qubit which is flipping between two different states | ↑ and
| ↓. When the qubit flips, the qubit field acting on the k-th satellite spin rapidly changes, from
↑ ↓
γk to γk (or vice versa). Between flips, the spin precesses around the qubit field, accumulating
an extra “precessional” phase. Averaging over this phase gives precessional decoherence. The
sudden change of qubit field also perturbs the satellite spin phase, giving further decoherence
(the “topological decoherence” mechanism [23]). (c) shows the important parameters for a spin
network – the typical tunneling splitting o , the characteristic energy Vo of interspin interactions,
and the energy scale ξo governing interactions with the environment (which in insulating magnetic
systems at very low T comes from the coupling to nuclear spins). For definiteness, we show the
parameter range covered in this space by experiments in crystals of Mn-12 and F e-8 molecular
magnets, and in LiH ox Y1−x F4 ; energy scales are in temperature units. In these systems, o is
controlled by varying the transverse field, and Vo is varied by changing x (in LiH ox Y1−x F4 ), or
by diluting the molecules in solution (in F e-8 and Mn-12)
268 G. Aeppli and P. Stamp
Notice that decoherence may involve very little energy transfer – it is not
necessarily a dissipative process. In magnetic systems, the worst low-T decoherence
will come from very low-energy localized modes, particularly nuclear spins,
which cause very little dissipation, but lots of precessional decoherence [19, 25].
Delocalized modes like phonons, photons, and electrons cause strong decoherence
(and strong dissipation) at higher energy, where they have a high density of states.
Thus, at intermediate energies (typically around 0.01 − 0.5 K), decoherence is at a
minimum. This “window” of low decoherence is of great practical importance – it
also exists for many other solid-state systems [26].
The basic problem with our toy model (2) for a quantum computer is now
clear – it ignores decoherence. If we couple each of the spins in the spin net to
an environment, there are now three main energy scales (Fig. 2c). A “quantum”
parameter o (the typical value of i ) drives the dynamics, along with interspin
interactions of typical strength Vo ; but a coupling of each spin to the environment,
having some effective energy scale ξo , destroys phase coherence. If we could switch
off ξo (i.e., stay in the Vo − o plane in Fig. 2c), we would have perfect quantum
behavior, with Vij correlating the entangled dynamics of vast numbers of qubits –
this would be true macroscopic quantum spin entanglement. But how close are we
to this goal?
In fact most work has been done on systems with dipolar interspin couplings, having
non-negligible environmental interactions – i.e., near the Vo − ξo plane in Fig. 2c.
These systems are very complex – but a simple theoretical picture can be given.
Consider first a single spin qubit τi . The net bias i on τiz now includes a dynamic
contribution from the nuclear spin environment. This typically fluctuates over an
energy range ξo ∼ Eo , where Eo defines the energy width of the multiplet of nuclear
spin states coupled to S; this width is easy to calculate if the hyperfine couplings are
known. Then if i is within a “tunneling window” of width ξo around zero bias, the
fluctuating field can actually bring the qubit to resonance (recall Fig. 2a), where it
can make inelastic (i.e., incoherent) transitions [25].
Now consider an interacting network – assuming here for definiteness that go =
o /Vo
1 (the “dipolar-dominated” regime in Fig. 2c). As the resonant spins
tunnel, a “hole” of width ξo should appear in the distribution of longitudinal
fields
in the system, around zero (see Fig. 3a). The interaction contribution j Vij τj to i
then plays a key role – it slowly changes as the τj relax, bringing more spins into
the tunneling window (hole “refilling”). The total spin distribution is then predicted
5 Quantum Magnetism 269
a [P (ξ,t) - P ( ξ,t)]
εo
Vo
2ξo
0 ξ
Fig. 3 (Continued)
270 G. Aeppli and P. Stamp
to relax, with a characteristic “square root” relaxation [27] ∼ (t/τQ )1/2 . One gets
−1
τQ (o ) ∼ (2o /Vo )ξo N(o ), where N(ξ ) is the “density of states” of spins in a bias
energy ξ , i.e., ξo N (H ) is the number of spins in the tunneling window, centered at
the external field bias energy o = gμB SHoz .
Many experiments, using ensembles of magnetic nanomolecules such as F e-8
and Mn-12 (which truncate to two-level systems at low T ), have now tested this
theory. Square root relaxation was found at short times [28, 29, 30]. Wernsdorfer et
−1
al. [30] found the time-evolving hole, of width ξo , by measuring τQ (ξ = o ) for
many different values of o (Fig. 3b). In strongly annealed samples (where M(ξ )
is a known Gaussian independent of sample shape), they also extracted 2o from
measurements of τQ , and showed how it oscillated in a transverse field (Fig. 3c),
and then confirmed this in independent “Landau-Zener” relaxation measurements.
We emphasize these oscillations are not evidence for coherent tunneling, quite the
5 Quantum Magnetism 271
measurements of ξo which were consistent with the calculated value. This is fairly
direct evidence for the nuclear spin-mediated tunneling mechanism. The Leiden
group [33] has also done low-T NMR on Mn-12, seeing not only how nuclear
spins control the tunneling dynamics but also how the nuclear dynamics in turn is
controlled by the molecular tunneling dynamics.
Notice these are all results for short-time quantum relaxation. At longer times,
multi-spin correlations intervene, causing a breakdown of the square root – the
system moves into the quantum spin glass regime, of fundamental interest [35, 36].
Only quantum tunneling, simultaneously involving many spins, allows the system
to escape local potential minima. Experiments on the insulator LiH o0.44 Y0.56 F4 , in
which the lowest magnetic doublets (i.e., two-level systems) of J = 8 H o3+ ions
interact primarily via dipolar interactions, have looked at this tunneling relaxation
(Fig. 4a). Remarkably, much of the relaxation (here to a ferromagnetic ground state)
goes via collective dissipative tunneling of domain walls (see Fig. 4a); this purely
quantum effect has been definitively confirmed by observing its dependence on an
applied transverse field [37]. For these dense H o arrays, we can also reinterpret
the long-time relaxation as a quantum optimization process. One relaxes the system
toward the ground state not by reducing the temperature (as in thermal annealing
optimization protocols [38]), but by “quantum annealing” – exposing the system at
very low T to a large transverse field H⊥ o , allowing it to quantum relax, and then
reducing H⊥ o to zero, thence freezing the dynamics [39]. One then reads the final
state – which is the “solution” to the problem of energy optimization.
Finally, one can also explore the regime where ξo Vo , i.e., where dipolar
interspin interactions are unimportant, and the nuclear environment dominates
completely. Here, a “toothcomb” structure was expected in the quantum relaxation
rate, reflecting the level structure of nuclear spins [25]. This was recently found
(Fig. 4b) in experiments [40] on dilute concentrations of H o ions in LiH ox Y1−x F4
(there was also an interesting catch – residual inter-H o interactions can cause pairs
of spins to co-flip, giving a doubling of the teeth).
We see that the study of the quantum relaxation of a spin net reveals the essential
physics governing the incoherent spin dynamics. Now we can turn to the coherent
spin dynamics.
The acid test of our understanding comes with large-scale quantum effects – where
decoherence must be rigorously suppressed. Of course the traditional view has been
that too many microstates are involved in any macrostate for this to be possible [41].
However, the modern picture is different.
Macroscopic tunneling: In pioneering work, predictions of macroscopic tun-
neling between different flux states in superconducting SQUID rings [20] were
272 G. Aeppli and P. Stamp
Fig. 4 (Continued)
5 Quantum Magnetism 273
c 70
60 0.11 K
0.11 K
χ'' (emu/mole Ho)
with pump
50
0.15 K
40
30
20
10
0
1 10 100 1000
f (Hz)
Fig. 4 Tunneling dynamics of the LiH ox Y1−x F4 system. In (a), we show typical behavior for
the rate of microscopic domain wall depinning in LiH o0.44 Y0.56 F4 , as a function of inverse
temperature (from Ref. [37]); the crossover from thermal activation to T -independent tunneling
−1
relaxation occurs when T ∼ 50 mK. (b) shows the relaxation rate τQ (H ) of the H o spins in a
−3
very dilute system (x = 2 × 10 ), from Ref. [40]. The main peaks in the “toothcomb” pattern,
each separated by the H o hyperfine energy, come from nuclear spin-mediated tunneling of single
H o ions between the lowest doublet states. The n = 8, 9 peaks shown in the inset come from co-
flip tunneling of pairs of H o ions, mediated by residual inter-H o interactions. (c) shows spectral
hole burning for x=0.045, from Ref. [57]. The absorptive part of the magnetic susceptibility is
measured as a function of frequency in the linear response regime using a probe amplitude of 0.04
Oe, giving a broad maximum centered at a frequency which depends strongly on temperature. The
same spectroscopy in the presence of a 0.2 Oe pump at 5 Hz shifts the spectrum, cuts off its tails,
and most important, inserts a sharp hole at 5 Hz.
quantitatively verified in the 1980s [42, 43]. In magnets, similar tunneling was
predicted for large domain walls pinned to defects [44], and also found in
experiments [45,46]. In experiments on large domain walls in mesoscopic Ni wires
(of thickness ∼20 − 80 nm), one sees a crossover to a T -independent escape rate
of the walls from a pinning center, in an applied field; the dependence of the rate
on field can be compared with theory [46]. This tunneling involved roughly 107
spins – not far short of the number of Cooper pairs involved in SQUID tunneling.
A revealing set of experiments [46] also looked at microwave absorption between
different levels – these represented the quantized dynamics of the wall center of
mass, trapped in the pinning potential well. A fairly detailed picture can be given of
these experiments [47, 48].
Such tunneling phenomena involve a collective degree of freedom (SQUID flux,
magnetic domain wall position) which does indeed involve a huge number of
274 G. Aeppli and P. Stamp
microstates. So how can it happen? One reason is that all electronic microstates
(Bogoliubov quasiparticles, magnons) are strongly gapped, by energies EG ∼
10 K. To such high-energy excitations, the collective coordinate tunneling, over a
timescale τo , seems very slow. The amplitude to excite them is then exponentially
small, ∼ O(e−EG τo ), by elementary time-dependent perturbation theory. Of course
there are also many very low-energy excitations (defects, paramagnetic impurities,
nuclear spins, etc. – the “satellite spins” discussed in section “The Importance
of Decoherence”), which can entangle with the collective tunneling coordinate.
However, they cause little dissipation, because their energy is so low – their direct
effect on “single-shot” tunneling is then rather weak.
Large-scale coherence: Coherent superpositions, on the other hand, require phase
coherence between many successive tunneling events [21,22]. Now, the low-energy
environmental microstates are indeed very dangerous [19]. So is macroscopic state
superposition feasible?
In superconductors, the answer to this question came a considerable time ago,
including early experimental evidence for macroscopic flux state superpositions
[49, 50, 51]. The decoherence times τφ for superconducting qubits have undergone
a spectacular rise since the year 2000 so that today, they are viewed as leading
candidates for the fundamental building blocks of quantum computers.
Analogous macroscopic superpositions in magnets - e.g., of “giant qubit”
superpositions of two different magnetization states in a large magnetic particle –
have not yet been confirmed. Some years ago, absorption experiments in very large
ferritin molecules (with Neél vector ∼ 23, 000 μB ) showed sharp resonances,
attributed to coherent tunneling of individual ferritin molecules [53]. However, these
results were hard to understand theoretically, and no other group has confirmed
them; and experiments on much smaller molecules like Mn-12 or F e-8 have
never seen coherence. The basic difficulty is that low-energy decoherence from the
hyperfine coupling to nuclear spins is expected to be large (in ferritin, the hyperfine
coupling to a single 57 F e nucleus is much larger than the tunnel splitting!), and at
higher energies, phonon contributions are not negligible [25, 19].
However, experiments may have simply been looking in the wrong place. The
“window of opportunity” between nuclear spin and phonon energy scales is actually
very wide; by applying strong transverse fields, one can increase o to values
much higher than hyperfine couplings (compare Fig. 1c), but still much lower than
most phonon energies, and optimize the decoherence rate. By combining isotopic
purification with choice of material, one can also remove almost all nuclear spins.
Experimentalists like to define a decoherence Q-factor Qφ = o τφ , which tells us
how many coherent oscillations the system can show before decoherence sets in.
Elementary theory [25, 52] then indicates that for an spin S in an insulator, we have
an optimal Qφ ∼ θD 2 /SK E , where K is the anisotropy energy per electronic spin
o o o
of the magnet, θD the Debye energy, and Eo is again the spreading of the nuclear
multiplet. For example, if θD = 300 K, Ko = 1 K, and S = 106 , then by reducing
Eo to
0.1 K, we should get “mesoscopic” coherent dynamics (i.e., Qφ > 1).
Large-scale entanglement: We next turn to multi-qubit entangled states, but now
involving microscopic spins. It is estimated that quantum information processing
5 Quantum Magnetism 275
(QUIP) will be possible, using error correction [14,16], if the single qubit coherence
Q-factor Qφ > 104 − 105 . This should easily be possible with microscopic spins –
note from above that the optimal Qφ ∼ O(1/S). Thus, theory clearly indicates
that QUIP is feasible with microscopic magnetic qubits, provided electronic deco-
herence is absent (e.g., magnetic ions in insulators or semiconductors, or perhaps
insulating molecular crystals). Many proposals have appeared along these lines – as
an example, consider that due to Kane [54] in Fig. 5, using networks of nuclear spins
in semiconductors to do the computation. Reasonable estimates of decoherence rates
[54] give very small numbers here – problems should only arise, as before, from
very low-energy excitations (e.g., 1/f noise from charge defects). Again, applying
strong fields should help [55], and measurements of the decoherence rates will be
crucial, in this and other designs [56].
Experiments over the last years have given very long spin relaxation times for the
spins associated with isolated impurities and quantum dots in silicon. While this is
very interesting for quantum information science, the finding of sharp resonances in
a strongly interacting many-body system using spectral hole-burning [57, 64, 69]
in LiH o0.045 Y0.995 F4 (see Fig. 4c) is important for the science of disordered
magnetism. The decoherence was remarkably small, in spite of the long-range inter-
H o dipole interactions. The data were explained as a collective effect, involving
tunneling of large clusters of H o spins. These results are both surprising and
exciting – they indicate that we may be close to manipulating entangled mesoscopic
spin states.
To do fully fledged quantum computations will require controlling individual
spins or groups of spins, i.e., control of the parameters i , i , and Vij . Control of i
and i can obviously be done by varying transverse and longitudinal external fields –
in fact, all quantum logic operations can be implemented by varying only one of
these three parameters, and one can also use timed pulses in creative ways (which
also help with decoherence [58,59]), so control of Vij is not crucial. One possibility
276 G. Aeppli and P. Stamp
is to use engineered heterostructures to control the local fields [54]; another would
be to use magnetic STM tips, although the practicality of this for anything other than
demonstration experiments involving a very small number of qubits is questionable.
A more difficult problem will be to measure the quantum state of the spin qubits,
without affecting their operation. One can imagine many possibilities – for example,
bringing in superconducting or magnetic devices, whose tunneling into the qubit
depends on its polarization [60], or using optical methods. Over the last two decades,
great progress has been made on both adiabatic and gated quantum computation.
For solid-state implementations, the leading contenders have been superconducting
qubits, whose decoherence times have dramatically improved, and for which very
complex circuits can be constructed. It is beyond the scope of this chapter on
magnetism to review these developments on magnetism, except to mention that
the quantum annealer manufactured by D-wave systems [62] is built to simulate
the transverse field Ising model, and can therefore be viewed as a programmable
version of LiH o1−x Yx F4 . Equally relevant here and for the future of magnetism are
experiments showing control of the magnetic interactions between the very simple
S=1/2 spins associated with either donors [34] or quantum dots [67] in silicon.
When many of the authors of this volume began graduate work in the 1980s, the
idea of large-scale quantum phenomena in magnetic systems was hardly a topic for
discussion – for ∼70 years, quantum mechanics was only used in magnetism to
discuss atomic and nuclear spins and the microscopic interactions (exchange, spin-
orbit, etc.) operating on them. Now we are discussing and even seeing quantum
phenomena at much larger scales, where magnetic variables were previously treated
as classical – it is in this sense that the “quantum” is being put back into magnetism.
We are on the threshold of a very different era – in which coherent spin states, having
no classical analogue, may come to play a role as important as the macroscopic wave
function in superconductors.
As always, it is difficult to make predictions about a fast-moving field. The
preparation and readout of coherent multi-spin states may well require techniques
from spintronics [61], implemented on submicron scales. The key challenges
here will be (i) to marry spintronics with the science of collective quantum spin
states, under progressively less extreme experimental conditions of magnetic field
and temperature, and (ii) to understand how to suppress electronic decoherence
in conducting magnets. This latter is a hard problem because spin current is not
a conserved quantity, which has made it difficult to find a rigorous theory of
spin dynamics in conducting magnets, although moving to antiferromagnets where
mesoscopic quantum tunneling of domain walls has been identified (in the common
metal chromium) [68] may be a promising route. The development of new materials
having the correct mix of optical, electronic, and magnetic properties will be crucial,
and theory will need to be developed to model candidate materials and devices.
It is sobering that even for an insulator as simple as LiH ox Y1−x F4 , many key
5 Quantum Magnetism 277
discoveries – e.g., the coherent hole burning for x=0.045 – were unexpected, and
dictated by such factors as the availability of samples with particular compositions
at sale prices.
We also note that there are many interesting spin systems apart from electronic
magnets. Magnetic superfluids like 3 H e (see, e.g., [63]), or spin-1 Bose-Einstein
condensates (BECs) of alkali atoms [65, 66], and quantum Hall spin condensates,
offer examples where a spin coherent wave function coupled to another order
parameter can display very rich dynamics, and where large-scale quantum effects
are worth exploring.
Finally, we emphasize a crucial change of perspective in the field. Condensed
matter physicists are accustomed to dealing with only one- and two-spin correlation
functions, whereas quantum information theory requires manipulation and measure-
ment of multi-qubit correlations. We still have a great deal to learn about these, and
the next decades promise to be a very exciting one for quantum magnetism.
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019-11985-1
280 G. Aeppli and P. Stamp
Philip Stamp received his PhD from the Univ of Sussex. After
postdoctoral work in Massachusetts, Grenoble, and Santa Bar-
bara, he held positions in the Univ of British Columbia, and as
a Spinoza Professor in Utrecht. He is currently director of the
Pacific Institute of Theoretical Physics in Vancouver. He works
on theoretical quantum gravity and condensed matter theory.
Spin Waves
6
Sergej O. Demokritov and Andrei N. Slavin
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
Spin Waves in 3D and 2D Systems: Theory and Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . 284
Theory of Spin Waves in 3D and 2D Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
Brillouin Light Scattering a Powerful Tool for Investigation of Spin Waves . . . . . . . . . . . . 288
Spin Waves in 1D Magnetic Elements: Standing and Propagating Waves . . . . . . . . . . . . . . . . 291
BLS in Laterally Confined Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Lateral Quantization of Spin Waves in Magnetic Stripes . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Spin Wave Wells and Edge Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
Implementation of Micro-Focus BLS for Laterally Patterned Magnetic Systems . . . . . . . . 300
Propagating Waves in 1D Magnetic Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
Control and Conversion of the Propagating Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
Inductive Excitation of Spin Waves in 1D Waveguides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
Spin-Torque Transfer Effect and Spin Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
Spin Waves in 0D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
Spin-Torque Nano-Oscillator (STNO) and Emitted Spin Waves . . . . . . . . . . . . . . . . . . . . . 321
Spin-Hall Nano-Oscillator (SHNO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Nature of Spin Wave Modes Excited in 0D Magnetic Nanocontacts . . . . . . . . . . . . . . . . . . 329
Coupling of a STNO and 1D Spin-Wave Waveguide to Each Other . . . . . . . . . . . . . . . . . . 336
Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
S. O. Demokritov ()
Institute for Applied Physics and Center for Nanotechnology, University of Muenster, Muenster,
Germany
e-mail: [email protected]
A. N. Slavin
Department of Physics, Oakland University, Rochester, MI, USA
e-mail: [email protected]
Abstract
Introduction
Felix Bloch introduced the concept of spin waves (SPW), as the lowest-energy mag-
netic states above the ground state of a magnetic medium [1]. Bloch theoretically
considered quantum states of magnetic systems with spins slightly deviating from
their equilibrium orientations, and found that these disturbances were dynamic: they
propagate as waves through the medium. It is interesting to note that the concept
of dynamic spin waves was introduced to explain experimental data obtained
in static measurements. From spin-wave theory Bloch was able to predict that
the magnetization of a three-dimensional (3D) ferromagnet at low temperatures
should deviate from its zero-temperature value with a T3/2 dependence (the famous
Bloch law), instead of the exponential dependence given by the mean field theory.
Albeit the Bloch theory has restricted itself by assuming the dominating exchange
interaction, now we know that the relativistic magnetic dipole interaction plays
a decisive role in the properties of spin waves having the wavelengths that are
much smaller than the interatomic distance in the magnetic medium. Moreover, phe-
nomenologically, spin waves in a wide interval of wavevectors (30 < k < 106 cm−1 )
that is most important for the practical applications are, on one hand, almost entirely
determined by the magnetic dipole-dipole interaction, and, on the other hand, can
be correctly described when the retardation effects are neglected. Such spin waves
are usually called dipolar magnetostatic waves or magnetostatic modes. Due to the
anisotropic properties of the magnetic dipole interaction, the frequency of a spin
6 Spin Waves 283
where M = MS + m(R, t) is the total magnetization, MS and m(R , t) are the vectors
of the saturation and the variable magnetization correspondingly, γ is the modulus
of the gyromagnetic ratio for the electron spin (γ/2π = 2.8 MHz/Oe), and
δW
H eff = − (1a)
δM
is the effective magnetic field calculated as a variational derivative of the energy
function W, where all the relevant interactions in the magnetic substance have
been taken into account (see, e.g., [33–35]). For the case of an unbounded 3D
ferromagnetic medium the variable magnetization m(R, t) depends on time t and
on the three-dimensional radius-vector R. In the spin-wave analysis it is usually
assumed that the variable magnetization m(R, t) is small compared to the saturation
magnetization MS , i.e., the angle of magnetization precession is small. In this case
the variable magnetization can be expanded in a series of plane spin waves (having
a 3D wavevector q):
m (R, t) = mq exp (iqR) . (2)
q
6 Spin Waves 285
where A is the exchange stiffness constant, H is the applied magnetic field, and θ q
is the angle between the directions of the wavevector q and the static magnetization
MS with sin2 θ q being the matrix element of the dipole-dipole (magnetostatic)
interaction. Analyzing Eq. (3), one concludes that if the exchange can be neglected
q2 < < HMS /2A and q 2 << 2π MS2 /A, the spin-wave frequency is independent of q.
It depends solely on θ q demonstrating that the nonexchange (magnetostatic) spin-
wave spectrum is anisotropic and nondispersive. In contrast, for q2 > > HMS /2A
and q 2 >> 2π MS2 /A the spectrum of purely exchange spin waves is isotropic since
the spin wave frequency solely depends on q = |q|.
The transition from 3D to 2D can be made if one considers a magnetic film
with a finite thickness d. In the following, we assume a Cartesian coordinate system
oriented in such a way that the film normal is along the x-axis, and axes y and z are
in the film plane, with the external field H and the static magnetization MS being
aligned along the z-axis. Correspondingly, because the translational invariance along
the direction normal to the film surfaces (axis x) is broken, the three-dimensional
spin wave wavevector is represented as a sum of a two-dimensional continuous in-
plane wavevector q and quantized wavevector κ p ex (p = 0,1,2 . . . ) along the film
thickness: q = q + κ p ex , while the three-dimensional radius vector is represented
as R = R + x ex . Then, the distribution of the variable magnetization along the
film thickness (axis x) can be represented as a Fourier series in a complete set of
orthogonal functions mp (x) [37]:
m (R, t) = mp (x) exp iq R . (2a)
q ,p
These functions mp (x) are chosen in such a way that they satisfy the exchange
differential operator of the second order and the exchange boundary conditions at
the film boundaries [38]:
∂m
+ D m|x=±d/2 = 0, (4)
∂x
x=±d/2
with the boundary conditions Eq. (4). Note that in an finite-in-plane nonellipsoidal
magnetic film samples, the “pinning” of the dynamic magnetization at the lateral
edges of the sample could be determined by the local inhomogeneity of internal
dynamic magnetic field, and a different set of the “in-plane” eigenfunctions for the
expansion of the in-plane components of the variable magnetization can be obtained
in that case [39, 40].
Assuming that the thickness spin-wave modes mp (x) do not hybridize, it is
possible to obtain an approximate “diagonal” dispersion equation for the spin-wave
modes in a magnetic film of a finite thickness that is similar to the classical Kittel
equation (3) [37]:
2A
2
ωp = 2πfp = γ H + q + κp2
Ms
(5)
2A
2 1/2
H+ q + κp + 4π Ms Fpp κp , q , d
2
,
Ms
where
pπ 2
pπ 2
q 2 = qy2 + qz2 + = q2 + , (8)
d d
which for qy d < < 1 is similar to the dispersion equation obtained by Damon and
Eshbach for the dipolar surface mode [19]:
ωDE qy d = 2πfDE qy d
1/2 (11)
= γ H (H + 4π MS ) + (2π MS )2 1 − exp −2qy d .
which is obtained from Eq. (5) using the expressions for the dipole-dipole matrix
elements Fpp (qy d) calculated in [37].
Figure 1 illustrates the typology of the lowest quasi-uniform (p = 0) dipole-
dominated spin-wave modes in the quasi-2D case of a magnetic film for different
mutual orientations between the in-plane wavevector, q , and the static magneti-
zation, MS . Three different geometries are shown. If MS is in the film plane, and
if q is perpendicular to MS , the surface or Damon-Eshbach (DE) mode exists (see
Eqs. (10) and (11)). If q and MS are collinear in the film plane, a mode with a
negative dispersion, or, so-called, the backward volume magnetostatic mode (BV)
exists and has the group velocity that is antiparallel to the wavevector. Finally, if
the magnetization MS is perpendicular to the film plane, the existing mode is the,
so-called, forward volume magnetostatic mode. (FV) In the latter case the dipole-
dipole matrix element F00 (q) in Eq. (5) can be expressed as:
288 S. O. Demokritov and A. N. Slavin
Fig. 1 Typology of spin wave modes in a magnetic film for different orientations of the
magnetization, MS , and the in-plane wavevector, q
F00 q d = P00 q d , (13)
hq, hω
q S = q I ± q (15)
Measuring the frequency shift of the scattered light one obtains the frequency
of the spin wave participating in the BLS process. From Eq. (15) it is evident that
the wave vector qS − qI , transferred in the scattering process, is equal to the wave
vector q of the spin wave. Changing the scattering geometry one can sweep the value
of q and measure the corresponding ω(q). Thus, the spin-wave dispersion ω(q) can
be studied. Note here that for the 3D scattering process the maximum accessible
wavevector q = 2qI , the double value of the light wave vector, corresponds to the
backscattering geometry with the scattering angle θ = 180◦ .
The electromagnetic field of the scattered wave is proportional to the product
of the Faraday/Kerr and other magneto-optical constants of the medium and the
amplitude of the dynamic magnetization, corresponding to the spin wave [45]. Thus,
the BLS intensity, determined by the squared field, is directly proportional to the
dynamic magnetization squared. Magneto-optical effects relate the dielectric tensor
of the medium with Cartesian components of its magnetization. Usually the nondi-
agonal elements of the tensor, the magneto-optical effects (magnetic birefringence
and the Faraday effect and the corresponding dichroisms) are responsible for the
scattering. Therefore, the plane of polarization of the scattered light is rotated by
90◦ with respect to that of the incident light.
The conservation laws, given by Eqs. (14) and (15), follow from the time
invariance of the problem and the translation invariance of an infinite medium,
290 S. O. Demokritov and A. N. Slavin
correspondingly. However, if the scattering volume is finite, the selection rule for
the momentum is broken. For the scattering volume with a size less or comparable
with the wavelength of the light, any spin wave with a wavevector comparable
with that of light contributes to the scattering process. The confinement of the
scattering volume can come from the finite size of the element under consideration
and/or from a small scattering volume of the laser beam. For a thin film or for
nontransparent bulk materials, the thickness of the scattering volume is strongly
confined along the direction normal to the surfaces. Therefore, only the in-plane
wave vector is conserved in the light scattering experiments. As shown in Fig. 3, in
the backscattering geometry the transferred in-plane wavevector q|| is determined
by the angle of incidence q|| = 2qsinα, with q being the absolute value of the wave
vector of the incident light. For green laser light q|| varies in the typical range of
(0–2.5) × 105 cm−1 . This approach is illustrated in Fig. 4 showing the spin-wave
dispersion of a permalloy (Ni80 Fe20 ) film with a thickness of 20 nm, measured in
the DE geometry at the applied magnetic field H = 500 Oe. The experimental data
presented in Fig. 4 were obtained by varying α . The solid line in the figure is the
result of calculation based on Eq. (11) with the value of the permalloy magnetization
4πMS = 9.8 kG.
Fig. 3 Backscattering
process from a thin film. qi is
the wavevector of the incident qs α
light; qs is the wavevector of
the incident light; α is the
angle between the
qi
wavevectors and the film
normal
dispersion of a permalloy 14
(Ni80 Fe20 ) film with
parameters listed in the text
12
measured using BLS. The
solid line is the result of
calculation based on Eq. (11) 10
6
0.0 0.5 1.0 1.5 2.0 2.5
5 -1
q|| (10 cm )
6 Spin Waves 291
Before we consider new effects resulting from the lateral confinement in stripes, let
us first focus on BLS from laterally confined excitations.
It has been already mentioned in the previous sections that the form of the
conservation laws, which determine the BLS process, depends on the dimensionality
of the studied system: due to lack of translational invariance of a thin magnetic film
along the normal to the film surface, the corresponding component of the wavevector
is not conserved. Instead, the scattering angle (see Fig. 3) determines the 2D in-
plane vector, q|| only, whereas all the thickness modes possessing this q|| contribute
to BLS, albeit with different intensity according to their thickness profiles. If now
the in-plane translational invariance of the magnetic film is broken by patterning,
the in-plane wavevector is no longer fully conserved in the BLS process. In the case
of a spin-wave mode localized in a long stripe, the only conserved component is
the component of along the stripe axis. In analogy with the films, all the laterally
confined modes contribute to BLS, whereas the mode profile along the stripe width
(more specific: the corresponding Fourier component of the dynamic magnetization)
defines the contribution of the mode to BLS. Finally, if the confinement takes
place in all three dimensions, no conservation laws for wavevectors can be applied.
One should perform a Fourier analysis of the 3D distribution of the dynamic
magnetization of a particular mode to calculate its contribution to the BLS intensity.
Mathieu et al. [22] and Jorzick et al. [48] investigated spin-wave excitations by BLS
in arrays of permalloy stripes. They have found the effect of lateral quantization of
spin waves due to a finite width of the stripes and observed several dispersionless
spin-wave modes. Since these experiments provide the first account for spin-wave
modes in 1D magnetic systems and heavily contribute to quantitative understanding
of spin wave quantization effects in systems with reduced dimensions, we consider
them in detail.
The samples were made of 20–40 nm thick permalloy films deposited in
UHV onto a Si(111) substrate by means of e-beam evaporation using using
292 S. O. Demokritov and A. N. Slavin
Fig. 5 Scanning electron micrographs of permalloy stripes with a width of 1.8 μm and a
separation of 0.7 μm. (Reprinted with permission from [45], © 2001 by Elsevier)
X-ray lithography with a following lift-off process. Several types of periodic arrays
of stripes with stripe widths w = 1.7 and 1.8 μm and distances between the
stripes above 0.5 μm were prepared. Thus, the interaction between the stripes were
negligible. The length L of the stripes was 500 μm, ensuring 1D-properties of the
stripes. The patterned area was 500 × 500 μm2 , allowing BLS investigation with
a large beam diameter, providing a good wavevector resolution. One of the studied
arrays is shown in Fig. 5. In agreement with the shape-anisotropy arguments, the
magnetic easy axis of the array was along of the stripe axis.
Let us consider a magnetic stripe magnetized in plane along the z-direction
and having a finite width w along the y-direction as shown in Fig. 5. A boundary
condition similar to Eq. (6) at the lateral edges of the stripe should be imposed:
m|x=±d/2 = 0 (16)
One should emphasize that the internal field in the stripe is strongly nonho-
mogeneous due to the nonellipsoidal shape. This nonhomogeneity is of particular
importance close to the edges. In the considered geometry, only the dynamic
internal field is nonhomogeneous, since the static magnetization is along the
edge and does not contribute to the demagnetizing effects. Nevertheless, this
nonhomogeneous dynamic internal field results in specific mechanism for pinning
of the magnetization [39]. Therefore, the Eq. (16) differs from Eq. (6) written for
6 Spin Waves 293
nπ
qyn = (17)
w
where n = 1,2, . . . . Using Eqs. (4), (11), and (12) and the quantization expression
(17) one can calculate the frequencies of these so-called width (or laterally
quantized) modes. The profile of the dynamic part of the magnetization m in the
nth mode can be written as follows:
nπ
w
mn (y) = An sin y+ (18)
w 2
PSSW
3000
1000
0
6 10 14
Frequency Shift (GHz)
Fig. 6 Experimental BLS spectrum obtained from the stripe array with a stripe thickness of 40 nm,
a width of 1.8 μm, and a separation of 0.7 μm. The applied field is 500 Oe orientated along the
stripe axis. The transferred wavevector of q|| = 0.3 × 105 cm−1 is oriented perpendicular to the
wires. The discrete spin-wave modes are indicated by arrows. PSSW stands for perpendicular
standing spin-wave mode. (Reprinted with permission from [45], © 2001 by Elsevier)
24
Spin Wave Frequency [GHz]
n=3
PSSW n=2
20 n=1
16
12
8 Q-DE
4
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Magnetic Field [kOe]
Fig. 7 Frequencies of the in-plane quantized Damon-Eshbach modes (Q-DE) as a function of the
applied field, obtained from the BLS spectra similar to that shown in Fig. 6. The lines are calculated
using Eq. (11) with quantized wavevectors, determined by the quantization numbers n = 1,2,3.
The line labeled PSSW shows the frequency of the first perpendicular standing spin-wave mode.
(Reprinted with permission from [45], © 2001 by Elsevier)
6 Spin Waves 295
17
9 n=2
8
n=1
7
6
0.0 0.5 1.0 1.5 2.0 2.5
5 -1
q|| (10 cm )
Fig. 8 Obtained spin-wave dispersion curves for an array of stripes with a stripe thickness of
40 nm, with a width of 1.8 μm and a separation of 0.7 μm (open symbols) and 2.2 μm (solid
symbols). The external field applied along the stripe axis is 500 Oe. The solid horizontal lines
indicate the results of a calculation using Eq. (11) with the quantized wavevectors, determined by
the quantization numbers n = 1,2,3,4,5. The dashed lines showing the hybridized dispersion of the
Damon-Eshbach mode and the first PSSW mode were calculated numerically for a continuous film
with a thickness of 40 nm. (Reprinted with permission from [45], © 2001 by Elsevier)
14
Spin Wave Frequency (GHz)
d = 20 nm
13
12
11
10 n=5
n=4
9 n=3
8 n=2
7 n=1
6
0.0 0.5 1.0 1.5 2.0 2.5
5 -1
q|| (10 cm )
Fig. 9 Obtained spin-wave dispersion curves for an array of stripes for the same conditions as in
Fig. 8, but with a stripe thickness of 20 nm. (Reprinted with permission from [45], © 2001 by
Elsevier)
296 S. O. Demokritov and A. N. Slavin
The main features of the observed spin wave modes in magnetic stripes can be
summarized as follows: (i) For low wavevector values (0–0.8 × 105 cm−1 ) the
discrete modes do not show any noticeable dispersion, behaving like standing wave
resonances. (ii) Each discrete mode is observed over a continuous range of the
transferred wavevector qy . (iii) The lowest two modes appear very close to zero
wavevector, the higher modes appear at higher values. (iv) The frequency splitting
between two neighbored modes is decreasing for increasing mode number. (v)
There is a transition regime (qy = 0.8–1.0 × 105 cm−1 ) where the well-resolved
dispersionless modes converge towards the dispersion of the continuous film (see
dashed lines in Figs. 8 and 9).
All these features can be explained if one implies that the observed discrete,
dispersionless spin wave modes result from a confinement of the DE modes in
the stripes. The confinement causes width-dependent quantization of the in-plane
wavevector of the mode, as discussed above. Considering the corresponding Fourier
component of the dynamic magnetization one can reproduce the measured BLS
intensity of each modes [48].
The frequency of the observed modes can be derived by substituting the
obtained quantized values of the wavevector, qyn , determined by Eq. (17) into the
dispersion equation of the DE mode, Eq. (11). The results of these calculations
are shown in Figs. 8 and 9 by the solid horizontal lines. For the calculation
the geometrical parameters (stripe thickness d = 20 or 40 nm, stripe width
w = 1.8 pm) and the independently measured material parameters 4πMs = 10.2 kG
and γ = 2.95 GHz/kOe were used. Without any fit parameters the calculation
reproduces all mode frequencies very well.
In the previous subsection, the simplest geometry with the applied magnetic field
aligned along the stripe axis was considered. In this case, the static field is
homogeneous, while the dynamic field is not homogeneous resulting in the pinned
boundary conditions for the dynamic magnetization. If, however, the applied field is
directed along the width of a thin stripe, both the static and the dynamic internal field
are strongly inhomogeneous. Spin waves propagating along the field are affected in
this case not only by the confinement effects but also by the above inhomogeneities.
Since in unconfined media a wave with q||MS is called the backward volume (BV)
magnetostatic wave, we refer to this experimental geometry as the BV geometry,
contrary to the geometry described in the previous subsection, which we call the
DE geometry. Figure 10 shows two typical BLS spectra obtained from an array of
stripes for the external in-plane magnetic field He = 500 Oe for different orientations
of the field. The spectrum (a) is recorded with both transferred wavevector and He
aligned along the width of the stripe (the BV geometry), whereas the spectrum (b)
is obtained for He oriented along the stripe axis, thus presenting the DE geometry
6 Spin Waves 297
LM
Band
BLS Intensity (a.u.)
(a)
(b)
0 5 10 15 20
Frequency shift (GHz)
Fig. 10 BLS spectra obtained on the stripe array described in the text, q = 0.3 × 105 cm−1 and
He = 500 Oe for (a) the DE geometry and (b) the BV geometry. LM indicates the localized mode.
(Reprinted with permission from [23], © 2002 by the American Physical Society)
discussed in detail above. As it is seen in Fig. 10, both spectra contain several
distinct peaks corresponding to spin-wave modes. The high-frequency peaks can
easily be identified as exchange-dominated PSSW modes. Thus, a narrow PSSW
peak in spectrum (b) confirms the homogeneity of the static internal field in the DE
geometry. On the contrary, a broad PSSW peak in spectrum (a) clearly indicates
a strong inhomogeneous distribution of the internal field across the stripe in the
BV geometry. For a large He the magnetization is parallel to the applied field within
almost the entire stripe. Therefore, poles are created at the edges of the stripe, which
decrease the internal magnetic field in those regions. A detailed analysis shows that
the internal static field, Hi , has a broad maximum in the center of the stripe while it
is vanishing completely near the edges of the stripe [49, 50].
To get further inside into the physics of the observed spin-wave modes, their
dispersion was measured by varying q. It is displayed in Fig. 11 for both orientations
of He . Figure 11a representing the DE geometry is very similar to Figs. 8 and 9: it
clearly demonstrates the lateral quantization of the DE spin waves, resembling a
typical “staircase” dispersion. The frequency of the PSSW mode coincides with
that of the PSSW mode for the unpatterned film and corresponds to an internal
field of Hi = He = 500 Oe, thus corroborating a negligible static demagnetizing
field in the stripes magnetized along their long axes. The dispersion presented in
Fig. 11b and representing the BV geometry differs completely from that shown
in Fig. 11a. First, the PSSW mode is split into two modes, with frequencies
298 S. O. Demokritov and A. N. Slavin
Fig. 11 Spin wave dispersion of the stripe array measured at He = 500 Oe for (a) the DE geometry
with the quantization numbers of the quantized modes as indicated and (b) the BV geometry. In
the latter case, the shadowed region represents the band of non-localized spin modes, whereas LM
indicates the localized mode. The solid lines represent the results of calculation. (Reprinted with
permission from [23], © 2002 by the American Physical Society)
2 q (H (z), f ) dz +
ψ1 +
ψ2 = 2rπ (20)
where r = 1,2,3, . . . and q(H(z),f ) is found from the spin-wave dispersion Eqs. (4)
and (5), and
ψ l ,
ψ 2 are the phase jumps at the left and right turning points,
between which Eq. (4) has a real solution q(z) for a fixed frequency f.
We will illustrate these ideas in the following. The dispersion curves for spin
waves with q||He and p = 0 calculated using Eqs. (4) and (5) for different constant
values of the field are presented in Fig. 12. A dashed horizontal line shows the
frequency of the lowest spin-wave mode f1 = 4.5 GHz obtained from Eq. (20) for
the lowest value r = 1 in good agreement with the experiment. It can be seen from
Fig. 12 that for H > 237 Oe there are no spin waves with the frequency f1 = 4.5 GHz.
Therefore, the lowest mode can exist only in the spatial regions in the magnetic
stripe where 0 Oe < H < 237 Oe. The corresponding turning points are indicated in
the inset of Fig. 12 by the vertical dashed lines. Thus, the lowest mode is localized
in the narrow region
z near the lateral edges of the stripe where 0.26 < |z/w| < 0.39.
The mode is composed of exchange-dominated plane waves with qmin < q < qmax ,
as indicated in Fig. 12.
The higher-order spin-wave modes with r > 1 having their frequencies above
5.3 GHz are not strongly localized under the used experimental conditions and exist
everywhere in the stripe where the internal field is positive (0 < |z/w| < 0.39). In
the experiment, they show a band, since the frequency difference between the fr and
fr + 1 modes is below the frequency resolution of the BLS technique. Note here that
several localized modes can be observed at higher values of He [51].
300 S. O. Demokritov and A. N. Slavin
Fig. 12 Dispersion of plane spin waves in the BV geometry at constant internal fields as indicated.
Inset: the profile of the internal field in a stripe.
z shows the region of the lowest mode
localization. (Reprinted with permission from [23], © 2002 by the American Physical Society)
All the above BLS data were obtained in the so-called Fourier microscope mode
[48]. In this case, the diameter of the laser beam was kept quite large (typically
30–50 μm), allowing fulfilling the wavevector conservation law Eq. (15), and the
frequencies and the intensities of the studied spin-wave modes were investigated as
a function of transferred wavevector.
A complimentary approach is the micro-focus BLS [46]. Here the coherent laser
light focused onto the surface of the magnetic system into a diffraction-limited spot
by using a high-quality microscope objective lens with a large numerical aperture.
While the frequency shift of the scattered light is equal to the frequency of the
magnetization oscillations, its intensity (referred to as BLS intensity) is proportional
to the intensity of magnetization oscillations at the position of the probing spot.
The latter fact enables direct spatial imaging of the spin-wave intensity by two-
dimensional rastering of the probing spot over the sample surface (Fig. 13a). The
acquired intensity maps, such as that shown in Fig. 13b, allow one to obtain
information about the spatial characteristics of spin waves. In the case of spin-wave
6 Spin Waves 301
a)
Microwave
current
Probing
Antenna
light
H0 Magnonic
waveguide
Substrate
b) 1 BLS c)
intensity,
-1
a.u.
10
-2
10 1
cos (ϕ) 0
500 nm
-1
that the phase of the scattered light is directly correlated to the phase of the
magnetization oscillations in the spin-wave mode. This phase information can be
acquired by utilizing interference of the scattered light with the light modulated
by the signal used to excite the magnetization oscillations. This approach enables
direct measurements of the phase difference between the excitation signal and
the phase of a propagating spin wave at the given spatial location, providing, for
example, direct information about the spin-wave wavelength. The phase-resolution
technique was first demonstrated for standard macro-BLS apparatus [53] and was
subsequently adapted for micro-focus BLS measurements [54, 55]. Figure 13c
shows a representative example of the measured spatial phase map for spin waves
propagating in a submicrometer-width magnonic waveguide, excited by microwave
current in the antenna. The plotted value is cos(ϕ), where ϕ is the phase difference
between the microwave current and the magnetization oscillations in the spin wave.
The spatial period of cos(ϕ)-function is equal to the spin-wave wavelength at a given
excitation frequency. Therefore, by varying the latter and measuring the spatial
period, one can obtain the complete information about the spin-wave dispersion
characteristics of the studied waveguide.
By analyzing the lateral quantization of spin waves in stripes in the previous sub-
sections, we have considered standing waves, i.e., we implied that the component of
the wavevector along the stripe axis is zero. To extend this approach to propagating
waves in such a waveguide we should consider two components of the wavevector:
one component quantized due to finite width of the stripe and another component
continuously varying as illustrated in Fig. 14. In fact, if the quantized components
qzn are known, the spectrum of normal waveguide modes can be obtained from the
two-dimensional dispersion surface described by Eq. (4) and by cutting it along qy
at the fixed qzn as illustrated in Fig. 14a by the curves labeled as DE1 − DE3 . For
the sake of clearness we project these curves onto the frequency- qy plane, as shown
in Fig. 14b, keeping in mind that the different curves correspond to different qzn .
As seen from Fig. 14b, the considered modes propagate perpendicular to He , i.e.,
they are analogues of the DE mode in an extended film, their dispersion curves are
shifted to lower frequencies with respect to that of the unconfined DE mode, and this
shift increases with the increase of the mode number. This is not surprising, since all
these modes are characterized by a nonzero component of the wavevector qz parallel
to He . Since the dipolar magnetic energy is known to decrease with the increase
of this component causing the backward dispersion of the BV modes (Fig. 14a),
the dispersion curves of the waveguide modes shift to lower frequencies with the
increase of the mode number, which corresponds to the increase in qz .
We emphasize that the above-described approach to calculation of the dispersion
curves of the normal waveguide modes is a rough approximation, since they do not
take into account the reduction of the static magnetic field inside the waveguide
6 Spin Waves 303
Frequency
z DE
dispersion spectrum of spin
waves in an extended in-plane y DE1
magnetized ferromagnetic
film. Inset shows the DE3
geometry of the stripe DE2 f0 DE2
waveguide and transverse DE1 BV
profiles of the dynamic
magnetization for normal DE3 qy
waveguide modes. (b)
Calculated (solid lines) and H0
qz
measured (symbols)
dispersion curves for a b)
waveguide with the width
10
DE1
w = 800 nm and the Frequency, GHz DE
thickness d = 20 nm DE2
f1
magnetized by the static field 9 DE3
He = 900 Oe. Dashed line
shows the dispersion curve
for Damon-Eshbach mode in 8
an extended film. (© 2015 q1 q2 q3
IEEE. Reprinted, with 0 1 2 3 4 5 6
permission, from [47]) -1
qy, μm
caused by the demagnetization effects, which can be further taken in account using
Eq. (19).
The data of Fig. 14b show that the dispersion spectrum of waveguide modes
supports multimode propagation of spin waves at all frequencies above f0 . For exam-
ple, by exciting spin waves at the frequency f1 (see Fig. 14b), one simultaneously
excites a number of modes with different longitudinal wavevectors qy . Neglecting
attenuation of spin waves, the spatial distribution of the intensity of the dynamic
magnetization in these patterns can be described as (cf. Eq. 18):
2
nπ
w
I (y, z) = An sin z+ exp −iq n y (21)
n w 2
where An are the amplitudes of the modes and qn are their longitudinal wavevectors
at the given excitation frequency (see Fig. 14b). Figure 15 shows the results of
calculations based on Eq. (21) performed for different ratios between the amplitudes
An and the dispersion data taken from Fig. 14b. In the simplest case, where the
only present mode is the fundamental mode with n = 1 (Fig. 15a), the intensity
distribution is uniform in the longitudinal direction and shows a half-sine profile
in the transverse direction. The co-propagation of the fundamental mode and the
mode with n = 2 (Fig. 15b) results in an appearance of a “snake”-like pattern,
which becomes more pronounced with the increase of A2 . We note that, because
of the symmetry reasons, the mode n = 2 possessing an antisymmetric distribution
of the dynamic magnetization across the waveguide width (inset in Fig. 14a) is
304 S. O. Demokritov and A. N. Slavin
z, μm
waveguide modes calculated 0
for different ratios between
their amplitudes, as labeled. -0.4
Calculations were performed b) A1=1, A2=0.15, A3=0
for the waveguide with the 0.4
z, μm
width of 800 nm and the 0
thickness of 20 nm
magnetized by the field -0.4
A1=1, A2=0.3, A3=0
He = 900 Oe. (© 2015 IEEE. 0.4
z, μm
Reprinted, with permission,
0
from [47])
-0.4
c)
A1=1, A2=0, A3=0.15
0.4
z, μm
0
-0.4
A1=1, A2=0, A3=0.3
0.4
z, μm
0
-0.4
0 1 2 3 4 5
y, μm
normally not excited in axially symmetric guiding systems and can only be observed
if this symmetry is broken. In contrast, a significant contribution of the mode
with n = 3 is detected in most of the experiments. As seen from Fig. 15c, the
co-propagation of this mode and the fundamental mode of the waveguide results
in a periodic spatial beating pattern, where the spin-wave energy is periodically
concentrated in the middle of the waveguide, while the transverse width of the spin-
wave beam shows a periodic modulation. By analogy with the light focusing in
optics, this effect was given a name of “spin-wave focusing” [56]. Figure 16a shows
a typical measured spin-wave intensity map for a 2.4 μm wide and 36 nm thick
Py waveguide clearly demonstrating this effect (compare with Fig. 15c). In order
to highlight the details of the interference pattern in Fig. 16a, the spatial decay
of spin waves is numerically compensated by multiplying the experimental data
by exp.(2y/ξ), where ξ is the spin-wave decay length – the distance over which
the wave amplitude decreases by a factor of e. The latter is determined from the
dependence of the BLS intensity integrated across the transverse waveguide section
versus the propagation coordinate (solid symbols Fig. 16b). As seen from Fig. 16b,
spin waves in the studied waveguide exhibit clear exponential decay characterized
by ξ = 6.4 μm. Figure 16b also shows by open symbols the transverse width
of the spin-wave beam versus the propagation coordinate, which can be used to
quantitatively characterize the strength of the focusing effect. In particular, for the
data of Fig. 16b, the modulation of the beam width caused by the focusing is equal to
about 70%, while the smallest width observed at the focal point is equal to 0.65 μm.
6 Spin Waves 305
a) Propagation
z, μm
0 0.5
-1 0
0 1 2 3 4 5 6 7
y, μm
b) 1 1.5
Beam width, μm
intensity, a.u.
Integral
1.0
0.1 0.5
0 1 2 3 4 5 6 7
y, μm
Fig. 16 (a) Measured map of the spin-wave intensity for a waveguide with the width of 2.4 μm
and the thickness of 36 nm magnetized by the field of 900 Oe. Excitation frequency is 9.4 GHz.
Spatial decay of spin waves is numerically compensated. (b) Solid symbols – BLS intensity
integrated across the transverse waveguide section versus the propagation coordinate in the log-
linear scale. Line is the exponential fit to the experimental data. Open symbols – transverse width
of the spin-wave beam measured at one half of the maximum intensity versus the propagation
coordinate. (© 2015 IEEE. Reprinted, with permission, from [47])
Figure 17a shows this distribution calculated for the waveguide with the width
of w = 2.1 μm and the thickness of d = 20 nm magnetized by the static field
He = 1100 Oe. As seen from this data, close to the edges of the waveguide, the
internal field is drastically reduced resulting in the appearance of field-induced
channels, where spin waves can be localized, as discussed in previous subsection.
306 S. O. Demokritov and A. N. Slavin
a)
1000
field, Oe
Internal
500 Field-induced
channels
0
-1.0 -0.5 0.0 0.5 1.0
z, μm
0 0
-1
0 2 4 6 8 10
y, μm
c) 1.5 0.6
Distance between
Beam width, μm
the beams, μm
1.0 0.5
0.5 0.4
9.0 9.2 9.4 9.6 9.8
Frequency, GHz
Fig. 17 (a) Calculated distribution of the internal static magnetic field across the width of a
waveguide with the width of 2.1 μm and the thickness of 20 nm magnetized by the static field of
1100 Oe. Horizontal dashed line marks the value of the external magnetic field. (b) Measured maps
of the spin-wave intensity for two excitation frequencies, as labeled. Spatial decay of spin waves
is numerically compensated. (c) Distance between the centers of the spin-wave beams and their
transverse width measured at one half of the maximum intensity versus the spin-wave frequency.
(© 2015 IEEE. Reprinted, with permission, from [47])
Since these modes are mostly concentrated in the areas of the reduced field,
their typical frequencies are lower than the frequencies of the “center” modes as
discussed above. Therefore, in order to address them experimentally, one needs
to excite the waveguide at frequencies below the frequency of the uniform ferro-
magnetic resonance f0 (see Fig. 14a). Figure 17b shows two decay-compensated
spin-wave intensity maps measured for a waveguide with the parameters given
above by applying the excitation signal at the frequencies of 9.0 and 9.8 GHz, which
are smaller than f0 equal to about 10 GHz for the used experimental conditions.
6 Spin Waves 307
The data of Fig. 17b show that, in agreement with the simple qualitative model,
at these frequencies, the spin waves do not occupy the entire cross-section of
the waveguide. Instead, they form two narrow beams with the submicrometer
width whose spatial positions depend on the spin-wave frequency. The quantitative
analysis (see Fig. 17c) shows that, in the wide frequency interval, the widths of
the beams vary moderately staying in the range 400–500 nm, while the distance
between their centers monotonously increases with the decrease of the frequency
from 0.8 μm to 1.4 μm, i.e., by more than 70%.
Frequency, GHz
measurements by 7
phase-resolved BLS
technique. (c) Longitudinal 6
wavevector qy and the I=-12 mA
wavelength of the spin wave 5 I=0
at the frequency of 7 GHz
versus the control current. 0 1 2 3 4 5 6
Symbols – experimental data, -1
qy, μm
lines – guides for the eye. (©
2015 IEEE. Reprinted, with c) 5 2.5
permission, from [47])
Wavelength, μm
-1
2.0
qy, μm
1.5
3
1.0
-15 -10 -5 0 5 10 15
Current, mA
for technical applications. Based on the data of Fig. 18c, one can conclude that by
applying the control current of ±12 mA, the phase accumulated by the spin wave
can be changed by ±π radians at the propagation distance of about 3.2 μm which is
smaller than the spin-wave propagation length. This makes the proposed mechanism
well suited for implementation of magnonic logic devices [57], where the digital
information is coded into the phase of propagating spin waves.
In addition to the use of magnetic fields created by electric currents, the control
of spin-wave propagation can also be realized by using demagnetizing fields. Since
the demagnetizing field depends on the ratio between the width and the thickness of
the waveguide (Eq. 22), simple variation of one of these parameters enables efficient
manipulation of spin waves [58, 59].
A waveguide with the varying width is schematically shown in Fig. 19a: while
the thickness of the waveguide d = 36 nm remains constant, its width w varies from
1.3 to 2.4 μm over a transition region with the length L. According to Eq. (22),
such a variation results in a spatial variation of the internal field, which changes
from 870 Oe in the narrow part of the waveguide to 950 Oe in the wide part
(Fig. 19b). Due to this variation, the dispersion curves of the fundamental center
waveguide mode are shifted in the two parts by about 500 MHz in the frequency
domain (Fig. 19c). If the excitation frequency is chosen to be located between the
6 Spin Waves 309
a) z b)
waveguide
y 1.3 μm 950
Narrow
field, Oe
waveguide
Internal
He
Wide
900
L
850
2.4 μm
0 1 2 3 4 5 6
y, μm
c) 11
Frequency, GHz
Wide
f2 waveguide
10
f1 Narrow
9 waveguide
0 1 2 3
-1
qy, μm
d)
Propagation
8.7 GHz 9.1 GHz
1 μm
e) L=3 μm L=1 μm
Fig. 19 (a) Schematic of a spin-wave waveguide with a varying width. (b) Calculated distribution
of the internal static magnetic field in the section along the axis of the waveguide with the
thickness of 36 nm and the geometrical parameters given in (a). The external static magnetic field
He = 1000 Oe. (c) Calculated dispersion curves for the fundamental center waveguide mode in the
wide and the narrow parts of the waveguide. (d) Maps of the spin-wave intensity measured at the
excitation frequencies of 8.7 and 9.1 GHz, as labeled. Width of the transition region L = 2 μm. (e)
Maps of the spin-wave intensity measured at the excitation frequency of 9.7 GHz in waveguides
with L = 3 and 1 μm, as labeled. In (d) and (e) the spatial decay of spin waves is numerically
compensated. (© 2015 IEEE. Reprinted, with permission, from [47])
cut-off frequencies of the two dispersion curves, i.e., between 8.7 and 9.2 GHz (f1 in
Fig. 19c), the center mode propagating in the narrow part of the waveguide cannot
pass into the wide part. Instead, it should be transformed into the edge mode, whose
frequency range is located below that of the center modes. This case is illustrated
in Fig. 19d showing two spin-wave intensity maps measured for the excitation
frequencies of 8.7 and 9.1 GHz. These maps clearly demonstrate the conversion
of the center mode into the edge mode characterized by two narrow spin-wave
beams with frequency-dependent spatial separation (see Sect. “Implementation of
Micro-Focus BLS for Laterally Patterned Magnetic Systems”). Since the two beams
310 S. O. Demokritov and A. N. Slavin
propagate in the field-induced channels and are independent from each other, the
observed transformation can be used for implementation of a spin-wave splitter.
One also observes interesting behaviors in the case, when the frequency of
spin waves is larger than cut-off frequencies in both parts of the waveguide (f2 in
Fig. 19c). In the waveguides with the relatively long transition region (L = 3 μm
in Fig. 19d) the propagation of spin waves from the narrow to the wide part
is quasi-adiabatic. It is only accompanied by the increase in the wavelength,
while the spatial structure of the spin-wave beam remains unchanged. However,
in systems with shorter transitions (e.g., L = 1 μm in Fig. 19e), the propagation
is accompanied by an appearance of a complex intensity pattern, which can be
recognized as an interference pattern created by several waveguide modes with
comparable amplitudes (see Fig. 15c). This is due to the strong coupling of the
waveguide modes mediated by the spatial nonuniformity in the waveguide, which
results in the efficient energy transfer from the fundamental mode to the higher-
order modes. As seen from Fig. 19e, this effect causes a strong concentration of
the spin-wave energy in the middle of the waveguide at a certain distance from the
transition region, which can be treated as an enhanced spin-wave focusing.
A particularly interesting case is a junction between a 1D waveguide and 2D
film [60, 61] (Fig. 20a). Because of the abrupt transition in such a system, the
wavevector of spin waves is not conserved during the conversion of the waveguide
modes into the modes of the extended film. In other words, being radiated from
the open end of the waveguide, the waveguide mode excites spin waves within
a large range of wavevectors. Because of the temporal translation symmetry, the
frequency of radiated spin waves is equal to that of the waveguide mode. Therefore,
the characteristics of the radiated waves can be obtained by considering constant-
frequency contours of the two-dimensional dispersion surface (Fig. 14a), as shown
in Fig. 20b. Figure 20c shows such contours projected onto the qz − qy plane,
calculated for the conditions used in the experiment: d = 36 nm, He = 690 Oe.
In this representation the vector of the group velocity of spin waves Vg is directed
along the normal to the constant-frequency contour: Vg = 2π ∇ f (qy , qz ). As
seen from Fig. 20c, except for the region of small qz , the direction of the group
velocity is practically constant and builds a well-defined angle with the direction
of the static magnetic field He . This indicates that a large group of spin waves with
different wavevectors transmits energy in the same direction. Therefore, one expects
predominant radiation of the spin-wave energy from the waveguide along this
direction. Figure 20d shows an experimental spin-wave intensity map corresponding
to the frequency of 8.2 GHz. The shown experimental data confirm the conclusions
of the above analysis: the spin waves are radiated in a form of two narrow beams and
their directions coincide well with the direction of the group velocity obtained from
the analysis of the 2D dispersion surface (arrows in Fig. 20d). Since the direction
of the beams is determined by He , it can be electronically steered. In general, the
phenomenon enables a directional, 1D transmission of spin waves in an extended
2D magnetic film without utilization of the geometrical confinement. Recently, this
phenomenon was also observed for spin waves radiated by a spin-torque nano-
oscillator [62], which, due to its small size, also emits spin waves within large
interval of wavevectors.
6 Spin Waves 311
a) b)
Frequency
z DE
y
f2
Waveguide
He f0 f1
BV f0
qy
Extended film
qz
-2 He
-4
0 2 4 6 1 μm
-1
qy, μm
Fig. 20 (a) Schematic of a junction between 1D waveguide and 2D extended film. (b) Two-
dimensional dispersion surface of spin waves in an extended magnetic film with marked constant-
frequency contours. (c) Constant-frequency contours projected onto the qz -qy plane calculated for
t = 36 nm and He = 690 Oe. (d) Measured map of the intensity of spin waves with the frequency
of 8.2 GHz radiated from a waveguide with the width of 2 μm into an extended magnetic film.
The spatial decay of spin waves is numerically compensated. (© 2015 IEEE. Reprinted, with
permission, from [47])
w/2 ∞
An ∝ n
hy (z)my (z)dz · hy (y)my (y)dy
n
(23)
−w/2 −∞
nb
1 − (−1) sin
n q y
An ∝ (24)
n qyn
6 Spin Waves 313
x Antenna
a)
Microwave z hy(y)
current y
b
h
He
my(y)
Magnetic
waveguide y
b)
Edge DE
BLS Intensity,
Modes Modes
a.u.
f0
c) 8
n=3
6
-1
2π/d
qy, μm
n=1
4
2
0
d)
1.0
n=1
An, a.u.
0.5
n=3
0.0
7 8 9 10 11 12 13
Frequency, GHz
Fig. 21 (a) Schematic of a waveguide with the spin-wave antenna on top. Inset schematically
shows the y- and z-profiles of the dynamic field of the antenna and those of the dynamic
magnetization in the spin-wave modes. (b) Spin-wave excitation curve measured in a waveguide
with the width of 2 μm and the thickness of 36 nm magnetized by the static field of 900 Oe. (c)
Calculated dispersion curves for the first two symmetric waveguide modes. Horizontal dashed line
shows the value of qy , at which the excitation efficiency vanishes. Arrows show the corresponding
frequencies for the two modes. (d) Calculated amplitudes of the first two symmetric waveguide
modes versus the excitation frequency. The vertical dashed line in (b)–(d) marks the frequency of
the uniform ferromagnetic resonance f0 . (© 2015 IEEE. Reprinted, with permission, from [47])
314 S. O. Demokritov and A. N. Slavin
The first term in Eq. (24) shows that the amplitudes of the modes decrease
with the increase of the mode number as 1/n and that only modes with symmetric
transverse profiles can be excited. The second term shows that the excitation
efficiency has a maximum at qy = 0, exhibits an oscillatory behavior in agreement
with the experimental data of Fig. 21a, and vanishes for qy = 2π m/b or b = mλ,
where m = 1,2,3 . . . and λ is the wavelength of the spin wave.
Figure 21d presents the frequency dependences of the amplitudes of the first
two symmetric waveguide modes calculated based on Eq. (23) and the dispersion
curves obtained by using Eqs. (4) and (5) (shown in Fig. 21c). The calculations
were performed for the conditions used to acquire the experimental excitation curve
shown in Fig. 21b: w = 2 μm, d = 36 nm, He = 900 Oe, and b = 1.5 μm. As
seen from Fig. 21d, the fundamental mode with n = 1 clearly dominates over
the mode with n = 3 and the nodes of the corresponding curve match well with
those seen in the experimental data. We note that, due to the shift of the dispersion
curves corresponding to different modes (Fig. 21c), the frequencies, at which the
excitation efficiency vanishes, are different for the modes with n = 1 and 3. Since
the contribution of the mode with n = 3 is relatively small, vanishings of its
amplitude cannot be seen in the experimental curve in Fig. 21b. Nevertheless, this
vanishing can be proven by the spatial imaging of the spin-wave propagation. These
measurements show a strong reduction in the spatial transverse modulation of the
spin-wave beam at the frequency of about 10 GHz in agreement with the data
of Fig. 21d. We emphasize that the dependence of the relative amplitudes of the
waveguide modes on the excitation frequency allows one to control the strength of
the spin-wave focusing effect. If the transverse modulation of the spin-wave beam
is not desired, one can choose the spin-wave frequency in the vicinity of the point
of the vanishing excitation efficiency of the mode with n = 3, while by choosing
the frequency in the region, where the excitation efficiencies of both modes are
approximately equal, one obtains the strongest mode interference.
The above-described simple model can be extended by additionally taking
into account the out-of-plane component of the dynamic magnetic field of the
antenna [65]. This extension does not significantly modify the discussed frequency
dependence of the excitation efficiency. However, it results in different excitation
efficiencies of spin waves propagating in the positive and the negative direction of
the y-axis. This excitation non-reciprocity is often confused with the intrinsic non-
reciprocity of DE modes [19], which has no effect for spin waves with qy < <1/d
addressed in most of the experiments utilizing the inductive spin-wave excitation.
For typical parameters of the Py micro-waveguides, the excitation non-reciprocity
results in the factor of 4–5 difference between the intensities of waves propagating
in the opposite directions from the antenna.
The above analysis shows that by using an inductive spin-wave antenna one
can only efficiently excite spin waves within a certain interval of wavevectors
corresponding to the first oscillation lobe of the excitation efficiency function
(Fig. 21d), whose spectral width is determined by the width of the spin-wave
antenna b. This limits the applicability of standard inductive excitation, since, in
order efficiently to excite short-wavelength spin waves necessary for most of the
magnonic applications, one has to reduce the width of the antenna, which inevitably
6 Spin Waves 315
causes the microwave impedance matching problems and increases the microwave
losses in magnonic devices. This drawback can be partially overcome [59] by
utilizing the spin-wave controllability by the demagnetizing fields discussed in
Sect. “Propagating Waves in 1D Magnetic Structures”.
Figure 22a schematically shows a system enabling inductive excitation of spin
waves with the wavelength smaller than the width of the antenna: the width of
the waveguide equal to 2 μm in the excitation area gradually reduces to 0.5 μm,
while the thickness of the waveguide d = 40 nm stays unchanged. As discussed
in detail in Sect. “Propagating Waves in 1D Magnetic Structures”, the variation of
the waveguide width leads to the variation of the internal field along the waveguide
axis, which causes the shift of the dispersion curves of the waveguide modes in
the frequency domain. As a result, spin waves excited in the 2 μm-wide part of
the waveguide continuously decrease their wavelength propagating in the tapered
part. This process is illustrated by the two-dimensional phase map (Fig. 22b) and its
section along the waveguide axis (Fig. 22c) obtained by using the phase-resolved
micro-focus BLS technique. The experimental data clearly show a significant
reduction of the wavelength, which, after passing the tapered part, becomes smaller
than the width of the antenna equal to 2.2 μm. Figure 22d further characterizes
this wavelength conversion process. It shows the dependence of the spin-wave
wavelength at the output of the tapered part on the wavelength in the excitation
area. These data show that the discussed conversion process enables the reduction
of the wavelength by up to a factor of 15 and allows one to efficiently excite
spin waves with the wavelength below 1 μm, which is more than by a factor of 2
smaller than the antenna width. We also note that, as shown in [59], the conversion
process is not accompanied by noticeable additional losses associated with the spin-
wave reflection in the transition region, which makes it favorable for technical
applications.
Since the first demonstration [25, 27–29, 66, 67] of the possibility to excite
magnetization dynamics by spin-polarized electric currents due to the spin-transfer
torque (STT) effect [6, 7], dynamic spin-torque phenomena have become the subject
of intense research. The ability to control high-frequency magnetization dynamics
by dc currents is promising for the generation of microwave signals [68–72] and
propagating spin waves [16, 30, 73–75] in magnetic nanocircuits. Electronically
controlled local generation of spin waves is particularly important for the emerging
field of nanomagnonics, which utilizes propagating spin waves as the medium for
the transmission and processing of signals, logic operations, and pattern recognition
on nanoscale [3–5].
Initially, STT phenomena have been studied in 0D-nanodevices based on the
tunneling or giant magnetoresistance spin-valve structures, where STT is induced
by the electric current flowing through a multilayer that consists of a “fixed”
magnetic spin-polarizer and the active magnetic layer, separated by a nonmagnetic
316 S. O. Demokritov and A. N. Slavin
a) z 2 μm b)
y
cos (ϕ)
He 2.2 μm 1
L
on
0
ati
ag
0.5 μm
op
-1
Pr
c) 1
cos (ϕ)
-1
0 2 4 6 8 10
y, μm
d) 1.5
wavelength, μm
Converted
1.0
0 5 10 15 20 25
Excited wavelength, μm
Fig. 22 (a) Schematic of a tapered waveguide with the spin-wave antenna located in the wide
part. (b) Measured phase map of spin waves propagating in a 40 nm thick tapered waveguide
magnetized by the static field He = 900 Oe. The length of the tapered part L = 5 μm. Excitation
frequency is 9.8 GHz. (c) Section of the phase map along the waveguide axis. (d) Dependence of
the spin-wave wavelength at the output of the tapered part on the wavelength in the excitation area.
(© 2015 IEEE. Reprinted, with permission, from [47])
metallic or insulating spacer. In these structures, the electric charges must cross
the active magnetic layer to excite its magnetization dynamics. To enable current
flow through the active magnetic layers, STT devices operating with spin-polarized
electric current require that current-carrying electrodes are placed both on top and
on the bottom of the spin valve. To keep the electric current below a reasonable
limit, the devices should have sub-100-nm dimensions in both lateral directions.
An alternative approach to the implementation of STT devices that avoids
these shortcomings utilizes pure spin currents – flows of spin not accompanied
by directional transfer of electrical charge. This approach does not require the
flow of electrical current through the active magnetic layer, resulting in reduced
Joule heating and electromigration effects. One can also eliminate the electrical
leads attached to the magnetic layer to drain the electrical current, enabling novel
geometries and functionalities of the STT devices. Moreover, it becomes possible to
use insulating magnetic materials such as Yttrium Iron Garnet (YIG) [12, 76].
6 Spin Waves 317
Among the physical mechanisms for creation of pure spin currents, the spin-
Hall effect (SHE) [9–11, 77] plays the most important role so far. The effect is
generally significant in nonmagnetic materials with strong spin-orbit interaction,
such as Pt and Ta. An electrical current in these materials produces a spin current
in the direction perpendicular to the charge flow, due to a combination of spin-
orbit splitting of the band structure (intrinsic SHE), and the spin dependence of the
electron scattering on phonons and impurities (extrinsic SHE) [11, 77]. When a SHE
layer is brought in contact with a ferromagnetic film, the spin current flows through
the interface into the ferromagnet and exerts STT on its magnetization [78]. The
ability to exert STT on ferromagnets over extended areas is a significant benefit of
SHE. Indeed, when an in-plane current flows through an extended bilayer formed by
a SHE material and a magnetic film, the spin current produced by SHE is injected
over the entire area of the sample, which can be as large as several millimeters
[78]. This feature makes SHE uniquely suited for the control of the spatial decay
of propagating spin waves in 1D waveguides, when STT partially compensates the
natural magnetic damping.
The effect of pure spin current on the magnetization is similar to that of
spin-polarized electric currents. Both can be described by the Slonczewski-Landau-
Lifshitz-Gilbert equation [8]:
dM α dM β
= −γ M × H eff + M× + 2 M × M × ŝ (25)
dt Ms dt Ms
I
Pt
Spin-wave Microwave IS
YIG
antenna current
M
He
Spin wave
I
z y Pt (8 nm) /
x YIG (20 nm)
waveguide
Probing
laser light GGG substrate
Fig. 23 Schematic of the experiment on compensation of the spin-wave damping by pure spin
current. Inset illustrates the generation of the pure spin current by the spin-Hall effect. (Reprinted
from [79], with the permission of AIP Publishing)
static magnetic field, the spin current either compensates or enhances the effective
magnetic damping in the YIG film.
The effects of spin current on the decay length of propagating spin waves were
performed by applying a microwave signal at the frequency corresponding, for the
given conditions, to a spin wave with the wavelength of about 5 μm, which can be
efficiently excited by the used 3 μm wide inductive antenna and possess sufficiently
large group velocity. The propagation of spin waves was mapped by rastering
the probing laser spot over the surface of the YIG waveguide with step sizes of
200 and 250 nm in the transverse and the longitudinal directions, respectively.
Figure 24a shows a representative map of the BLS intensity, proportional to the
local intensity in the spin wave, obtained for I = 2.55 mA. As seen from these data,
the spin wave propagates along the waveguide nearly uniformly without changing
its transverse profile (inset in Fig. 24a), which is a clear signature of the single-
mode propagation regime caused by the strong separation of the transverse modes
in a narrow waveguide. The intensity of the wave decreases by only 60% over the
propagation path of 10 μm. To characterize the decay length of spin waves and its
dependence on the current, we plot in Fig. 24b the dependences of the spin-wave
intensity on the propagation coordinate obtained for different dc currents in the Pt
layer. These data show that spin waves in the waveguide experience well-defined
exponential decay (note the logarithmic vertical scale) ∼ exp(−2y/ξ), where ξ is the
decay length defined as a distance over which the wave amplitude decreases by a
factor of e. As seen from the figure, the decay length strongly increases with the
increase of the dc current, as expected for the effect of spin current on the effective
magnetic damping.
6 Spin Waves 319
Fig. 24 (a) Normalized spatial intensity map of the propagating spin wave excited by the antenna.
The map was recorded for I = 2.55 mA. The mapping was performed by rastering the probing spot
over the area 1.6 by 10 μm, which is larger than the waveguide width of 1 μm. Dashed lines
show the edges of the waveguide. Inset shows the transverse profile of the spin-wave intensity. (b)
Dependences of the spin-wave intensity on the propagation coordinate for different currents, as
labeled, in the log-linear scale. Lines show the exponential fit of the experimental data. (c) Current
dependences of the decay length and the decay constant. Vertical dashed line marks IC . Solid line is
the linear fit of the experimental data at I < IC . The data were obtained at He = 1000 Oe. (Reprinted
from [79], with the permission of AIP Publishing)
320 S. O. Demokritov and A. N. Slavin
Figure 24c summarizes the results of the spatially resolved measurements. The
decay length (up-triangles) monotonously increases with the increase of I < IC
and then shows an abrupt decrease at I > IC in contradiction to naive expectations
that for large values of I the magnetic damping should be overcompensated by the
spin current, and the propagating spin wave should be amplified. This experimental
observation can be attributed to the strong nonlinear scattering of the propagating
spin waves from large-amplitude current-induced magnetic fluctuations, which have
been observed independently. To characterize the variation of the decay length
with current in detail, we plot in Fig. 24c its inverse value – the decay constant
(down-triangles), which is proportional to effective Gilbert damping constant αeff .
In agreement with the simple theoretical model assuming the linear variation of αeff
with current, the decay constant shows a linear dependence on I. By extrapolating
this dependence to I = 0, we obtain the propagation length at zero current
ξ0 = 2.4 μm. Additionally, one expects the linear dependence in Fig. 24c to cross
zero at I = IC , which corresponds to an infinitely large decay length under conditions
of the complete damping compensation. The data of Fig. 24c show, however, that
the linear fit yields the intercept value larger than IC . This disagreement can be
attributed to the Joule heating of the waveguide by the electric current in Pt resulting
in the significant reduction of the effective magnetization. Since the decay length is
proportional to the group velocity, which is known to decrease with the decrease
in Meff , the effects of the heating on the propagation length counteract those of the
spin current and do not allow one to achieve the decay-free propagation regime. We
note, however, that the maximum achieved propagation length of 22.5 μm is nearly
by a factor of two larger compared to the value of 12 μm estimated for a waveguide
made of a bare YIG film without Pt on top (α = 5 × 10−4 ).
Spin Waves in 0D
The STT effect discussed above is of a particular importance for magnetic systems
fully confined in all three directions. It is now well established that a spin-polarized
electric current or, alternatively, a pure spin current, injected into a ferromagnetic
layer through a nanocontact exerts a torque on the magnetization, leading to a
strongly localized microwave-frequency precession of magnetization, which can be
considered as a 0D spin-wave mode. This phenomenon can serve as a basis for the
development of tunable nanometer-size microwave oscillators, the so-called spin-
torque nano-oscillators (STNO) [25, 27–29, 66, 67]. The density of magnetic energy
in auto-oscillations excited by STT in a magnetic nanocontact could be very high.
Therefore, the STT-induced precession modes are, usually, strongly nonlinear. Also,
since the spin precession excited in a magnetic nanocontact is, usually, surrounded
by a 2D film or is coupled to a 1D waveguide, it may radiate propagating spin waves.
All these makes the phenomena connected with the STT-driven magnetization
dynamics multifarious and intriguing. This section is devoted to the 0D spin-wave
modes driven by spin-polarized electric or pure spin currents.
6 Spin Waves 321
Top electrode
Current
flow
Insulator
nm
200
nm
500 Py film
Nanopillar
Bottom electrode
Fig. 25 Schematic of the studied STNO with an AFM image superimposed. The devices consist
of an extended 6 nm thick Permalloy free layer and an elliptical nanopillar formed by a 9 nm thick
Co70 Fe30 polarizing layer and a 3 nm thick Cu spacer. The nanopillar is located close to the edge of
the top electrode enabling optical access to the free layer for BLS microscopy. Magnetic precession
in the device is induced by dc current flowing from the polarizer to the free layer. The spatially
resolved detection of spin waves is accomplished by focusing the probing laser light into a 250 nm
spot, which is scanned over the surface of the Py film. (Reprinted from [31], with the permission
of Springer Nature)
He 5° He He
25° 45°
Fig. 26 Pseudo-color logarithmic maps of the power spectral density (PSD) of the signal
generated by the device due to the magnetoresistance effect at different angles ϕ between the
in-plane magnetic field and the easy axis of the nanopillar, as labeled. (Reprinted from [31], with
the permission of Springer Nature)
effects in Py and the dipolar field of the structured Co70 Fe30 polarizer. For small ϕ,
the nonlinear shift is strongly negative. It becomes less pronounced with increasing
ϕ and changes to positive at small I and ϕ > 20◦ . The region of positive nonlinear
frequency shift is reduced at larger He and eventually disappears for He > 1200 Oe,
suggesting its origin from the dipolar field of the polarizer. The possibility to control
the nonlinear behaviors by varying the angle ϕ makes the studied STNOs uniquely
suited for the analysis of the effects of the nonlinearity on the spin-wave emission.
Figure 27 shows two-dimensional intensity maps of spin waves emitted by
STNO at I = 5 mA, measured for different in-plane directions of the applied field
He = 900 Oe. As seen in Fig. 27, the emission mainly occurs in the direction
perpendicular to the in-plane field, regardless of its orientation, the generation
frequency, or the magnitude of the nonlinear frequency shift. We note that although
the sign of the nonlinear shift is expected to be important for the efficiency of
spin-wave emission, the maps of Fig. 27 corresponding to significantly different
nonlinear behaviors of the STNO (see Fig. 26) differ predominantly by the direction
of emission, which rotates together with the field.
Figure 28 illustrates the spin-wave characteristics determined at the location of
the maximum spin wave intensity. Figure 28a–c show the BLS spectra of the emitted
spin waves for I increasing from 3 to 5 mA, together with the spectrum of the
thermal spin waves. The spectra exhibit a small nonlinear frequency shift at ϕ = 45◦ ,
which increases as ϕ is reduced, in agreement with the electrical measurements
shown in Fig. 26. Figure 28d summarizes the dependences of the frequency-
integrated spin-wave intensity on the current I. As seen from these data, the intensity
of the emitted spin waves increases linearly with current for the angle ϕ = 45◦
characterized by a small nonlinear frequency shift. In contrast, the data for ϕ = 25◦
6 Spin Waves 323
a b He
He
He
He
500 nm
c d
He
He He
He
Normalized
intensity 0.0 0.2 0.4 0.6 0.8 1.0
Fig. 27 Normalized color-coded intensity maps of spin waves emitted by the STNO, recorded
at different angles ϕ between the in-plane magnetic field He = 900 Oe and the easy axis of the
elliptical nanopillar: (a) ϕ = 5◦ o, (b) ϕ = 25◦ o, (c) ϕ = 45◦ o, (d) ϕ = − 45◦ o. The bias current is
I = 5 mA. The schematic of the top electrode is superimposed on each map, with a cross indicating
the location of the nanocontact. The intensity maps acquired at I = 0 were subtracted to eliminate
the contribution from the thermal spin waves. Arrows show the direction of the static magnetic
field, and the dashed lines indicate the direction of the spin-wave emission. (Reprinted from [31],
with the permission of Springer Nature)
a He 5° b He
7 8 9 10 11 7 8 9 10 11
Frequency, GHz Frequency, GHz
c He d
45°
BLS intensity, a.u.
Integral intensity
7 8 9 10 11 3 4 5
Frequency, GHz I, mA
Fig. 28 (a–c), Dependence of BLS spectra on the current for different in-plane directions of
He = 900 Oe, as indicated. Shadowed regions show the spectrum of the thermally excited spin
waves determined by measurement at I = 0. Color lines show the spectra acquired at the currents
of 3.0 mA (black), 3.5 mA (blue), 4.0 mA (green), 4.5 mA (red), and 5.0 mA (pink). Dashed
vertical lines mark the frequency of the ferromagnetic resonance (FMR). (d) Dependences of the
integrated intensity of emitted spin waves on current for ϕ = 5◦ (triangles), 25◦ (squares), and 45◦
(dots). (Reprinted from [31], with the permission of Springer Nature)
spin waves emitted by STNOs: the decay length of 540 nm for the auto-emission was
increased to 940 nm for the pumping-induced emission. Moreover, the phenomenon
of the pumping-induced emission does not disturb the unique directionality found
for the emission in the auto-oscillation regime, as illustrated by Fig. 29.
Fig. 29 Pseudocolor spatial intensity maps of the emitted spin waves, acquired at I = 5 mA.
A schematic of the top electrode and a cross indicating the location of the nanocontact is
superimposed on each map. (a) Spin-wave auto-emission, in the absence of the external pumping
microwaves. (b) Spin-wave emission under influence of parametric pumping. Note an extended
spin-wave propagation area for (b). (Reprinted with permission from [80], © 2011 by the American
Physical Society)
Fig. 30 (a) a
Scanning-electron
DC
microscopy image of the test Probing laser Current
spin-Hall nano-oscillator. The light
device consists of a 4 μm
diameter disk formed by a
8 nm thick Pt on the bottom
and a 5 nm thick Py layer on
top, covered by two pointed
Au(150 nm) electrodes Py(5)Pt(8)
He Disk
separated by a 100 nm gap.
(b) Normalized calculated Au(150)
distribution of current 1μ Top electrodes
m
through the section of the b
device shown in the inset by a
dashed line. (Reprinted from 1
current density
Normalized
0
-2 -1 0 1 2
z, μm
section across the middle of the gap (Fig. 30b) shows that most of the current flows
through a 250 nm wide Pt strip. This electric current creates a pure spin current
flowing into Py, due to the spin-Hall effects. The spin current injected into Py exerts
spin-transfer torque on its magnetization. As a result, the damping is compensated,
and the dynamic magnetic modes are enhanced.
Figure 31 shows the BLS spectra obtained with the probing spot positioned in
the center of the gap between the electrodes, at different values of the dc current
I. At I = 0, the BLS spectrum exhibits a broad peak corresponding to incoherent
thermal magnetization fluctuations in the Py film (Fig. 31a). As this thermal peak
grows with increasing current, its rising front becomes increasingly sharper than
the trailing front, consistent with the preferential enhancement of the low-frequency
modes. Analysis of the dependence of the frequency-integrated BLS intensity on
current (Fig. 31b) shows that the intensity of magnetic fluctuations diverges as the
current approaches a critical value of Ic ≈ 16.1 mA. In contrast to confined systems
driven by spatially uniform spin currents [81], the intensity of fluctuations does
not saturate as the current approaches Ic , indicating that the nonlinear processes
preventing the onset of auto-oscillations are avoided.
At I ≥ Ic , a new peak appears in the BLS spectrum below the thermal peak, as
indicated in Fig. 31a by an arrow. The calculated current density in the center of the
gap at the onset is 3 × 108 A/cm2 , which is only slightly larger than the extrapolated
value 1 × 108 A/cm2 obtained for a similar system without radiation losses [81].
Since this peak is not present in the thermal fluctuation spectrum, we can conclude
that it corresponds to a new auto-oscillation mode that does not exist at I < Ic . The
peak rapidly grows and then saturates above 16.3 mA (Fig. 31c–d). Comparing the
6 Spin Waves
Fig. 31 (a) BLS spectra of thermal fluctuation amplified by the spin current at currents below the onset of auto-oscillation. (b) Integral intensity of amplified
thermal fluctuations and its inverse versus current. Both dependencies are normalized by their values at I = 0. (c) BLS pectra of the magnetization auto-
oscillation driven by the spin current. Filled areas are the results of fitting by the Gaussian function. Note, that the spectral widths are determined by the
327
resolution of the BLS setup. (d) The intensity and the center frequency of the auto-oscillation peak versus current. Curves are guides for the eye. Reprinted
from [30], with the permission of Springer Nature
328 S. O. Demokritov and A. N. Slavin
spectra for I = 16.1 mA and 16.3 mA, we see that the onset of auto-oscillations is
accompanied by a decrease in the intensity of thermal fluctuations, suggesting that
the energy of the spin current is mainly channelled into the auto-oscillation mode.
The spectral width of the auto-oscillation peak characterizing the coherence
of auto-oscillations decreases just above Ic , and stabilizes above 16.3 mA. Note
that the linewidth in the spectra shown in Fig. 31a and c is determined by the
spectral resolution of our optical technique under usual conditions. Additional
measurements at our instrument’s ultimate spectral resolution of 60 MHz show that
the actual linewidth in the saturated regime is below this value, suggesting a high
degree of coherence of the observed auto-oscillation mode.
The frequency of the auto-oscillation peak monotonically decreases with increas-
ing I (Fig. 31d). We note that the generated frequency is significantly below the
frequencies of magnetic fluctuations even at the onset of auto-oscillations. We draw
three important conclusions based on this observation. First, the auto-oscillation
mode does not belong to the thermal spin-wave spectrum. Second, this mode is
formed abruptly at the onset current, and not by gradual reduction of frequency
from the spin-wave spectrum due to the red nonlinear frequency shift. Third, since
the energy can be radiated only by propagating spin waves and there are no available
spin-wave spectral states at the auto-oscillation frequency, the auto-oscillation mode
is not influenced by the radiation losses.
To determine the spatial profile of the auto-oscillation mode, we performed
two-dimensional mapping of the dynamic magnetization at the frequency of auto-
oscillations, by rastering the probing laser spot in the two lateral directions and
simultaneously recording the BLS intensity. An example of the obtained maps
is presented in Fig. 32. These data show that the auto-oscillations are localized
in a very small area in the gap between the electrodes. The spatial distribution
Fig. 32 Normalized
color-coded map of the
measured BLS intensity over
the auto-oscillation area, and
two orthogonal sections
through its center. Symbols
are the experimental data, and
filled areas under solid curves
are the results of fitting by a
Gaussian function. Dashed
lines on the map show the
contours of the top electrodes.
The data were recorded at
I = 16.2 mA. (Reprinted from
[30], with the permission of
Springer Nature)
6 Spin Waves 329
of the BLS intensity is well described by a Gaussian function with the width
of 250 ± 10 nm, close to the diameter of the probing laser spot. The measured
spatial distribution is a convolution of the actual spatial profile with the instrumental
function determined by the shape of the laser spot. Therefore, we estimate that
the size of the auto-oscillation region is less than 100 nm, significantly smaller
than the characteristic size of the current localization (Fig. 30b). Therefore, we
conclude that the auto-oscillation area is determined not by the spatial localization
of the driving current, but by the nonlinear self-localization processes defining the
geometry of a standing spin-wave “bullet” [82]. We emphasize that the observed
quick saturation of the intensity of the auto-oscillation peak above the onset and
its monotonic red frequency shift are the intrinsic characteristics of the “bullet”
mode. Only one “bullet” mode exists at the frequency of the auto-oscillations and
this frequency is well separated from the continuous spectrum of non-localized spin
waves, Therefore, our findings provide strong evidence for that auto-oscillations
involve only a single mode in the studied system.
The nature of the auto-oscillation spin wave mode excited by either spin-polarized
or pure spin current in magnetic nanocontacts (0D objects) is of a fundamental
importance for the current-induced magnetization dynamics.
The first theoretical analysis of the nature of the spin-wave eigen-mode excited
by spin-polarized current in a nano-contact geometry was performed by J. Slon-
czewski [8]. He developed a spatially nonuniform linear theory of spin wave
excitations in a nano-contact, where the “free” ferromagnetic layer is infinite in
plane, while the spin-polarized current traversing this layer has a finite cross-section
S = π Rc2 , where Rc is the contact radius. Considering a perpendicularly magnetized
nano-contact Slonczewski showed that in the linear case the lowest threshold
of excitation by spin-polarized current is achieved for an exchange-dominated
propagating cylindrical spin wave mode having wave number q0 = 1.2/Rc and
frequency [8]:
D (H )
lin
Ith = 1.86 + . (27)
σ Rc2 σ
∂b
= −i ω0 b − DD
b + N |b|2 b − b + f (r/Rc ) σ I b − f (r/Rc ) σ I |b|2 b.
∂t
(28)
√
Here ω0 ≡ ωH (ωH + ωM ) is the linear FMR frequency, (ωH ≡ γ H,
DD ≡ (2A/MS ) ∂ω0 /∂H = (2γ A/MS )(ωH + ωM /2)/ω0 is the dispersion coefficient
6 Spin Waves 331
1
ψ
+ ψ + ψ 3 − ψ = 0, (30)
x
We would like to stress that the frequency of the spin wave bullet lies below
the linear frequency ω0 of the ferromagnetic resonance (see Eq. (31), and note that
N < 0), i.e., outside the spectrum of linear spin waves. This is the main reason for
the self-localization of the spin wave bullet, as the effective wave number of the spin
332 S. O. Demokritov and A. N. Slavin
wave mode with frequency (6) is purely imaginary. It also follows from Eq. (29) and
the expansion condition |b| < 1 that the maximum magnitude of B0 for which our
perturbative approach is still correct is B0 = 0.46.
It is well known [87] that the bullet-like solutions of (2 + 1)-dimensional NSE
are unstable with respect to the small perturbations: the wave packets having the
bullet shape Eq. (29), but amplitudes smaller than B0 , decay due to the dispersion
spreading, while the wave packets having amplitudes higher than B0 collapse due
to the nonlinearity. At the same time, Eq. (28) with both Gilbert dissipation and
current I is a two-dimensional analog of a Ginzburg-Landau equation that is known
to have stable localized solutions (see, e.g., review [88]). One can assume that for
a small damping rate and current I the full nonconservative eq. (28) will have a
bullet-like solution, only slightly different from the exact solution Eq. (29) of the
conservative NSE equation. It is clear, however, that not all of such solutions can be
supported in our case. For example, small-amplitude bullets, for which > > Rc ,
practically do not interact with the spatially localized current and will decay due to
the linear dissipation. The large-amplitude (B0 ≥ 1) bullets, on the other hand, will
also decay because the effective damping − σ I(1 − |b|2 ) for them changes sign
and becomes positive.
The excitation threshold of the spin wave bullet mode was calculated in [82] and
the minimum value of this threshold turned out to be equal to the second term in Eq.
(27), i.e., sobstantially lower than the threshold of excitation of the propagating
spin-wave mode in the perpendicularly magnetized magnetic nanocontact
Eq. (27).
To find the spatial profile of the spin-wave bullet mode Eq. (28) was solved
numerically. The results of comparison of the spin-wave excitation profiles at
the threshold obtained for a typical set of experimental parameters [83] from the
analytical solution Eq. (29) (solid black line) and numerical solution of Eq. (28)
(black dots) are shown in Fig. 33. One clearly sees that the numerical profile of
the nonlinear eigen-mode is practically indistinguishable from the approximate
“bullet-like” profile, so the “bullet” model works exceptionally well in this case.
For comparison we present in Fig. 33 the spatial profile of the Slonczhewski-like [8]
linear mode, that is obtained from the solution of Eq. (28) where the nonlinear terms
(terms containing |b|2 ) are omitted (red line). The amplitude of this linear mode at
the threshold is vanishingly small, |b(r)|2 → 0. We also present the normalized
spatial profile of a bullet mode above the thershold numerically calculated form Eq.
(28), to show that with the increase of the bullet amplitude its width decreases in
accordance with the experssion shown in Eq. (31) (blue line).
As it was mentioned above, the bullet mode is excited in an in-plane magetized
nanocontact, while the linear propagating spin wave mode (Slonczewski mode [8])
could be excited in a perpendicularly magnetized nanocotact. It is also well-known
that in the case when the direction of the external bias magnetic field varies from in-
plane to the perpendicular the coefficient of the nonlinear frequency shift N changes
its sign from negative to positive [89, 90]. Therefore, it is interesting to see the nature
of the spin-wave mode excited by a spin-polarized (or pure spin) current under the
oblique magnetization of a nanocontact.
6 Spin Waves 333
1.0
0.8
Nonlinear "bullet"
0.6
Nonlinear "bullet"
0.4 above the threshold
0.2
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Normalized distance r/Rc
Fig. 33 Normalized profiles of the spin wave mode generated by spin-polarized current at (the
threshold: solid black line – bullet profile (29), circles – result of the numerical solution of Eq.
(28), red line – profile of the linear eigen-mode calculated from the linearized Eq. (28). Blue line
demonstrates the numerically calculated profile of the bullet mode above the thershold. Vertical
dash-dotted line shows the region of the current localization. The parameters are: 4π M0 = 16.6 kG,
Happ = Hex = 5 kOe, A = 2.85 · 10−6 erg/cm, α G = 0.015, d = 1.2 nm, Rc = 25 nm, ε = 0.3
The analytic [91], numerical [92], and experimental [93] studies of the spin wave
excitation in current-driven magnetic nanocontacts were successfully performed,
and confirmed the conclusions of the above-presented theory.
In particular, the experimental study [93] was performed on a nanocontact
2Rc = 40 nm to the thin film tri-layer Co81 Fe19 (20 nm)/Cu(6 nm)/Ni80 Fe20 (4.5 nm),
patterned into a 8 μ m × 26μ m mesa. On top of this mesa, a circular Al nanocontact
was defined through SiO2 using e-beam lithography and an external magnetic field
of a constant magnitude (μ0 He = 1.1 T) was applied to the sample at an angle
θ e with respect to the film plane. Microwave excitations were only observed for a
single current polarity, corresponding to electrons flowing from the “free” (thinner)
to the “fixed” (thicker) magnetic layer. All measurements were performed at room
temperature.
Figure 34 shows the detailed angular dependence of the microwave frequencies
generated at a constant current of I = 14 mA and a constant magnetic field amplitude
of μ0 He = 1.1 T. The generated frequencies are approximately independent of
the magnetic field angle up to about θ e = 35◦ , and then decrease from about
35 GHz to 10 GHz with the increasing angle. The most important feature of the
results presented in Fig. 34 is the existence of two distinct and different modes for
sufficiently small values of θ e – linear propagating spin wave Slonczewski mode,
having a higher frequency, and a nonlinear self-localized spin-wave bullet mode
having a lower frequency. The frequencies of these two modes differ by about
2.5 GHz at angles up to θ e = 40◦ , and then they start to approach each other
up to θ e ≈ 55◦ where the mode having lower frequency completely disappears.
334 S. O. Demokritov and A. N. Slavin
40
Propagating mode
Spin wave bullet
30
f [GHz]
40
20 f [GHz] 30
20
10 10
0
0 15 30 45 60 75 90
Applied field agle θe [deg]
0
0 15 30 45 60 75 90
Applied field agle θe [deg]
Fig. 34 Experimental frequencies of the current-induced spin wave modes as a function of the
applied field angle θ e between the external bias magnetic field and the nanocontavt plane at I = 14
mA and μ0 He = 1.1 T (symols). Inset: theoretically calculated frequencies of the propagating
(upper curve) and “bullet” (lower curve) modes at the threshold of their excitation for nominal
parameters of the nanocontact sample. (Reprinted with permission from [82], © 2005 by the
American Physical Society)
The behavior of the frequencies of the current-induced spin wave modes shown in
Fig. 34 remains the same for any magnitude of the bias current that is larger than
I ≈ 10 mA. This behavior is also qualitatively similar to the behavior of the mode
frequencies derived from analytic theory (see Fig. 2 in [91] and the inset in Fig. 34)
and from the numerical simulation (see Fig. 4 in [92]).
The experimental threshold currents for the two excited spin wave modes shown
in Fig. 35 as functions of θ e were determined using the method proposed in [90]. The
graph in Fig. 35 only shows the threshold currents determined from experiment for
the magnetization angles 20◦ < θ e < 80◦ , since outside this range the signal was too
weak to allow reliable determination of the excitation threshold. It is clear that the
lower-frequency (bullet) mode has a lower threshold current at low magnetization
angles. As the angle increases, the threshold currents for the two modes gradually
approach each other and become essentially equal close to the critical angle
θ e ≈ 50◦ , where the low-frequency mode disappears. These experimental data are
also qualitatively similar to the threshold curves calculated analytically in [91] (see
solid lines in Fig. 35) and the similar curves simulated numerically (see Fig. 3 in
[92]). The inset in Fig. 35 shows the numerically calculated profile of the both
modes: nonlinear self-localized bullet mode (left frame) and linear propagating
mode (right frame). Thus, the results of the laboratory experiment [93] and the
results of the numerical simulations [92] fully confirmed the theoretical ideas [8,
82] about the possibility of current-induced excitation of two qualitatively different
spin wave modes in magnetic nanocontacs.
6 Spin Waves 335
30
25 100
15
10
Propagating mode
5
Spin wave bullet
0
0 15 30 45 60 75 90
Applied field agle qe [deg]
Fig. 35 Measured threshold current for the propagating (empty triangles) and bullet (filled circles)
modes as a function of the applied field angle θ e . Solid lines: thresholds for the same modes versus
applied field angle theoretically calculated using the formalism of [91] (red line – bullet mode,
blue line- propagating mode). Upper inset demonstrates the numerically calculated spatial profiles
of the bullet mode (left) and propagating mode (right). (Reprinted with permission from [82], ©
2005 by the American Physical Society)
that at large droplet amplitudes the direction of magnetization at the droplet center
could be almost completely opposite to the similar direction at the droplet periphery
(see Fig. 2 in [96]). These rather exotic nonlinear dynamical magnetic modes
were observed experimentally in [97], and a more detailed description of magnetic
droplets is presented in [98].
a Top
electrode Current
200 nm
Py (5) film
z
CoFe (5) Nano-
nano-wire y pillar
He
Bottom Cu(40)
electrode
b c
2.5
7 mA 1.0 7 mA
2.0
BLS intensity, a.u.
PSD, pW/MHz
0.8
1.5
0.6 5.5 mA
6 mA
1.0
0.4
5 mA 4 mA
0.5 0.2
4 mA
0 0.0
13 14 15
Frequency, GHz Frequency, GHz
Fig. 36 (a) Layout of the studied STNO with an incorporated waveguide. Inset: SEM micrograph
of the device. He is the static magnetic field. Numbers in parentheses indicate the thicknesses of
the layers in nanometres. (b) Spectra of the current-induced oscillations of the STNO measured
by a spectrum analyzer at different driving dc currents, as indicated. (c) BLS spectra recorded at
different driving currents measured by positioning the probing laser spot on the nano-waveguide.
Note that the spectral widths are determined by the resolution of the BLS setup. (Reprinted from
[16], with the permission of Springer Nature)
show that the internal field is significantly reduced in the magnetic film in the region
of the CoFe nanostripe, as compared to the magnitude away from the nanostripe.
The reduction of the internal field results in lowering of the local spin-wave
spectrum, creating a one-dimensional channel with allowed spin-wave frequencies
below the bottom of the spectrum in the free Py film. Low-frequency magnons
excited by STNO are directionally guided along the CoFe nanostripe, since there
are no states available at these frequencies in the free Py film. Thus, the static-
field channel induced by the CoFe nanostripe plays the role of a compound dipolar
spin-wave waveguide formed by the strongly exchange-coupled bilayer of the CoFe
nanostripe and the Py film on top of it.
338 S. O. Demokritov and A. N. Slavin
Fig. 37 (a) Normalized decay-compensated spatial map of the spin-wave intensity. The positions
of the top device electrode and the CoFe nanostripe are schematically shown. (b) Measured
dependence of the integral spin-wave intensity on the propagation coordinate (symbols), on
the log-linear scale. The line shows the result of the fitting of the experimental data by the
exponential function. (c) Distribution of the spin-wave intensity in the section transverse to the
nano-waveguide. Symbols are experimental data, curve is a fit by the Gaussian function. w is
the full width at half maximum of the transverse intensity profile. (d) Dependence of w on
the propagation coordinate. Symbols are experimental data, horizontal line is the mean value.
(Reprinted from [16], with the permission of Springer Nature)
6 Spin Waves 339
The post-CMOS information technology will require radically new solutions for
digital and analog information processing. One promising approach is to employ the
spin degree of freedom of electron for information storage and computing, which
is the main focus of the rapidly growing field of spintronics [101–104]. In this
new signal-processing paradigm signals will be codes in terms of a spin angular
momentum that can be carried by either polarized electrons or spin waves.
The use of spin waves (magnons) as carriers of spin angular momentum is
preferable to the use of spin-polarized electrons, because Gilbert magnetic damping,
associated with the transport of spin waves, is, usually, lower than the Ohmic losses
associated with the transport of electrons. The typical medium for the spin wave
propagation in the existing nano-scale magnonics is a soft magnetic metal such
as permalloy (Py). This material choice is mainly dictated by the relative ease of
340 S. O. Demokritov and A. N. Slavin
effect [9–11] and inverse spin-Hall effect [119], and electric fields (e.g., through
the flexoelectric effect [109, 110]) for generation, reception, and manipulation of
signals coded in terms of the spin angular momentum and carried by different spin-
wave modes in magnetic nanostructures.
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346 S. O. Demokritov and A. N. Slavin
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Micromagnetics Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Magnetic Gibbs Free Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
Spin, Magnetic Moment, and Magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
Exchange Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Magnetostatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
Zeeman Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Magnetostatic Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Crystal Anisotropy Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Magnetoelastic and Magnetostrictive Energy Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
Characteristic Length Scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
Exchange Length . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
Critical Diameter for Uniform Rotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
Wall Parameter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
Mesh Size in Micromagnetic Simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
L. Exl ()
University of Vienna Research Platform MMM Mathematics – Magnetism – Materials,
University of Vienna, and Wolfgang Pauli Institute, Wien, Austria
e-mail: [email protected]
D. Suess
University of Vienna Research Platform MMM Mathematics – Magnetism – Materials, and
Physics of Functional Materials, Faculty of Physics, University of Vienna, Wien, Austria
e-mail: [email protected]
T. Schrefl
Christian Doppler Laboratory for Magnet Design Through Physics Informed Machine Learning,
Department of Integrated Sensor Systems, Danube University Krems, Wiener Neustadt, Austria
e-mail: [email protected]
Abstract
Introduction
Computer simulations are essential tools for product design in modern society. This
is also true for magnetic materials and their applications. The design of magnetic
data storage systems such as hard disk devices [1, 2, 3, 4, 5] and random access
memories [6, 7] relies heavily on computer simulations. Similarly, the computer
models assist the development of magnetic sensors [8, 9] used as biosensors or
position and speed sensors in automotive applications [10]. Computer simulations
give guidance for the advance of high performance permanent magnet materials
[11, 12, 13] and devices. In storage and sensor applications, the selection of
magnetic materials, the geometry of the magnetically active layers, and the layout
of current lines are key design questions that can be answered by computations. In
addition to the intrinsic magnetic properties, the microstructure including grain size,
grain shape, and grain boundary phases is decisive for the magnet’s performance.
Computer simulations can quantify the influence of microstructural features on the
remanence and the coercive field of permanent magnets.
The characteristic length scale of the abovementioned computer models is
in the range of nanometers to micrometers. The length scale is too big for a
description by spin polarized density functional theory. Efficient simulations by
atomistic spin dynamics [14] are possible for nano-scale devices only. On the other
hand, macroscopic simulations using Maxwell’s equations hide the magnetization
7 Micromagnetism 349
processes that are relevant for the specific functions of the material or device under
consideration. Micromagnetism is a continuum theory that describes magnetization
processes on significant length scales that are
For most ferromagnetic materials, this length scale is in the range of a few
nanometers to micrometers. The first aspect leads to a mathematical formulation
which makes it possible to simulate materials and devices in a reasonable time.
Instead of billions of atomic spins, only millions of finite elements have to be taken
into account. The second aspect keeps all relevant physics so that the influence of
structure and geometry on the formation of reversed domains and the motion of
domain walls can be computed.
The theory of micromagnetism was developed well before the advance of modern
computing technology. Key properties of magnetic materials can be understood by
analytic or semi-analytic solutions of the underlying equations. However, the future
use of powerful computers for the calculation of magnetic properties by solving the
micromagnetic equations numerically was already proposed by Brown [15] in the
late 1950s. The purpose of micromagnetics is the calculation of the magnetization
distribution as function of the applied field or the applied current taking into account
the structure of the material and the mutual interactions between the different
magnetic parts of a device.
Micromagnetics Basics
The key assumption of micromagnetism is that the spin direction changes only by
a small angle from one lattice point to the next [16]. The direction angles of the
spins can be approximated by a continuous function of position. Then the state
of a ferromagnet can be described by a continuous vector field, the magnetization
M(x). The magnetization is the magnetic moment per unit volume. The direction of
M(x) varies continuously with the coordinates x, y, and z. Here we introduced the
position vector x = (x, y, z). Starting from the Heisenberg model [17, 18] which
describes a ferromagnet by interacting spins associated with each atom, we derive
the micromagnetic equations whereby several assumptions are made:
5. The energy terms are derived either by the transition from an atomistic model to
a continuum model or phenomenologically.
T = μ0 MdV × H , (1)
We describe the state of the magnet in terms of the magnetization M(x). In the
following we will show how the continuous vector field M(x) is related to the
magnetic moments located at the atom positions of the magnet.
The local magnetic moment of an atom or ion at position x i is associated with the
spin angular momentum, h̄S,
|e|
μ(x i ) = −g h̄S(x i ) = −gμB S(x i ). (2)
2m
Here e is the charge of the electron, m is the electron mass, and g is the Landé factor.
The Landé factor is g ≈ 2 for metal systems with quenched orbital moment. The
constant μB = 9.274 × 10−24 Am2 = 9.274 × 10−24 J/T is the Bohr magneton.
The constant h̄ is the reduced Planck constant, h̄ = h/(2π ), where h is the Planck
constant. The magnetization of a magnetic material with N atoms per unit volume is
7 Micromagnetism 351
M = Nμ. (3)
The magnetic moment is often given in Bohr magnetons per atom or Bohr
magnetons per formula unit. The magnetization is
where μfu is the magnetic moment per formula unit and Nfu is the number of
formula units per unit volume.
The length of the magnetization vector is assumed to be a function of temperature
only and does not depend on the strength of the magnetic field:
|M| = Ms (T ) = Ms , (5)
Exchange Energy
The exchange energy is of quantum mechanical nature. The energy of two ferromag-
netic electrons depends on the relative orientation of their spins. When the two spins
are parallel, the energy is lower than the energy of the antiparallel state. Qualitatively
this behavior can be explained by the Pauli exclusion principle and the electrostatic
Coulomb interaction. Owing to the Pauli exclusion principle, two electrons can only
be at the same place if they have opposite spins. If the spins are parallel, the electrons
tend to move apart which lowers the electrostatic energy. The corresponding gain in
energy can be large enough so that the parallel state is preferred.
352 L. Exl et al.
where Jij is the exchange integral between atoms i and j and h̄S i is the angular
momentum of the spin at atom i. For cubic metals and hexagonal closed packed
metals with ideal c over a ratio there holds Jij = J . Treating the exchange energy
for a large number of coupled spins, we regard Eij as a classical potential energy
and replace S i by a classical vector. Let mi be the unit vector in direction −S i . Then
mi is the unit vector of the magnetic moment at atom i. If ϕij is the angle between
the vectors mi and mj , the exchange energy is
m(x i + a j ) =m(x i )+
∂m ∂m ∂m
aj + bj + cj +
∂x ∂y ∂z (9)
1 ∂ 2m 2 ∂ 2m 2 ∂ 2m 2
a + b + c + ....
2 ∂x 2 j ∂y 2 j ∂z2 j
6 6
∂ 2 mi 2 ∂ 2 mi 2 ∂ 2 mi 2
Eij = − J S 2 mi · a + mi · b + mi · c
∂x 2 j ∂y 2 j ∂z2 j
j =1 j =1
(10)
∂ 2 mi ∂ 2 mi ∂ 2 mi
= − 2J S 2 a 2 mi · + mi · + mi ·
∂x 2 ∂y 2 ∂z2
To get the exchange energy of the crystal, we sum over all atoms i and divide by 2
to avoid counting each pair of atoms twice. We also use the relations
7 Micromagnetism 353
∂ 2m ∂m 2
m· = − , (11)
∂x 2 ∂x
The sum in (12) is over the unit cells of the crystal with volume V . In the continuum
limit, we replace the sum with an integral. The exchange energy is
2 2 2
∂m ∂m ∂m
Eex = A + + dV . (13)
V ∂x ∂y ∂z
Expanding and rearranging the terms in the bracket and introducing the nabla
operator, ∇, we obtain
2
Eex = A (∇mx )2 + ∇my + (∇mz )2 dV . (14)
V
354 L. Exl et al.
J S2
A= n. (15)
a
In cubic lattices, n is the number of atoms per unit cell (n = 1, 2, and 4 for
simple cube, body-centered cubic, and face-centered cubic lattices, respectively).
In a hexagonal
√ closed packed structures, n is the ideal nearest neighbor distance
(n = 2 2). The number N of atoms per unit volume is n/a 3 . At non-zero
temperature, the exchange constant may be expressed in terms of the saturation
magnetization, Ms (T ). Formally we replace S by its thermal average. Using
equations (2) and (3), we rewrite
J [Ms (T )]2
A(T ) = n. (16)
(NgμB )2 a
The calculation of the exchange constant by (15) requires a value for the
exchange integral, J . Experimentally, one can measure a quantity that strongly
depends on J such as the Curie temperature, TC ; the temperature dependence of
the saturation magnetization, Ms (T ); or the spin wave stiffness parameter, in order
to determine J. According to the molecular field theory [20], the exchange integral
is related to the Curie temperature given by
3 k B TC 1 3 k B TC S n
J = or A = . (17)
2 S(S + 1) z 2 a(S + 1) z
The second equation follows from the first one by replacing J with the relation (15).
Here z is the number of nearest neighbors (z = 6, 8, 12, and 12 for simple cubic,
body-centered cubic, face-centered cubic, and hexagonal closed packed lattices,
respectively) and kB =1.3807×10−23 J/K is Boltzmann’s constant. The use of (17)
together with (15) underestimates the exchange constant by more than a factor of 2
[21]. Alternatively one can use the temperature dependence of the magnetization as
arising from the spin wave theory
Equation (18) is valid for low temperatures. From the measured temperature
dependence Ms (T ), the constant C can be determined. Then the exchange integral
[21, 22] and the exchange constant can be calculated from C as follows:
2/3 2/3
0.0587 kB 0.0587 kB
J = or A = . (19)
nSC 2S n2 S 2 C 2a
This method was used by Talagala and co-workers [23]. They measured the
temperature dependence of the saturation magnetization in NiCo films to determine
7 Micromagnetism 355
the exchange constant as function of the Co content. The exchange constant can also
be evaluated from the spin wave dispersion relation (see Chapter SPW) which can
be measured by inelastic neutron scattering, ferromagnetic resonance, or Brillouin
light scattering [24]. The exchange integral [22] and the exchange constant are
related to the spin wave stiffness constant, D, via the following relations:
D 1 D
J = 2
or A = NS. (20)
2 Sa 2
For the evaluation of the exchange constant, we can use S = Ms (0)/(NgμB ) [25]
for the spin quantum number in equations (17), (19), and (20). This gives the relation
between the exchange constant, A, and the spin wave stiffness constant, D,
DMs (0)
A= , (21)
2gμB
when applied to (20). Using neutron Brillouin Scattering, Ono and co-workers [26]
measured the spin wave dispersion in a polycrystalline Nd2 Fe14 B magnet, in order
to determine its exchange constant.
Ferromagnetic exchange interactions keep the magnetization uniform. Depend-
ing on the sample, geometry external fields may lead to a locally confined
non-uniform magnetization. Probing the magnetization twist experimentally and
comparing the result with the computed equilibrium magnetic state (see sec-
tion “Brown’s Micromagnetic Equation”) is an alternative method to determine the
exchange constant. The measured data is fitted to the theoretical model whereby
the exchange constant is a free parameter. Smith and co-workers [27] measured
the anisotropic magnetoresistance to probe the fanning of the magnetization in a
thin permalloy film from which its exchange constant was calculated. Eyrich and
co-workers [24] measured the field-dependent magnetization, M(H ), of a trilayer
structure in which two ferromagnetic films are coupled antiferromagnetically. The
M(H ) curve probes the magnetization twist within the two ferromagnets. Using
this method the exchange constant of Co alloyed with various other elements was
measured [24].
The interplay between the effects of ferromagnetic exchange coupling, magneto-
static interactions, and the magnetocrystalline anisotropy leads to the formation of
domain patterns (for details on domain structures, see Chapter Domains). With mag-
netic imaging techniques, the domain width, the orientation of the magnetization,
and the domain wall width can be measured. These values can be also calculated
using a micromagnetic model of the domain structure. By comparing the predicted
values for the domain width with measured data, Livingston [28, 29] estimated
the exchange constant of the hard magnetic materials SmCo5 and Nd2 Fe14 B. This
method can be improved by comparing more than one predicted quantity with
measured data. Newnham and co-workers [30] measured the domain width, the
orientation of the magnetization in the domain, and the domain wall width in foils
356 L. Exl et al.
of Nd2 Fe14 B. By comparing the measured values with the theoretical predictions,
they estimated the exchange constant of Nd2 Fe14 B.
Input for micromagnetic simulations: The high temperature behavior of perma-
nent magnets is of utmost importance for the applications of permanent magnets
in the hybrid or electric vehicles. For computation of the coercive field by
micromagnetic simulations, the exchange constant is needed as input parameter.
Values for A(T ) may be obtained from the room temperature value of A(300 K)
and Ms (T ). Applying (16) gives A(T ) = A(300 K) × [Ms (T )/Ms (300 K)]2 .
Magnetostatics
∇ ×H = j (22)
∇ ·B = 0 (23)
Here B is the magnetic induction or magnetic flux density, H is the magnetic field,
and j is the current density. The charge density fulfills ∇ · j = 0 which expresses
the conservation of electric charge. We now have the freedom to split the magnetic
field into its solenoidal and nonrotational part
By definition, we have
∇ · H ext = 0, (25)
∇ × H demag = 0. (26)
Using (22) and (24), we see that the external field, H ext , results from the current
density (Ampere’s law)
∇ × H ext = j . (27)
On a macroscopic length scale, the relation between the magnetic induction and the
magnetic field is expressed by
B = μH , (28)
7 Micromagnetism 357
B = μ0 (H + M) . (29)
The energy of the magnet in the external field, H ext , is the Zeeman energy. The
energy of the magnet in the demagnetizing field, H demag , is called magnetostatic
energy.
Zeeman Energy
is the interaction energy of the magnet with the external field. To obtain the Zeeman
energy in a continuum model, we introduce the magnetization M = Nμ, define the
volume per atom, Vi = 1/N, and replace the sum with an integral. We obtain
Eext = −μ0 (M · H ext )Vi → −μ0 (M · H ext )dV . (31)
i V
Using (6), we express the Zeeman energy in terms of the unit vector of the
magnetization
Eext = − μ0 Ms (m · H ext )dV. (32)
V
Magnetostatic Energy
The magnetostatic energy is also called dipolar interaction energy. In a crystal each
moment creates a dipole field, and each moment is exposed to the magnetic field
created by all other dipoles. Therefore magnetostatic interactions are long range.
The magnetostatic energy cannot be represented as a volume integral over the
magnet of an energy density dependent on only local quantities.
358 L. Exl et al.
1 (μj · r ij )r ij μj
H dip (x i ) = 3 − 3 . (33)
4π
j =i
rij5 rij
The vectors r ij = x i − x j connect the source points with the field point. The
distance between a source point and a field point is rij = |r ij |. In order to obtain
a continuum expression for the field, we split the sum (33) into two parts. The
contribution to the field from moments that are far from x i will not depend strongly
on their exact position at the atomic level. Therefore we can describe them by a
continuous magnetization and replace the sum with an integral. For moments μj
which are located within a small sphere with radius R around x i , we keep the sum.
Thus we split the dipole field into two parts [34]:
Here
1 (μj · r ij )r ij μj
H near (x i ) = 3 − (35)
4π
rij <R
rij5 rij3
is the contribution of the sum of the dipoles within the sphere (see Fig. 2). For
the dipoles outside, the sphere we use a continuum approximation. Introducing the
magnetic dipole element MdV , we can replace the sum in (33) with an integral for
rij ≥ R
1 M(x ) · (x i − x ) (x i − x ) M(x )
H demag (x i ) = 3 |5
− |3
dV .
4π V* |x i − x |x i − x
(36)
The integral is over V *, the volume of the magnet without the small sphere around
the field point x i .
The sum in (35) is the contribution of the dipoles inside the sphere to the total
magnetostatic field. The corresponding energy term is local. It can be expressed
as an integral of an energy density that depends only on local quantities [34].
The term depends on the symmetry of the lattice and has the same form as the
crystalline anisotropy. Therefore it is included in the anisotropy energy. When the
anisotropy constants in (58) are determined experimentally, they already include the
contribution owing to dipolar interactions.
Applying −∇ to
1 x − x
U (x) = − M(x ) · dV (38)
4π V* |x − x |3
x − x 1 1 1
= −∇ and ∇ = −∇ (39)
|x − x |3 |x − x | |x − x | |x − x |
we obtain
1 1
U (x) = M(x ) · ∇ dV . (40)
4π V* |x − x |
M(x ) ∇ · M(x ) 1
∇ ·
=
+ M(x ) · ∇ , (41)
|x − x | |x − x | |x − x |
Magnetostatic Energy
For computing the magnetostatic energy, there is no need to take into account
(35). The near field is already included in the crystal anisotropy energy. We now
compute the energy of each magnetic moment μi in the field H demag (x i ) from the
surrounding magnetization. The sum over all atoms is the magnetostatic energy of
the magnet
μ0
Edemag = − μi · H demag (x i ). (43)
2
i
The factor 1/2 avoids counting each pair of atoms twice. Similar to the procedure
for the exchange and Zeeman energy, we replace the sum with an integral
μ0 1
H demag = −N M, (46)
where N is the demagnetizing factor. For a sphere the demagnetizing factor is 1/3.
Using (44), we find
μ0
Edemag = NMs2 V (47)
2
for the magnetostatic energy of a uniformly magnetized sphereoid with volume V .
In a cuboid or polyhedral particle, the demagnetizing field is nonuniform. However
we still can apply (47) when we use a volume averaged demagnetizing factor
which is obtained from a volume-averaged demagnetizing field. Interestingly the
volume-averaged demagnetizing factor for a cube is 1/3 the same value as for
the sphere. For a general rectangular prism, Aharoni [37] calculated the volume
averaged demagnetizing factor. A convenient calculation tool for the demagnetizing
7 Micromagnetism 361
factor, which uses Aharoni’s equation, is given on the Magpar website [38]. A
simple approximate equation for the demagnetizing factor of a square prism with
dimensions l × l × pl is [39]
1
N= , (48)
2p + 1
where p is the aspect ratio and N is the demagnetizing factor along the edge with
length pl.
∇ · H demag = −∇ · M. (49)
Plugging (37) into (49), we obtain a partial differential equation for the scalar
potential
∇ 2 U = ∇ · M. (50)
Equation (50) holds inside the magnet. Outside the magnet M = 0 and we have
∇ 2 U = 0. (51)
where n denotes the surface normal. The first condition follows from the continuity
of the component of H parallel to the surface (or ∇ ×H = 0). The second condition
follows from the continuity of the component of B normal to the surface (or ∇ ·B =
0). Assuming that the scalar potential is regular at infinity,
1
|U (x)| ≤ C for |x| large enough and constant C > 0 (54)
|x|
the solution of equations (50) to (53) is given by (42). Formally the integrals in (42)
are over the volume, V *, and the surface, ∂V *, of the magnet without a small sphere
surrounding the field point. The transition from V *→ V adds a term −M/3 to the
field and thus shifts the energy by a constant which is proportional to Ms2 . This is
usually done in micromagnetics [34].
362 L. Exl et al.
The above set of equations for the magnetic scalar potential can also be derived
from a variational principle. Brown [16] introduced an approximate expression
μ0
Edemag = μ0 M · ∇U dV − (∇U )2 dV (55)
V 2
for the magnetostatic energy, Edemag . For any magnetization distribution M(x), the
following equation holds
Edemag (M) ≥ Edemag (M, U ), (56)
Examples
Magnetostatic energy in micromagnetic software: For physicists and software engi-
neers developing micromagnetic software, there are several options to implement
magnetostatic field computation. The choice depends on the discretization scheme,
the numerical methods used, and the hardware. Finite difference solvers including
OOMMF [41], MuMax3 [42], and FIDIMAG [43] use (45) to compute the mag-
netostatic energy and the cell-averaged demagnetizing field. For piecewise constant
magnetization only, the surface integrals over the surfaces of the computational cells
remain. MicroMagnum [44] uses (42) to evaluate the magnetic scalar potential.
The demagnetizing field is computed from the potential by a finite difference
approximation. This method shows a higher speed up on Graphics Processor Units
[45] though its accuracy is slightly less. Finite element solvers compute the magnetic
scalar potential and build its gradient. Magpar [46], Nmag [47], and magnum.fe
[48] solve the partial differential equations (50) to (53). FastMag [49], a finite
element solver, directly integrates (42). Finite difference solvers apply the Fast
Fourier Transforms for the efficient evaluation of the involved convolutions. Finite
element solvers often use hierarchical clustering techniques for the evaluation of
integrals [50].
Magnetic state of nano-elements: From (45), we see that the magnetostatic
energy tends to zero if the effective magnetic charges vanish. This is known as
pole avoidance principle [34]. In large samples where the magnetostatic energy
dominates over the exchange energy, the lowest energy configurations are such that
∇ · M in the volume and M · n on the surface tend to zero. The magnetization
is aligned parallel to the boundary and may show a vortex. These patterns are
known as flux closure states. In small samples, the expense of exchange energy
7 Micromagnetism 363
for the formation of a closure state is too high. As a compromise the magnetization
bends towards the surface near the edges of the sample. Depending on the size,
the leaf state [51] or the C-state [52] or the vortex state has the lowest energy.
Figure 3 shows the different magnetization patterns that can form in thin film
square elements. The results show that with increasing element size the relative
contribution of the magnetostatic energy, Fdemag /(Fex + Fdemag ) decreases. All
micromagnetic examples in this chapter are simulated using FIDIMAG [43]. Code
snippets are given in the appendix.
Fig. 4 Initial magnetization curves with the field applied in the easy direction (dashed line) and
the hard direction (solid line) computed for a uniaxial hard magnetic material (Nd2 Fe14√ B at room
temperature: K1 = 4.9 MJ/m3 , μ0 Ms = 1.61 T, A = 8 pJ/m, the mesh size is h = 0.86 A/K1 =
1.1 nm). The magnetization component parallel to the field direction is plotted as a function of the
external field. The field is given in units of HK . The sample shape is thin platelet with the easy
axis in the plane of the film. The sample dimensions are 200 × 200 × 10 nm3 . The insets show
snapshots of the magnetization configuration along the curves. The initial state is the two domain
state shown at the lower left of the figure
of the magnetic states show that domain wall motion occurs along the easy axis and
rotation of the magnetization occurs along the hard axis.
The crystal anisotropy energy is the work done by the external field to move
the magnetization away from a direction parallel to the easy axis. The functional
form of the energy term can be obtained phenomenologically. The energy density,
eani (m), is expanded in a power series in terms of the direction cosines of the
magnetization. Crystal symmetry is used to decrease the number of coefficients.
The series is truncated after the first two non-constant terms.
Cubic Anisotropy
Let a, b, and c be the unit vectors along the axes of a cubic crystal. The crystal
anisotropy energy density of a cubic crystal is
eani (m) = K0 + K1 (a · m)2 (b · m)2 + (b · m)2 (c · m)2 + (c · m)2 (a · m)2
+ K2 (a · m)2 (b · m)2 (c · m)2 + . . . .
(57)
7 Micromagnetism 365
Uniaxial Anisotropy
In hexagonal or tetragonal crystals, the crystal anisotropy energy density is usually
expressed in terms of sin θ , where θ is the angle between the c-axis and the
magnetization. The crystal anisotropy energy of a hexagonal or tetragonal crystal
is
eani (m) = −K1 (c · m)2 + . . . . (59)
as expression for a uniaxial crystal anisotropy energy density. Here we used the
identity sin2 (θ ) = 1 − (c · m)2 , dropped two constant terms, namely, K0 and K1 ,
and truncated the series. When keeping only the terms which are quadratic in m,
the crystal anisotropy energy can be discretized as quadratic form involving only a
geometry-dependent matrix.
The crystalline anisotropy energy is
Eani = eani (m)dV , (60)
V
Anisotropy Field
An important material parameter, which is commonly used, is the anisotropy
field, HK . The anisotropy field is a fictitious field that mimics the effect of the
crystalline anisotropy. If the magnetization vector rotates out of the easy axis, the
crystalline anisotropy creates a torque that brings M back into the easy direction.
The anisotropy field is parallel to the easy direction, and its magnitude is such that
for deviations from the easy axis, the torque on M is the same as the torque by the
crystalline anisotropy. If the energy depends on the angle, θ , of the magnetization
with respect to an axis, the torque, T , on the magnetization is the derivative of the
energy density, e, with respect to the angle [20]
∂e
T = . (61)
∂θ
Let θ be a small angular deviation of M from the easy direction. The energy density
of the magnetization in the anisotropy field is
366 L. Exl et al.
TK = μ0 Ms HK sin(θ ) ≈ μ0 Ms HK θ. (63)
2K1
HK = (66)
μ0 Ms
Anisotropy field, easy and hard axis loops: K1 and – depending on the material
to be studied – K2 are input parameters for micromagnetic simulation. The
anisotropy constants can be measured by fitting a calculated magnetization curve to
experimental data. Figure 4 shows the magnetization curves of a uniaxial material
computed by micromagnetic simulations. For simplicity we neglected K2 and
described the crystalline anisotropy with (59). The M(H ) along the hard direction
is almost a straight line until saturation where M(H ) = Ms . Saturation is reached
when H = HK .
The above numerical result can be found theoretically. A field is applied
perpendicular to the easy direction. The torque created by the field tends to increase
the angle, θ , between the magnetization and the easy axis. The torque asserted by
the crystalline anisotropy returns the magnetization towards the easy direction. We
set the total torque to zero to get the equilibrium condition
The value of H that makes M parallel to the field is reached when sin(θ ) = 1. This
gives H = 2K1 /(μ0 Ms ). If higher anisotropy constants are taken into account the
field that brings M into the hard axis is H = (2K1 + 4K2 )/(μ0 Ms ).
When the atom positions of a magnet are changed relative to each other the
crystalline anisotropy varies. Owing to magnetoelastic coupling a deformation
produced by an external stress makes certain directions to be energetically more
7 Micromagnetism 367
favorable for the magnetization. Reversely, the magnet will deform in order to
minimize its total free energy when magnetized in certain directions.
0
εij = λij kl αk αl , (67)
kl
The magnetostriction constants λ100 and λ111 are defined as follows: λ100 is the
relative change in length measured along [100] owing to saturation of the crystal in
[100]; similarly λ111 is the relative change in length measured along [111] owing
to saturation of the crystal in [111]. The term with 1/3 in (68) results from the
definition of the spontaneous deformation with respect to a demagnetized state with
the averages
αi2 = 1/3 and
αi αj = 0.
∂eani (αi , 0)
eani = eani (αi , 0) + εij (71)
∂εij
ij
368 L. Exl et al.
gives the change of the energy density owing to the strain εij . Owing to symmetry,
the expansion coefficients ∂eani (αi , 0)/∂εij do not dependent on the sign of the
magnetization vector and thus are proportional to αi αj . The second term on the
right-hand side of (71) is the change of the crystal anisotropy energy density
with
deformation. This term is the magnetoelastic coupling energy density. Using
ij Bij kl αi αj as expansion coefficients, we obtain
eme = Bij kl αi αj εkl , (72)
ij kl
where Bij kl is the tensor of the magnetoelastic coupling constants. For cubic
symmetry, the magnetoelastic coupling energy density is
eme,cubic = B1 (ε11 α12 + ε22 α22 + ε33 α32 )+ 2B2 (ε23 α2 α3 + ε13 α1 α3 + ε12 α1 α2 ) + . . .
(73)
1
eel = cij kl εij εkl , (74)
2
ij kl
where cij kl is the elastic stiffness tensor. For cubic crystals the elastic energy is
1
eel,cubic = c1111 (ε11
2
+ ε22
2
+ ε33
2
)+
2
c1122 (ε11 ε22 + ε22 ε33 + ε33 ε11 )+ (75)
2
2c2323 (ε12 + ε23
2
+ ε31
2
).
Minimizing eme + eel with respect to εij under fixed αi gives the equilibrium strain
or spontaneous magnetostrictive deformation
0
εij = εij
0
(Bij kl , cij kl ). (76)
7 Micromagnetism 369
in terms of the magnetoelastic coupling constants and the elastic stiffness constants.
Comparison of the coefficients in (76) and the experimental relation (67) allows to
express the magnetoelastic coupling coefficients in terms of the elastic stiffness con-
stants and the magnetostriction constants. For cubic symmetry the magnetoelastic
coupling constants are
3
B1 = − λ100 (c1111 − c1122 ) (77)
2
B2 = −3λ111 c1212. (78)
External Stress
A mechanical stress of nonmagnetic origin will have an effect on the magnetization
owing to a change of magnetoelastic coupling energy. The magnetoelastic coupling
energy density owing to an external stress σ ext is [54]
eme = − σijext εij
0
. (79)
ij
3
eme,cubic = − λ100 (σ11 α12 + σ22 α12 + σ33 α22 )
2 (80)
− 3λ111 (σ12 α1 α2 + σ23 α2 α3 + σ31 α3 α1 )
The above results can be derived from the strain induced by the external stress
which is
ext
εij = sij kl σklext , (81)
kl
where sij kl is the compliance tensor. Inserting (81) into (72) gives the magnetoelastic
energy density owing to external stress. For an isotropic material, for example, an
amorphous alloy, we have only a single magnetostriction constant λs = λ100 =
λ111 . For a stress σ along an axis of a unit vector a, the magnetoelastic coupling
energy reduces to
3
eme,isotropic = − λs σ (a · α)2 . (82)
2
This equation has a similar form as that for the uniaxial anisotropy energy density
(59) with an anisotropy constant Kme = 3λs σ/2.
Magnetostrictive Self-Energy
A nonuniform magnetization causes a nonuniform spontaneous deformation owing
to (67). As a consequence, different parts of the magnet do not fit together. To
370 L. Exl et al.
1
emagstr = el el
cij kl εij εkl . (83)
2
ij kl
εij = εij
el
+ εij
0
, (84)
forces are known, the displacement field can be calculated as usual by linear
elasticity theory. The situation is similar to magnetostatics where the demagnetizing
field is calculated from effective magnetic charges. The procedure is as follows [56].
First we compute the spontaneous magnetostrictive strain for a given magnetization
distribution with (67) or in case of cubic symmetry with (68) and (69). Then we
apply Hooke’s law to compute the stress
σij0 = 0
cij kl εkl (86)
kl
∂
fi = − σ0. (87)
∂xj ij
j
∂
σij = fi with σij = cij kl εkl . (88)
∂xj
j kl
Equations (85) to (88) lead to a system of partial differential equations for the
displacement field u(x). This is an auxiliary problem similar to the magnetostatic
boundary value problem (see section “Magnetostatic Boundary Value Problem”)
which is to be solved for a given magnetization distribution.
7 Micromagnetism 371
Based on the above discussion, we can identify two contributions to the total
magnetic Gibbs free energy: The magnetoelastic coupling energy with an external
stress
Eme = − σijext εij
0
dV (89)
V ij
Exchange Length
It describes the relative importance of the exchange energy with respect to the
magnetostatic energy. Inspecting the factor (lex /L)2 in front of the brackets in (92),
7 Micromagnetism 373
we see that the exchange energy contribution increases with decreasing sample
size L. The smaller the sample, the higher is the expense of exchange energy for
nonuniform magnetization. Therefore small samples show a uniform magnetization.
If the magnetization remains parallel during switching, the Stoner-Wohlfarth [59]
model can be applied.
In the literature, the exchange length is either defined by (96)
= 2A/(μ M 2 ) [61].
[60] or by lex 0 s
2K1
Hc = for D ≤ Dcrit . (97)
μ0 Ms
2K1 1 34.66A
Hc = − Ms + for D > Dcrit . (98)
μ0 Ms 3 μ0 Ms D 2
In cuboids and particles with polyhedral shape, the nonuniform demagnetizing field
causes a twist of the magnetization near edges or corners [62]. As a consequence
nonuniform reversal occurs for particle sizes smaller than Dcrit . The interplay
between exchange energy and magnetostatic energy also causes a size dependence
of the switching field [63, 64].
Grain size dependence of the coercive field. The coercive field of permanent
magnets decreases with increasing grain size. This can be explained by the different
scaling of the energy terms [64, 65]. The smaller the magnet, the more dominant is
the exchange term. Thus it costs more energy to form a domain wall. To achieve
magnetization reversal, the Zeeman energy of the reversed magnetization in the
nucleus needs to be higher. This can be accomplished by a larger external field.
Figure 6 shows the switching field a Nd2 Fe14 B cube as a function of its edge
length. In addition we give the theoretical switching field for a sphere with the same
volume according to (97) and (98). Magnetization reversal occurs by nucleation
and expansion of reversed domains unless the hard magnetic cube is smaller
than 6lex .
374
Wall Parameter
The square root of the ratio of the exchange length and the prefactor of the crystal
anisotropy energy gives another critical length. The Bloch wall parameter
A
δ0 = (99)
K
denotes the relative importance of the exchange energy versus crystalline anisotropy
energy. It determines the width of the transition of the magnetization between two
magnetic domains. In a Bloch wall, the magnetization rotates in a way so that no
magnetic volume charges are created. The mutual competition between exchange
and anisotropy determines the domain wall width: Minimizing the exchange energy
favors wide transition regions, whereas minimizing the crystal anisotropy energy
favors narrow transition regions. In a bulk uniaxial material the wall width is
δB = π δ0 .
with the energy of the two domain state, Edemag2 + Ewall2 , and solving for L give
the single domain size of a cube
√
48 AK1
LSD ≈ . (100)
μ0 Ms2
The above equation simply means that the energy of a ferromagnetic cube with a
size L > LSD is lower in a the two domain state than in the uniformly magnetized
state. A thermally demagnetized sample with L > LSD most likely will be in a
multidomain state.
We have to keep in mind that the magnetic state of a magnet depends on its
history and whether local or global minima can be accessed over the energy barriers
that separate the different minima. The following situations may arise:
state by a high energy barrier. This behavior is observed in small Nd2 Fe14 B
particles [66].
(2) An initially saturated cube with L > LSD will not break up into domains
spontaneously if its anisotropy field is larger than the demagnetizing field.
The sample will remain in an almost uniform state until a reversed domain is
nucleated.
(3) Magnetization reversal of a cube with L < LSD will be nonuniform. Switching
occurs by the nucleation and expansion of a reversed domain for a particle size
down to about 5lex . For example in Nd2 Fe14 B, the single domain limit is LSD ≈
146 nm, and the exchange length is lex = 1.97 nm. The simulation presented in
Fig. 6 shows the transition from uniform to nonuniform reversal which occurs
at L ≈ 6lex .
(1) For computing the switching field of a magnetic particle, we need to describe
the formation of a reversed nucleus. A reversed nucleus is formed near edges
or corners where the demagnetizing field is high. We have to resolve the
rotations of the magnetization that eventually form the reversed nucleus. For
the computation of the nucleation field the required minimum mesh size has to
be smaller than the exchange length [61] at the place where the initial nucleus
is formed.
(2) For the simulation of domain wall motion, the transition of the magnetization
between the domains needs to be resolved. A failure to do so will lead to an
artificial pinning of the domain wall on the computational grid [67]. For the
study of domain wall motion in hard magnetic materials, the required minimum
mesh size has to be smaller than the Bloch wall parameter.
(3) In soft magnetic elements with vanishing crystal or stress-induced ansisotropy,
the magnetization varies continuously [68]. The smooth transitions of the mag-
netization transitions can be resolved with a grid size larger than the exchange
length. Care has to be taken if vortices play a role in the magnetization process
to be studied. Then artificial pinning of vortex cores on the computational grid
[67] has to be avoided.
In the following, we will derive the equilibrium equations for the magnetization.
The total Gibbs free energy of a magnet is a functional of m(x). To compute an
equilibrium state, we have to find the function m(x) that minimizes Etot taking into
account |m(x)| = 1. In addition the boundary conditions
7 Micromagnetism 377
hold, where n is the surface normal. The boundary conditions follow from (11) and
the respective equations for y and z and applying Green’s first identity to each term
of (14). The boundary conditions (101) can also be understood intuitively [15].
To be in equilibrium, a magnetic moment at the surface has to be parallel with its
neighbor inside when there is no surface anisotropy. Otherwise there is an exchange
torque on the surface spin.
Most problems in micromagnetics can only be solved numerically. Instead
of solving the Euler-Lagrange equation that results from the variation of (91)
numerically, we directly solve the variational problem. Direct methods [69, 70]
represent the unknown function by a set of discrete variables. The minimization
of the energy with respect to these variables gives an approximate solution to the
variational problem. Two well-known techniques are the Euler method and the Ritz
method. Both are used in numerical micromagnetics.
To approximate the magnetostatic energy, we use (42) and (45). Replacing the
integrals with sums over the computational cell, we obtain
μ0 (mij k · n)(mi j k · n )
Edemag ≈ Ms,ij k Ms,i j k |
dSdS .
8π ∂Vij k ∂V
i j k |x − x
ij k i j k
(104)
The volume integrals in (42) and (45) vanish when we assume that m(x) is constant
within each computational cell ij k. The magnetostatic energy is often expressed in
terms of the demagnetizing tensor Nij k,i j k
μ0 3
Edemag ≈ h Ms,ij k mTij k Nij k,i j k mi j k Ms,i j k (105)
2
ij k i j k
The total energy is now a function of the unknowns mij k . The constraint (5) is
approximated by
|mij k | = 1 (107)
where ij k runs over all computational cells. We obtain the equilibrium equations
from differentiation
⎡ ⎤
∂ ⎣ Lij k
Etot (. . . , mij k , . . . ) + (mij k · mij k − 1)⎦ = 0, (108)
∂mij k 2
ij k
⎡ ⎤
∂ ⎣ Lij k
Etot (. . . , mij k , . . . ) + (mij k · mij k − 1)⎦ = 0. (109)
∂Lij k 2
ij k
In the brackets we added a Lagrange function to take care of the constraints (107).
Lij k are Lagrange multipliers. From (108) we obtain the following set of equations
for the unknowns mij k
2Ai+1j k mi+1j k − mij k 2Ai−1j k mi−1j k − mij k
−2Aij k h3 + + · · ·
Ai+1j k + Aij k h2 Ai−1j k + Aij k h2
−μ0 Ms,ij k h3 H ext,ij k (110)
7 Micromagnetism 379
+μ0 Ms,ij k h3 N ij k,i j k mi j k Ms,i j k
i j k
∂eani
+h3 = −Lij k mij k .
∂mij k
The exchange field, the magnetostatic field, and the anisotropy field at the compu-
tational cell ij k are
2Aij k 2Ai+1j k mi+1j k − mij k 2Ai−1j k
H ex,ij k = +
μ0 Ms,ij k Ai+1j k + Aij k h2 Ai−1j k + Aij k
mi−1j k − mij k
+ · · · (112)
h2
H demag,ij k = − Nij k,i j k mi j k Ms,i j k (113)
i j k
1 ∂eani
H ani,ij k = − , (114)
μ0 Ms,ij k ∂mij k
respectively. The evaluation of the exchange field (112) requires values of mij k
outside the index range [1, Nx ] × [1, Ny ] × [1, Nz ]. These values are obtained by
mirroring the values of the surface cell at the boundary. This method of evaluating
the exchange field takes into account the boundary conditions (101).
Using the effective field, we can rewrite the equilibrium equations
Equation (115) states that the effective field is parallel to the magnetization at each
computational cell. Instead of (115) we can also write
Within, the framework of the Ritz method the solution is assumed to depend on a
few adjustable parameters. The minimization of the total Gibbs free energy with
respect to these parameters gives an approximate solution [15, 16]. In the following
we describe a famous and computationally efficient Ritz method, namely, the finite
element ansatz.
Most finite element solvers for micromagnetics use a magnetic scalar potential
for the computation of the magnetostatic energy. This goes back to Brown [16] who
introduced an expression for the magnetostatic energy, Edemag (m, U ), in terms of
the scalar potential for the computation of equilibrium magnetic states using the
Ritz method. We replace Edemag (m) with Edemag (m, U ), as introduced in (55), in
the expression for the total energy. The vector m(x) is expanded by means of basis
functions ϕi with local support around node x i
mfe (x) = ϕi (x)mi . (117)
i
The index i runs over all nodes of the finite element mesh. The expansion
coefficients mi and Ui are the nodal values of the unit magnetization vector and
the magnetic scalar potential, respectively. We assume that the constraint |m| = 1
is fulfilled only at the nodes of the finite element mesh. We introduce a Lagrange
function; Li are the Lagrange multipliers at the nodes of the finite element mesh.
By differentiation with respect to mi , Ui , and Li , we obtain the equilibrium
conditions
∂ Li
Etot (. . . , mi , Ui . . . ) + (mi · mi − 1) = 0, (119)
∂mi 2
i
∂ Li
Etot (. . . , mi , Ui . . . ) + (mi · mi − 1) = 0, (120)
∂Ui 2
i
∂ Li
Etot (. . . , mi , Ui . . . ) + (mi · mi − 1) = 0. (121)
∂Li 2
i
From (119) we obtain the following set of equations for the unknowns mi
7 Micromagnetism 381
2 A∇ϕi · ∇ϕj dV mj
j V
− μ0 Ms H ext ϕi dV
V
(122)
+ μ0 Ms ∇U ϕi dV
V
∂eani ( j ϕj mj )
+ dV = −Li mi .
V ∂mi
Equation (120) is the discretized form of the partial differential equation (50) for the
magnetic scalar potential. Equation (121) gives back the constraint |m| = 1.
In the following, we introduce the effective field at the nodes of the finite element
mesh
2
H eff,i = − A∇ϕi · ∇ϕj dV mj
μ0 M V
j
(123)
1 ∂eani
+ H ext,i + H demag,i − dV ,
μ0 M V ∂mi
where M = V Ms ϕi dV . H demag,i is the demagnetizing field averaged over the
finite elements surrounding node i. This average can be computed by plugging (118)
into the third line of (122) and dividing the resulting expression by −μ0 M.
The equilibrium equations are
μ0 MH eff,i = Li mi . (124)
We can write the equilibrium conditions in terms of a cross product of the magnetic
moment, Mmi , and the effective field at node i
The system is in equilibrium if the torque equals zero and the constraint |mi | = 1 is
fulfilled on all nodes of the finite element mesh.
Instead of a Lagrange function for keeping the constraint |m| = 1, projection
methods [72] are commonly used in fast micromagnetic solvers [73]. In the iterative
scheme for solving (125), the search direction d k+1 i is projected onto a plane
perpendicular to mki , corresponding to first-order approximation of the constraint
at node i. After each iteration k, the vector mk+1
i is normalized.
382 L. Exl et al.
Magnetization Dynamics
∂m |γ |μ0 |γ |μ0 α
=− m × H eff − m × (m × H eff ) (126)
∂t 1 + α2 1 + α2
2
t0 = . (128)
αγ μ0 Ms
Fig. 7 Switching of a thin film nano-element by a short field pulse in the (-1,-1,-1) direction for α = 0.06 (top row) and α = 0.02 (bottom row). (K1 = 0,
μ0 Ms = 1 T, A = 10 pJ/m, mesh size h = 0.56 A/(μ0 Ms2 ) = 2 nm). The sample dimensions are 100 × 20 × 2 nm3 . The sample is originally magnetized in
the +x direction. Left: Magnetization as function of time. The thin dotted line gives the field pulse, Hext (t). Once the field is switched off damped oscillations
occur which are clearly seen in My (t). The bold grey line is a fit to the envelope of the magnetization component parallel to the short axis. Right: Transient
383
magnetic states. The numbers correspond to the black dots in the plot of My (t) on the left
384 L. Exl et al.
Acknowledgments The authors thank the Austrian Science Fund (FWF) under grant No. F4112
SFB ViCoM and grant No. P31140-N32 for financial support. The financial support by the
Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research,
Technology and Development and the Christian Doppler Research Association is gratefully
acknowledged.
Appendix
The intrinsic material properties listed in Table 1 are taken from [77]. The exchange
lengths
√ and the wall parameter are calculated as follows: l ex = A/(μ0 Ms2 ), δ0 =
A/|K1 |.
Table 1 Intrinsic magnetic properties and characteristic lengths of selected magnetic materials
Material TC (K) μ0 Ms (T) A(pJ/m) K1 (kJ/m3 ) lex (nm) δ0 (nm)
Fe 1044 2.15 22 48 2.4 21
Co 1360 1.82 31 410 3.4 8.7
Ni 628 0.61 8 -5 5.2 40
Ni0.8 Fe0.2 843 1.04 10 -1 3.4 100
CoPt 840 1.01 10 4900 3.5 1.4
Nd2 Fe14 B 588 1.61 8 4900 2.0 1.3
SmCo5 1020 1.08 12 17200 3.6 0.8
Sm2 Co17 1190 1.25 16 4200 3.6 2.0
Fe3 O4 860 0.6 7 -13 4.9 23
import numpy a s np
from f i d i m a g . m i c r o import Sim
from f i d i m a g . common import CuboidMesh
from f i d i m a g . m i c r o import UniformExchange , Demag
from f i d i m a g . m i c r o import TimeZeeman
mu0 = 4 ∗ np . p i ∗ 1 e−7
7 Micromagnetism 385
A = 1 . 0 e −11
Ms = 1 . / mu0
d e f r e l a x _ s y s t e m ( mesh ) :
sim = Sim ( mesh , name= ’ r e l a x ’ )
sim . d r i v e r . s e t _ t o l s ( r t o l =1e −10 , a t o l =1e −10)
sim . d r i v e r . a l p h a = 0 . 5
sim . d r i v e r . gamma = 2 . 2 1 1 e5
sim . Ms = Ms
sim . d o _ p r e c e s s i o n = F a l s e
sim . s e t _ m ( ( 0 . 5 7 7 3 5 0 2 6 9 , 0 . 5 7 7 3 5 0 2 6 9 , 0 . 5 7 7 3 5 0 2 6 9 ) )
sim . r e l a x ( )
np . s a v e ( ’m0 . npy ’ , sim . s p i n )
d e f a p p l y _ f i e l d ( mesh ) :
sim = Sim ( mesh , name= ’ dyn ’ )
sim . d r i v e r . s e t _ t o l s ( r t o l =1e −10 , a t o l =1e −10)
sim . d r i v e r . a l p h a = 0 . 0 2
sim . d r i v e r . gamma = 2 . 2 1 1 e5
sim . Ms = Ms
sim . s e t _ m ( np . l o a d ( ’m0 . npy ’ ) )
s i g m a = 0 . 1 e−9
def gaussian_fun ( t ) :
r e t u r n np . exp ( −0.5 ∗ ( ( t −3∗ s i g m a ) / s i g m a ) ∗ ∗ 2 )
mT = 0 . 0 0 1 / mu0
zeeman = TimeZeeman ([ −100 ∗ mT, −100 ∗ mT, −100 ∗
mT] , t i m e _ f u n = g a u s s i a n _ f u n , name= ’H ’ )
sim . add ( zeeman , s a v e _ f i e l d = T r u e )
sim . r e l a x ( d t = 1 . e −12 , m a x _ s t e p s = 10000)
i f __name__ == ’ __main__ ’ :
mesh = CuboidMesh ( nx =50 , ny =10 , nz =1 , dx =2 , dy =2 ,
dz =2 , u n i t _ l e n g t h =1e −9)
r e l a x _ s y s t e m ( mesh )
a p p l y _ f i e l d ( mesh )
386 L. Exl et al.
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Dieter Suess received his PhD from the TU-Wien in 2002 where
he completed his Habilitation in 2007 in “Computational Material
Science.” In 2006 he proposed “Exchange Spring Media” for
recording. Since 2018 he is assoc. Prof. and Group Speaker of
the “Physics of Functional Materials” group at the University of
Vienna.
390 L. Exl et al.
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
Relevance of Domains and Domain Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
Domain Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
Magnetic Energies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Driving Forces for Domain Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
Interplay of Energies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
Domain Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
Domain Walls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414
Domain Wall Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
Domain Wall Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
Current-Driven Domain Wall Motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
Abstract
R. Schäfer ()
Institute for Metallic Materials, Leibniz Institute for Solid State and Materials Research (IFW)
Dresden, Dresden, Germany
Institute for Materials Science, Dresden University of Technology, Dresden, Germany
e-mail: [email protected]
domains can be classified. Domain walls and their dynamics, both field- and
current-driven, will be addressed.
Introduction
M/Ms 1
5. Magnetization Curve
(independent of scale)
H/Ha
1
lysis
na
eA
2. Micromagnetic tur
Analysis uc
str
cro
Mi
(1 - 1000 nm)
c
eti
gn H
Ma
3. Domain Analysis
(1 - 1000 µm)
4. Phase Analysis
1. Atomic Level Theory (> 100 µm)
(< 1 nm)
Fig. 1 Five descriptive levels of magnetically ordered materials, illustrating the link-function
of magnetic microstructure between atomic foundations and technical applications of magnetic
materials. The anisotropy field Ha , used in the magnetization curve, is defined as Ha = 2K1 /μ0 Ms
with K1 and Ms being the first-order cubic anisotropy constant and saturation magnetization,
respectively. Indicated are the sample dimensions for which the five concepts are applicable. The
domain image in level (3) was obtained by magneto-optical Kerr microscopy on the (100) surface
of an Fe3wt%Si-sheet of 0.5 mm thickness, and the M(H )-loop in level (5) was calculated by
magnetic phase theory for the configuration in level (4). (The domain image at level (3) is adapted
by permission from Ref. [1] (c) Springer 1998)
8 Magnetic Domains 393
level (1), are no longer considered. One rather sums them in a certain neighborhood
and represents the local average over a small volume of magnetic moments by a
classical magnetization vector M – the discrete, quantum mechanical, and statistical
properties of the spins and elementary moments are thus ignored. For a constant
temperature this vector has a constant length, the technical saturation magnetization
Ms . Then one can divide the M-vector by the saturation magnetization, leading
to the unit vector of magnetization m(r) = M(r)/Ms with m2 = 1. For this
mesoscopic approach in the description of magnetic materials, it does not matter
whether a material is ferromagnetic or ferrimagnetic, as the latter is also character-
ized by a net magnetization vector. The purpose of magnetic microstructure analysis
is the determination of the vector field m(r) and its response to a magnetic field.
The magnetization vectors are typically arranged as magnetic domains, so Domain
Analysis – level (3) – is in the center of magnetic microstructure analysis. Level
(2), the continuum theory of micromagnetics, deals with the connecting elements
between the domains, the domain walls, and their substructures. Level (4), phase
theory, ignores the specific arrangement of the domains and rather focuses on their
volume distribution by collecting all domains that are magnetized along a specific
direction in a domain phase. The rearrangement of the phases in a magnetic field
finally leads to the (idealized) magnetization curve. So the domains are at the end
responsible for magnetization curves.
In a conventional definition, magnetic domains are uniformly magnetized regions
that appear spontaneously in otherwise unstructured ferro- or ferrimagnetic samples
[1]. In the example presented in the center of Fig. 1, the domains are well-ordered
owing to the facts that the surface of the crystal is “well”-oriented, meaning
that it contains two easy anisotropy axes for the magnetization, that the crystal
is largely free from internal mechanical stress, and that no magnetic field is
applied to the specimen. In general, however, magnetic domains do not have to be
uniformly magnetized, and they can be more or less complex depending on many
circumstances. To give an impression of the variability of domain patterns, a collage
of selected domain images of various magnetic materials is shown in Fig. 2.
In this chapter a review of some basic aspects of magnetic domains is presented
that is based on an earlier textbook on magnetic domains [1]. The magneto-optical
Kerr images were partly taken and adapted from the book.
Co crysta Fe
l
cglass film
talli
me
et
she FeS
Si i sh
eet
Fe Ga
rne
t fi
lm
t
shee
NiFe FeSi
Fig. 2 Collection of domain images, obtained by Kerr microscopy on various magnetic materials.
(Most domain images are adapted by permission from Ref. [1] (c) Springer 1998)
0
µ0H
in mT
-1 20 µm
-40 -20 0 20 40
1 -7.0 mT -7.8 mT -7.9 mT -8.1 mT
-1 100 µm
-40 -20 0 20 40
1 -200 mT -300 mT -370 mT -400 mT
-1 10 µm
-1000 -500 0 500 1000
1 -1 mT -20 mT -67 mT -106 mT
-1 10 µm
-1000 -500 0 500 1000
Fig. 3 Domain nucleation and growth in magnetic films with strong perpendicular anisotropy,
together with the hysteresis loops along which the domains were imaged. First row: [Co
(0.3 nm)/Pt (0.7 nm)]3 multilayer (sample courtesy D. Makarov, Dresden). Second row: Pt
(3 nm)/Co (1 nm)/Pt (1.5 nm) trilayer (sample courtesy P.M. Shepley and T.A. Moore, Leeds).
Third row: FePt film, 16 nm thick (sample courtesy P. He and S.M. Zhou, Tongji [4]). Fourth
row: FePd(11 nm)/FePt (24 nm) double layer (Sample courtesy L. Ma and S.M. Zhou, Tongji [3])
in the figure) or proceeding nucleation (lower row). For such polycrystalline thin
films, the domain character is more determined by domain wall coercivity effects
due to defects and roughness, randomness of the sample nanostructure, etc. rather
than by an equilibrium of magnetic energies [2, 3]. Typical for such films is a slow
creeping of the nucleated reversed domains into the still saturated area, indicating
thermally activated processes. The domains shown can therefore hardly be predicted
by domain theory – the only way to interpret the hysteresis curves is by observation
of the domains that are responsible for the loops.
This is also true for the M(H )-loop of the amorphous ribbon in Fig. 4. Rather
than revealing a rectangular loop as expected for such material, a predominantly
flat curve is measured inductively with two distinct steps at small field. Domain
observation immediately discloses the reason for such behavior: perpendicularly
magnetized domains across most of the ribbon’s cross section are seen from the side,
whereas longitudinal 180◦ domains are found on the surface. The perpendicular
domains are magnetized by reversible rotational processes in an applied magnetic
396 R. Schäfer
1 Surface M(H)-
ld ic
fie net
curve
M/Ms
ag
(by MOKE
M
magnetometry)
Volume M(H)-
curve (inductively
µm
–1 measured)
20
–8 –6 –4 –2 0 2 4 6 8
H in kA/m
field along the ribbon axis, leading to the flat portions of the loop, while the surfaces
are magnetized by the coercive motion of 180◦ domain walls, which is responsible
for the low-field behavior. In fact, a rectangular surface loop is measured by
magneto-optical Kerr (MOKE) magnetometry with the same coercivities as found
inductively. From the relative induction amplitude at the switching fields of the
surface, a depth of about one micrometer for the longitudinally magnetized surface
regions can be derived. The reason for this behavior is a crystallized surface that
sets the volume under planar compression stress, whereas the surface itself is under
tension. By magnetoelastic interaction, this inhomogeneous stress state leads to a
perpendicular anisotropy in most of the volume and longitudinal anisotropy at the
surfaces.
There are also cases where the interpretation of a hysteresis loop is apparently
simple: the rectangular loop measured on a permalloy film that is in direct exchange
contact with an antiferromagnetic NiO film (Fig. 5) suggests 180◦ wall motion as
dominating magnetization process. In fact this can be proven by domain imaging.
However, the domain walls surprisingly change character between symmetric Néel
and cross-tie wall (see section “Domain Walls”) on the descending and ascending
branches of the loop, respectively. This subtle difference can by no means be derived
from the magnetization loop. These reversible wall alterations indicate the existence
of bi-modal coupling strengths due to pinned and unpinned spins at the interface
between ferro- and antiferromagnet [6].
Surprising domain phenomena may also be found when magnetic samples are
excited by high-frequency magnetic fields. The ground domain state of a nanocrys-
talline FeNbSiCuB tape wound core with a week circumferential anisotropy, for
example, consists of 180◦ domains that are running along the circumferential
direction (Fig. 6a). Excited quasistatically along the easy axis, i.e., in a slowly
changing magnetic field well below the Hertz regime, 180◦ walls are nucleated,
8 Magnetic Domains 397
M/Ms
10 µm
0
Heb
–1
–40 –20 0 20 40
µ0H in mT
Fig. 5 Field-shifted hysteresis loop in a Ni81 Fe7 (30 nm) / NiO (30 nm) exchange-bias double film
together with high-resolution domain wall images along the forward and backward branch of the
loop. A symmetric Néel wall (upper image) and an asymmetrically distorted cross-tie wall (lower
image) are observed. Obtained at IFW Dresden together with J. McCord. (Adapted and reproduced
from Ref. [6] by permission from IOP Publishing)
At 0.04 Hz At 1 kHz
Ground state
H
1
M/Ms
Ku
1 H in A/m
M/Ms
–10 –5 5 10
H in A/m –1
–5 5
0.2 mm
a) b)
Fig. 6 Difference between quasistatic and dynamic magnetization process, demonstrated for
a nanocrystalline Fe73 Cu1 Nb3 Si16 B7 tape wound core with circumferential anisotropy. The
quasistatic hysteresis loop in (a) is governed by the motion of 180◦ walls along the easy axis,
whereas dynamic excitation with a sinusoidal ac field of 1 kHz frequency results in a domain
nucleation-dominated reversal (b). Together with S. Flohrer, IFW Dresden. (Adapted and reprinted
from Ref. [7] with permission from Elsevier)
a) b)
From these examples we see that the correct interpretation of hysteresis curves
may indeed be strongly supported by the analysis of the domains that are responsible
for the loop. But magnetic domains can also be engineered on purpose to obtain
favorable properties in devices, and they can be actively used in devices as
functional units. The best-known example for domain engineering is the intended
domain refinement in transformer steel sheets by scratching or laser scribing
(Fig. 7a). The stress introduced locally in this way interrupts the basic domains,
acting like an artificial grain boundary. This mechanism works for well-textured
material, in which the basic domains would otherwise be wide thus causing large
anomalous eddy current losses when operated at power frequency.
A classical example for the application of magnetic domains is the bubble
memory which was developed back in the 1970s. In this device, cylindrical domains
as carriers of information were shifted in a magnetic garnet film along deposited
ferromagnetic structures on top of the film by applying a rotating magnetic field.
A modern concept of such a domain shift register device is the race track memory
(Fig. 7b), in which perpendicularly magnetized domains are shifted in a magnetic
nanowire by electrical current.
Domain Formation
Magnetic domains are formed to minimize the total free energy [9]. Under ideal
conditions (i.e., ignoring coercivity), a vector field of magnetization directions m(r)
arises in a ferro- or ferrimagnetic specimen so that the total energy reaches an
absolute or relative minimum under the constraint of a constant magnetization, i.e.,
m2 = 1. In this section the energies are reviewed, and it is demonstrated how they
act together to define the domain character.
8 Magnetic Domains 399
Magnetic Energies
The relevant magnetic energies are summarized in an illustrative way in Fig. 8. They
can be classified in local terms, which depend on the local magnetization direction
(anisotropy, applied field, and magnetoelastic coupling energy) and nonlocal terms
that give rise to torques on the magnetization vector, which depend at any point on
the magnetization direction at every other point. The stray field and magnetostrictive
self-energies belong to this class. The exchange energy may be seen as local, but it
depends on the derivatives of the magnetization direction. In the following the most
important aspects of the energy terms are listed. Given are energy densities Ex ,
which by integration lead to the energies εx = Ex dV with V being the sample
volume.
E ex = 0 M M
H ext = 0
M Easy
axis Ea = 0
E ex > 0 H ext
M
Ea > 0 H ext
Hd 100 >0
0]
M [10 0]
S N [01 0] Tensile
[10
stress
E ms > 0
Fig. 8 Summary of magnetic energies that are relevant for the formation and character of magnetic
domains
400 R. Schäfer
Anisotropy energy Most magnetic materials are anisotropic, i.e., there are easy
axes along which the magnetization vector is preferably aligned and along which
the saturated state can be “more easily” obtained than along other directions. These
can be preferred crystal axes (magnetocrystalline anisotropy) or an axis that arises
from some short-range ordering of atoms like Ni-Ni and Fe-Fe atomic pairs in NiFe
alloys. The driving force for this induced anisotropy is the magnetization of the
material that is present at an annealing temperature below the Curie temperature
and which can intentionally be aligned by an applied external magnetic field.
Also annealing under mechanical stress may result in a uniaxial anisotropy, called
creep-induced anisotropy. In amorphous and nanocrystalline ribbons, this type of
anisotropy may be dominating, and often an easy plane of magnetization transverse
to the stress axis is created by stress annealing. Shape effects are part of the stray
field energy, and they do not belong to the anisotropy terms.
Deflecting the magnetization out of an easy axis requires additional energy, called
anisotropy energy. In the most simple case of a uniaxial anisotropy (as it occurs
in crystal lattices with hexagonal or tetragonal symmetry or in case of an induced
anisotropy), the energy density is written as
where ϑ is the angle between anisotropy axis and magnetization direction and Ku1
and Ku2 are the anisotropy constants of first and second order – higher orders can
usually be neglected. An easy axis is described by a large positive Ku1 , whereas
‘planar’ and ‘conical’ anisotropies are found for large negative Ku1 and intermediate
Ku2 values. The anisotropy constant Ku1 corresponds to the energy needed to
saturate the sample in the so-called “hard” direction (ϑ = 90◦ ). In multiaxial
materials such as iron, all 100 directions are easy, whereas in nickel the 111
axes are the preferred crystal axes.
External field energy, also called Zeeman energy, is added to a magnet if an
external magnetic field H ext is applied. It is given by
where ϕ is the angle between magnetization and field. This interaction energy of
external field and magnetization vector field m(r) causes domain wall motion and
rotational processes and finally leads to saturation along the field direction if the
field is strong enough. The minimum of the Zeeman energy is achieved when the
magnetization is aligned to the magnetic field (ϕ = 0).
8 Magnetic Domains 401
Stray field energy Sinks and sources of the magnetization vector field (div m)
lead to magnetic poles, which act as sources and sinks for a magnetic stray field.
Magnetic poles can be present as volume or as surface poles if the magnetization
vector M is not parallel to the surface. The stray field H d , arising from the poles, is
illustrated in Fig. 8 for a finite ellipsoidal magnet that is homogeneously magnetized
to the right. This leads to north (N) and south (S) poles at the edges and a stray field
from (N) to (S). Within the magnet the stray field is called demagnetizing field as it
opposes the magnetization. The presence of poles and stray fields causes the stray
field energy
1
Ed = − μ0 H d · M with H d = −N · M . (4)
2
1
Ed = μ0 Ms2 = Kd . (5)
2
The stray field energy coefficient Kd is a measure for the maximum energy densities
which may be connected with stray fields. Independent of the complexity of real
stray fields, their energy always scales with the material parameter Kd . As the
demagnetizing field of a body along a short axis is stronger than along a long axis,
the applied magnetic field along the short axis has to be stronger to produce the same
field inside the specimen. The shape of the magnet is thus the source of magnetic
anisotropy (shape anisotropy). For an infinitely extended body that is magnetized
along an infinite direction, the demagnetizing factor N is zero, and there will be no
stray field energy at all.
9
Ems = − Cλ2100 , (6)
8
402 R. Schäfer
λs > 0
λs = +35·10–6 λs = +24·10–6
λs = 0
100 µm
λs = +8·10 –6
λs < 0.2·10–6
a) b)
Fig. 9 Illustration of magnetostrictive and magnetoelastic energies: (a) Closure domains,
observed on the surfaces of two amorphous ribbons with positive and zero magnetostriction as
indicated. A backward pointing magnetic field along the ribbon axis was applied. (b) Typical
domains in the as-quenched state of amorphous ribbons with different magnetostriction constants.
Frozen-in internal mechanical stress, which is present in all four materials after quenching, leads to
different complexity in domains depending on the magnetostriction constant. The ribbon thickness
is about 20 μm in each case
where λ100 is the magnetostriction constant for the 100 directions and C is the
relevant shear modulus for the given configuration. If not enforced for topological
reasons or by magnetic fields, nature tries to avoid such incompatible domain
arrangements. Figure 9a demonstrates this effect for amorphous ribbons with some
induced anisotropy perpendicular to the ribbon surface. A moderate magnetic field
along the ribbon axes was applied that enforces a certain longitudinal magnetization.
If magnetostriction is positive, domains running transverse to the field direction are
more favorable because here the sample elongation in the neighboring domains fits
together elastically. For a material without magnetostriction, a longitudinal domain
arrangement will cause no problem as the elastic distortion, indicated in Fig. 8, will
not occur. In fact this arrangement is even more favorable because here the specific
wall energy of the basic domain walls is lower than for the transverse case.
3
Eme = λs σ sin2 ϑ (7)
2
Domain wall energy The specific energy of domain walls is not an independent
term, but rather consists of exchange and anisotropy energy, owing to the deviation
of magnetization from the anisotropy axes and non-parallel magnetic moments
across the wall. In the most simple case of a Bloch√wall in an infinitely extended
uniaxial material the specific wall energy is γw0 = 4 A/Ku . See section “Domain
Walls” for more information on domain walls.
For summary, the characteristic coefficients of the magnetic energy terms and
their order of magnitude in typical magnetic materials are collected in Fig. 10.
Primarily it is the stray field energy that is responsible for the development of
magnetic domains: domains are formed to reduce or avoid stray field energy. This
fact is illustrated in Fig. 11 by comparing an infinitely extended with a finite sample.
The NiFe (permalloy) film was sputter-deposited in the presence of a magnetic
field, so it has a weak uniaxial anisotropy along the vertical direction in the images.
For Fig. 11a, a piece of the film was broken from the wafer which extends 30 mm
along the easy axis. In view of the thickness of just 240 nm, the specimen may be
considered as infinitely extended so that stray field energy does not play a role. In
fact, domains are not visible in that case: when a magnetic field along the easy axis is
applied, the film switches from magnetization up to down and vice versa, leading to
a magnetization curve with two steep, discontinuous steps at the coercivity field. The
switching occurs by the fast and abrupt motion of a 180◦ domain wall as indicated
schematically in the figure. The multidomain states at the discontinuity fields cannot
be captured in the experiment because the expense of domain wall energy makes
them statically unfavorable.
The situation changes if an open sample, prone to a demagnetizing field, is
considered. For Fig. 11b the infinite permalloy film was replaced by a 100×100 μm2
film element. For this finite specimen, the in-plane demagnetizing factor N has
raised to 0.0015, and a demagnetizing energy of N Kd m2 is added. A saturated state
at remanence, like in Fig. 11a, would thus be highly unfavorable as it would cost
30 x 5 mm2
M/Ms
1 1
Finite sample
( = 0)
Hext = Hint + M
µ0Hext in mT µ0Hext in mT
–5 5 –5 5
–1 –1
a) b)
Fig. 11 Comparison between infinitely extended and finite samples. Shown are the magneto-
optically measured magnetization curves along the (vertical) induced anisotropy axis in a Ni80 Fe20
Permalloy film of 240 nm thickness, which is infinitely extend in (a) and of finite size in (b). The
domain images in (b) show the full patterned element, whereas in (a, upper inset) only a part of
the extended film is shown. The lower inset in (a) is a schematics
8 Magnetic Domains 405
maximum stray field energy (| m |= 1). At zero field, the film element is rather
in a demagnetized, multidomain state that reveals a flux-closed, pole-free nature.
In the magnetization curve, this is expressed by the shearing transformation: for
a given magnetization value m, the external field Hext must be enlarged by the
demagnetizing field −Hd = N Ms m to reach the same magnetization state. Thus
the discontinuous magnetization curve is transformed into a finite-slope curve with
a well-defined magnetization value for every field value. For the finite element, the
domains can thus be followed along the sheared M(H )-loop.
So for the existence of magnetic domains, a finite sample size along the
magnetization direction (easy axis) is required as the stray field energy is the driving
force for domain observation. Infinitely extended films will consequently also have
domains if the easy axis is perpendicular to the film plane, compare Fig. 3.
There are two further cases in which magnetic domains or related objects can
exist even in the absence of demagnetizing effects:
• Consider a sample that is embedded in an ideal soft magnetic yoke to obtain flux-
closure. With a coil, wrapped around the yoke, a certain average magnetization
can be enforced in the yoke by some feedback mechanism. If a magnetization
value is then enforced in the sample that lies within the range of a discontinuous
jump in the magnetization curve, a multidomain state will be enforced in which
the two states at the endpoints of the jump will be mixed in a certain volume
ratio so that the enforced magnetization is achieved. In case of the previously
discussed uniaxial material, this would be a 180◦ domain state in which the 180◦
domain walls move as the enforced magnetization is varied. Such circuits are
realized in machines with an inductive load on a rigid voltage, such as an idling
transformer.
• The second case may be found in magnetic materials with broken inversion
symmetry in the atomic lattice in which the crystallographic handedness induces
a quantum-mechanical Dzyaloshinskii-Moriya interaction (DMI) [10] by spin-
orbit scattering. Unlike direct Heisenberg or superexchange, which favor parallel
or antiparallel alignment of neighboring magnetic moments according to a
Hamiltonian that is proportional to S i · S j , the DMI is proportional to S i × S j
thus favoring perpendicularly aligned neighboring spins S. In competition with
collinear coupling, the DMI can lead to nanoscale, homochiral magnetization
modulations like long-period helical spin-spiral phases. Most prominent is the
topologically stable skyrmion spin structure that was predicted theoretically by
A. Bogdanov [11, 12] and which has been directly observed in nanolayers of
cubic helimagnets with intrinsic DMI [13] and in Fe/Ir bilayers [14] with surface-
/interface-induced chiral interactions [15]. Magnetic skyrmions are axisymmetric
vortex patterns with a homochiral rotation of spins that can exist as isolated
entities in the saturated states of chiral magnets [14,16] or in form of skyrmionic
condensates (two-dimensional lattices and other mesophases) [12, 17].
whereas the modulated elements of multidomain states (domain walls, Bloch lines,
Bloch points, magnetic swirls etc. – compare Fig. 18) are commonly addressed as
being part of magnetic microstructure [1]. This different classification, however, is
questionable: spatially inhomogeneous spin structures arising in magnetic nanolay-
ers are formed under the mutual influence of intrinsic and dipolar forces [18]. This
levels out the difference between the terms magnetic microstructure and magnetic
micro- or spintextures [19].
Interplay of Energies
Once the precondition for domain formation is fulfilled, the domain character is
finally determined by an interplay of the magnetic energies. For demonstration of
this principle, let us have a look at the prominent example of domain formation in
grain-oriented Fe3wt%Si steel that is used as core material in transformers. Like
for pure iron, the easy directions of magnetization are the 100 directions for this
material. Transformer sheets are typically 0.3 mm thick, consist of wide grains in the
centimeter regime, and are Goss-textured. In this [001](110) texture the [001] easy
direction is oriented, within a few degrees deviation, along the rolling axis during the
manufacturing process of the sheets. The grain surfaces are (110) oriented within the
same accuracy, and the other two easy axes are oriented at angles of ±45◦ relative
to the surface. As shown in Fig. 12, the domain structure of such sheets consists
of simple slab domains that are separated by 180◦ walls in case of ideally oriented
grains. Their existence may, e.g., be enforced by some demagnetization effects at
the grain boundaries. For increasing out-of-plane misorientation of the [001] easy
direction, fine lancet-shaped domains of increasing density are superimposed on the
basic domains.
The formation of those so-called supplementary domains is a consequence of
energy optimization. Let us firstly assume an infinitely extended grain with ideal
(110) orientation. It will be homogeneously magnetized along the surface-parallel
easy axis (Fig. 13a), thus completely avoiding magnetic poles. As the grain is
infinitely extended, domains are not to be expected. A different situation arises if
the [001]-axis is misoriented by some degrees relative to the surface (b). Assuming
that the magnetization strictly follows the [001] axis, magnetic surface poles will
arise. The associated stray field energy can be reduced by forming ±180◦ basis
domains (c) which leads to the presence of opposite poles on the same surface, thus
allowing the field lines of the stray field to run along the surface. A further reduction
of stray field energy could be achieved by reducing the basic domain spacing as
this would bring the opposite poles in closer distance. However, the narrower the
domain width, the higher the expense of domain wall energy associated with the
rising wall area of the basic domain walls that extend all through the thickness.
Nature finds a more economic way to keep the overall energy low by adding
supplementary domains to the basic domains (d). The shallow lancet domains at
the surface collect the net flux that is transported toward the surface in the basic
domain. The lancets are oppositely magnetized to the basic domains, thus leading to
8 Magnetic Domains 407
(110) surface
Goss texture 100 easy axes
0.1 mm Out-of-plane
misorientation
2° miso
riented
4° miso
riented
idealy
oriente
d
8° mis
oriente
30 mm d
Fig. 12 Domains on a Goss-textured transformer sheet. Shown are the domains of four grains with
increasing out-of-plane misorientation as indicated. The ceramic insulation coating, by which such
sheets are usually covered to avoid eddy currents between the sheets, was removed for domain
imaging by Kerr microscopy. (The domain images are adapted by permission from Ref. [1] (c)
Springer 1998)
a narrow spacing of opposite surface poles as required for stray field reduction. The
flux is then transported to a surface of opposite polarity and distributed again. This
is achieved by internal domains that are magnetized along the internal, transverse
easy axes. Those transverse domains can extend all through the volume, or they
can be connected to a basic domain wall so that the neighboring basic domain
is used to lead flux downwards. Because this system of compensating domains is
superimposed on the basic domains that would be present without misorientation,
these domains are called supplementary domains.
If a (moderate) magnetic field is applied along the surface-parallel easy axis,
Zeeman energy is added and those basic domains with magnetization along the field
direction will grow on expense of the opposite basic domains by 180◦ wall motion.
The rise in stray field energy, caused by the absence of oppositely magnetized
basic domains, is then compensated by an increasing number of supplementary
domains. At the same time those internal transverse domains, which are connected
to the basic domain walls, have to extend across the whole sheet thickness. So the
transverse domain volume is larger compared to the demagnetized state. This change
in relative domain volumes has consequences for the stress state of the sheet: as the
magnetostriction constant is positive for FeSi, the cubic crystal lattice is tetragonally
distorted along the magnetization direction. The basic domains thus cause an
408 R. Schäfer
N N
N S
N N
N N N N
Easy N N
axes S S N S
S N
S S S S
a) b) c)
S S S
S N N
N S S S
N N
N
N
N S S N
N N Tensile stress
S e)
S
d)
µ*-corrected
N N N
N
N
N
N
elongation of the sheet along the rolling direction, while in the transverse domains
the sheet is transversely expanded. A change in the transverse domain volume will
thus result in a magnetostrictive change in length during remagnetization along the
[001] easy axis. Driven in a magnetic field at power frequency, the sheet will be
set in mechanical vibration leading to acoustic transformer noise. Furthermore, the
repeated destroying and rebuilding of supplementary domains forms an important
part of hysteresis loss as the energy bound in the supplementary domains is lost in
every cycle.
Magnetostrictive interaction can, however, also be favorably used in transformer
sheets. The supplementary domains are suppressed under tensile stress applied
along the preferred axis, because tensile stress magnetostrictively disfavors the
transverse domains that are attached to the supplementary domains. A domain state
as in Fig. 13c would thus result. Rather than superimposing supplementary domains
8 Magnetic Domains 409
to lower the stray field energy, which is forbidden now, a similar effect is achieved
by lowering the basic domain width (e). The domain images in (f) demonstrate this
effect. Obviously even ideally oriented grains assume a small domain width if they
are coupled to less well-oriented grains to achieve flux continuity. A narrow domain
with is favorable if the domains are excited by AC magnetic fields. The larger the
density of the walls, the smaller the velocity of every wall for a given induction level
which lowers domain wall-related eddy current effects (so-called anomalous eddy
current losses). In practice the tensile stress is created by the insulation coating that
is at the same time stress-effective. The planar stress exerted by the coating is for the
Goss texture equivalent to a uniaxial stress and will thus suppress the supplementary
domains.
Two further, energy-related aspects are worth to be noted: (i) so far it was
assumed that the domains are strictly magnetized along the easy crystal axes in the
demagnetized state and up to moderate applied magnetic fields. This is in fact true
for most of the volume domains. By approaching the (110) surface, however, the
magnetization bends toward the surface (Fig. 13g). So the surface poles are spread
over a certain volume and not just at the surface which helps to reduce the stray
field energy at the expense of some anisotropy energy, though. The phenomenon
is known as μ*-effect. (ii) The basic ±180◦ walls are zigzag folded across the
thickness as indicated in Fig. 13. Although the total wall area is larger than in case
of straight, perpendicular (110) walls that would have the smallest area, the total
wall energy is reduced by the folding. The reason is the specific wall energy, which
is lower for {100} wall orientations. The (110) wall therefore tends to rotate toward
these orientations, forming tilted or zigzag walls with a lower overall energy.
Domain Classification
The magnetic energy coefficients, listed in Fig. 10, can be combined in several ways
to obtain dimensionless parameters that reflect the interplay of energies and thus the
domain character. The ratio between anisotropy and stray field energy is the most
important. This ratio is called the quality factor, defined by
Keff
Q= . (8)
Kd
Here Keff is the effective anisotropy constant and Kd the stray field energy
coefficient defined in Eq. (5). If the anisotropy energy dominates over the stray field
energy (Q > 1), domains are formed that avoid an expense of anisotropy energy
while keeping the stray field energy as low as possible. If the stray field energy is
dominant (Q 1), stray fields are avoided by flux-closed domain patterns that
adapt to keep the anisotropy energy as low as possible. In the following discussion
we use the quality factor as primary criterion as it leads to the most fundamental
way of classifying domains and magnetic materials. In Fig. 14 a number of typical
materials are listed in the order of decreasing quality factor. Further criteria are the
410 R. Schäfer
0 0
µ0 Ms A K1 , Ku w w
Material Q 10
in Tesla in 10 J/m in J/m3 in 10 m in mJ/m2
1.7 107
SmCo5 1.05 12 39 0.84 57
hexagonal
4.9 106
CoPt (L10) 1.0 10 12 1.5 28
tetragonal
4.2 106
Sm2Co17 1.29 14 6.3 1.83 31
rhombohed.
4.5 106
Nd2Fe14B 1.61 7 4.4 1.25 23
tetragonal
3.2 105
BaFe12O19 0.48 7 3.5 4.68 6
hexagonal
Fe74Cu1Nb3Si15B7 ~20
1.24 6 4 10 0.2 550 0.04
nanocryst. ribbon Ku induced s
Amorph. ribbon, ~3
0.6 2.5 2 10 0.1 900 0.01
Co-based Ku induced s
Fig. 14 Material parameters that are important for domain analysis. The listed materials are
ordered in terms of decreasing quality factor Q. Listed are furthermore saturation polarization
μ0 Ms , exchange stiffness constant A, first order anisotropy constant K1,u , magnetostriction
constant λ, wall width parameter Δ0w [see Eq. (14)], and specific wall energy of a 180◦ Bloch
wall γw0 [see Eq. (13)]. (Data are taken from Refs. [20, 21])
manifold of easy directions and the surface orientation of the investigated specimen,
which we treat as secondary criteria to classify the wide variability of domain
phenomena.
In Fig. 15 the interplay of stray field and anisotropy energy is illustrated by
comparing three material classes with uniaxial anisotropy but highly different
Q-factors. In all cases the easy axis is perpendicular to the plate surface, on
which domain observation was performed by Kerr microscopy, i.e., the specimens
are extremely misoriented with respect to the imaged surface. Compared are the
domains of a NdFeB single crystal (left column) with those in amorphous films and
ribbons (right column). The strong magnetocrystalline anisotropy of 4.5 · 106 J/m3
8 Magnetic Domains 411
D Ku
Dominating Dominating
anisotropy energy (Q >1) stray-field energy (Q<<1)
Film: Surface
D = 5 µm 5 µm
W
1
D =
S N S N 1 µm
Q=
7 µm N S N S 0.01
a) e)
Towards bulk:
N S N
7 N S N D =
25 µm
Q=
14 µm 0.0003
b) f)
D =
25 µm
40 µm
Q=
0.001
c) g)
D =
25 µm
120 µm
Q=
20 µm 0.002
d) h)
(Q 1)
D =
1 mm
5 µm
Fig. 15 Classification of magnetic domains for three extrem cases of the quality factor. (a–d)
NdFeB single crystal, Q = 4.4. (e–h) FeBSi-based amorphous film and ribbons with stress-
induced perpendicular anisotropy and Q-values as indicated. (i) Cobalt single crystal, Q = 0.35.
In each case the domain images are taken on top surface, while the sketches show side views. The
Kerr images in (a–h) are adapted by permission from Ref. [1] (c) Springer 1998, while (i) was
obtained together with I. Soldatov, Dresden, and reproduced from Ref. [22] with the permission of
AIP Publishing
412 R. Schäfer
assuming the corrugated shape visible in the photograph and model. With a further
increase in anisotropy or sample thickness, the stripe domains do grow into regular
domains, the closure domains of which now decay into a further generation of
stripe pattern as shown in (h). This type of branching may be considered as multi-
phase branching which occurs despite the fact of having a uniaxial material rather
than cubic or other multiaxial materials. In any case, the overall domain patterns
(e - h) are completely free from stray field energy as required for such low-Q
material.
If anisotropy and stray field energy are competing with about equal magnitude
(Q ≈ 1), a hybrid structure is formed as shown in Fig. 15i for a thick cobalt
crystal. The character of the domain pattern is similar to that of NdFeB in the
macroscopic aspects, i.e., the branching mode in the bulk agrees with that of the
high-anisotropy material. The surface domain width, however, is smaller because of
the smaller wall energy of cobalt and theory predicts closure domains with a tilted
magnetization, owing to a lower anisotropy compared to NdFeB. By comparing
the two domain photographs in Fig. 15i, which show the out-of-plane and in-plane
magnetization components separately, it seems that the fine surface pattern of the
in-plane component resembles the branched domains of the amorphous ribbon in
image (h). Obviously the closure domains are modulated in a dense stripe domain
pattern. According to these findings, cobalt with its intermediate anisotropy forms
a kind of hybrid, following the high-anisotropy two-phase branching scheme in the
bulk and a low-anisotropy multiaxial branching scheme at the surface.
The classification principle discussed so far is generally valid – different crystal
symmetries or sample orientations just add modifications. Consider the case of
Fe3wt%Si material in which the three 100 axes are easy. The quality factor of 0.03
implies flux-closure domain configurations at zero field. Their character depends
on the surface orientation, and by having two further easy axis compared to the
uniaxial materials in Fig. 15, more degrees of freedom for the domain formation
are available. This becomes immediately apparent by looking at the domains of
the non-oriented sheet presented in Fig. 16a. The variety of flux-closed domain
patterns can be sub-classified according to the surface orientation: on an ideally
oriented surface, the principle of flux closure is immediately seen by wide domains
that are separated by well-oriented domain walls. Two grains with (110) and (100)
orientations are marked in the figure. A pole-free wall orientation requires that the
component of the magnetization perpendicular to the wall is the same on both sides
of the wall as indicated in Fig. 16b. For slight misorientation of a few degrees
flux collection is achieved by supplementary domains as seen for the (100)-related
surface in Fig. 16c (see Fig. 13 for a thorough explanation of this phenomenon for
a (110)-related surface). For stronger misorientation a domain branching scheme is
energetically preferred. In Fig. 16d this is illustrated for a (111) surface, i.e., the case
of extreme misorientation. Here in most of the volume a domain structure is formed
that occupies easy directions only, and these domains are joined so that no magnetic
stray fields are generated as required by Q 1. Near the surface zones, however,
the two requirements of using only easy directions and avoiding stray fields are
incompatible as the surface does not contain an easy direction. By branching nature
finds a compromise: the domains get finer toward the surface by adding several
414 R. Schäfer
~(111)
~(110)
(100) 10 µm e.a.
face
~(100) sur
1)-
(110) (11
100 µm
(100)-cut
a) d)
mn Pole-free
wall orientation
mn m2 requires:
m1 (m1 m2) n = 0
a)
n
b) c)
Fig. 16 The domains on a non-oriented Fe3wt%Si sheet (0.5 mm thick) reveal the influence
of the surface orientation on the domain character. (a) Low-resolution Kerr image giving an
overview. (b) Schematics of a 90◦ wall illustrating the condition for a pole-free wall orientation. (c)
Sketch of the fir tree structure, a supplementary pattern that appears on slightly misoriented (100)
surfaces of iron-like material. (d) High-resolution Kerr image on a (111) surface, together with
a schematics showing the phenomenon of multiaxial branching in iron-like material with cubic
crystal anisotropy. (The images in (a) are adapted by permission from Ref. [23] (c) Springer 2009)
Domain Walls
x x 0
–4 –2 0 2 4
x / A/Ku
Néel S N
path
Right domain a) b) W180
Fig. 17 (a) Bloch and Néel wall paths in an infinite uniaxial material. The magnetic poles for the
Néel wall are indicated in the vector plot. (b) Wall profiles of a 180◦ Bloch wall. The indicated
wall width, W180 , is defined on basis of the slope of the magnetization angle ϕ(x). (Adapted by
permission from Ref. [1] (c) Springer 1998)
Here x is the coordinate perpendicular to the wall, the angle ϕ rotates in the
wall from 90◦ to −90◦ , and ϕ(±∞) are the boundary conditions given by the
416 R. Schäfer
neighboring domains (see Fig. 17a). The solution of this ansatz is obtained by
variational calculus, which leads to a function ϕ(x) that minimizes γw0 under the
boundary conditions. Starting with Euler’s equation
2A(dϕ/dx)
A(dϕ/dx)
2 = Ku cos2 ϕ . (11)
According to this equation, the exchange and anisotropy energy densities are equal
at every point in the wall: at positions where the anisotropy energy is high, the
magnetization rotates rapidly leading to a large exchange energy. From Eq. (11) we
obtain
dx = A/Ku dϕ/ cos ϕ , (12)
which, inserted together with (11) into the total wall energy (9), yields
∞ π/2
γw0 = 2 Ku cos2 ϕ dx = 2 AKu cos ϕ dϕ = 4 AKu . (13)
−∞ −π/2
√
Integration of (12) leads to the functional dependence sin ϕ = tanh(x/ A/Ku ),
which is plotted in Fig. 17b. From the indicated definition, the classical Bloch wall
width is derived as
W180 = π Δ0w , with Δ0w = A/K (14)
Walls in thin films with Q < 1 From the micromagnetic point of view, magnetic
films are defined as “thin” if their thickness is below the classical Bloch wall width.
Then wall modes using a predominantly in-plane rotation of magnetization, known
as symmetric Néel wall and cross-tie wall, have a lower energy than the Bloch mode,
although magnetic poles cannot be avoided in those walls. The characteristics of
8 Magnetic Domains 417
D = 60 nm D = 460 nm
Asymmetric
Bloch wall
Cross-tie wall D = 10 nm
Symmetric
20 µm wall
Permalloy thickness in nm
50 100 200 375
Wall angle
Symmetric
S N Asymmetric
S S S N N N
S N
Tail Core Tail
Cross-tie Asymmetric
Symmetric Néel wall wall Bloch wall Vortex wall
//
1 2 3 4 5 6 7 10 12 15 20 25 30 40 50 60 5
D / A/K d D / A/K u
Side view
Fig. 18 Phase diagram for various types of domain walls that exist in low-Q thin and thick films
at zero applied field and in a hard-axis field that causes magnetization rotation in the domains,
thus reducing the wall angle. The corresponding thicknesses for permalloy are indicated. Shown
are high-resolution Kerr images of permalloy together with sketches (symmetric Néel and cross-tie
wall, Bloch lines and swirl) and micromagnetically simulated vector plots (asymmetric Bloch and
Néel wall, calculated for permalloy). The contour lines in the calculated wall profiles indicate the
center of the walls, i.e., the surfaces on which the magnetization is strictly aligned in the drawing
plane. The pictures are taken and adapted from Ref. [1]. Since the anisotropy has only a moderate
influence on the wall energy in films, the diagram is valid for a wider range of low-Q materials.
(Adapted by permission from Ref. [1] (c) Springer 1998)
the symmetric Néel wall is its decomposition in a sharply localized core and two
extremely wide tails that take over a large part of the total rotation. A dipolar pole
pattern appears at the core, which carries about half of the pole density, and the other
half of the poles are displaced in the tails, both of them adding stray field energy.
The two characteristic lengths of a 180◦ Néel wall in a film of thickness D are then
given by
Wcore = 2 A/(Ku + Kd ) and Wtail ≈ 0.56DKd /Ku . (15)
energy (Ku ). The stray field energy thus has an opposite effect on both parts of
the wall. The poles in the extended tails of symmetric Néel walls lead to strong
wall interactions as soon as the tails overlap. In thin permalloy films, for example,
this happens up to wall distances as high as 100 μm. This interaction can result
in attraction or repulsing of neighboring walls if the walls have opposite or equal
rotation senses, respectively, called unwinding and winding walls.
The pole density of a symmetric Néel wall can be drastically lowered by reducing
the wall angle, e.g., by applying a magnetic field perpendicular to the easy axis. If
the total√integrated pole density in each half of the wall is μ0 Ms , it is reduced to
(1 − 1/ 2)μ0 Ms D for a 90◦ wall. As the stray field energy varies quadratically
with the pole density, a 90◦ Néel wall has just 12% of the specific energy of a 180◦
wall, leading to strong preference for lower-angle Néel walls. As a consequence,
the symmetric 180◦ Néel wall at zero field is replaced in thin films by the cross-tie
wall, a composite wall that actually consist of crossing 90◦ walls. Although the total
length of the wall segments within this pattern is 3 to 4 times larger than the original
180◦ wall area, the total wall energy is smaller. Below a critical wall angle of about
135◦ the cross-tie wall is replaced by the symmetric Néel wall.
For very thin films (below about 50 nm for permalloy), the cross-tie wall becomes
unstable, however. The reason are the Bloch lines occurring for topological reasons
at the centers of the continuous transitions between the partial walls. Depending
on the magnetization environment, circular and cross Bloch lines (also known as
vortex and antivortex) are distinguished. Bloch lines are not singularities, because
the magnetization turns perpendicular to the surface when approaching their center.
As mainly stray field and exchange energy are √ competing in a Bloch line, its core
width scales with the characteristic length A/Kd (about 5 nm for permalloy),
which is small compared to the wall width. Bloch lines are therefore strongly pinned
at defects of similar size, thus acting as a source of wall coercivity in thin films. With
decreasing film thickness, the stray field energy of a Bloch line increases, so that for
very thin films the symmetric Néel wall is energetically preferred again despite its
higher specific wall energy. Bloch lines are present in such walls but much less
frequently compared to cross-tie walls.
Walls in thick films with Q < 1 Films with√a thickness beyond the Néel-Bloch
wall transition, which occurs typically at 20 A/Kd or ∼100 nm for permalloy
films, are defined as thick films. Asymmetric Bloch walls, favored for small or zero
field, are characteristic for such films. Due to a two-dimensional internal vortex
structure, which appears asymmetric relative to the wall plane, this wall mode is
completely stray field-free although it appears like a common Néel wall at the
surface. The eddy is geometrically √ determined so that the wall width scales with
the film thickness rather than with A/Kd as for the symmetric Néel wall. Because
the anisotropy energy plays a minor role (Q < 1) and stray field energy is excluded,
the exchange energy is the predominating term for the asymmetric Bloch wall. The
wall has four equivalent orientations, since the vortex can be on the left or right and
the center magnetization can be upward or downward. Usually all four orientations
appear within the same wall with the segments being separated by Bloch lines.
8 Magnetic Domains 419
The structure of the asymmetric Bloch wall loses its mirror symmetry in an
applied hard-axis field (i.e., for reduced wall angles). Beyond a certain field value,
another vortex wall mode, the asymmetric Néel wall, becomes favorable because it
is better adapted to the applied field. It is point-symmetric in the cross section, the
horizontal magnetization component is given by the field direction thus pointing in
the same direction at both surfaces, and the out-of-plane excursion in the volume
can be either up or down leading to two equivalent variants. Like the symmetric
Néel wall, the asymmetric Néel wall also splits off an extended, logarithmic tail but
with much less pole density as most of the poles are avoided by the two dimensional
vortex pattern [25]. Below a critical wall angle of ∼ 45◦ the asymmetry disappears
in favor of the symmetric Néel wall.
Walls in√bulk specimens with Q < 1 The upper limit for thick films can be set at
about 5 A/Ku for uniaxial films (or 1.5 μm for permalloy), when the characteristic
thick-film Bloch wall gradually transforms into the classical Bloch-type wall at
least inside the sample, whereas the vortices are confined to the neighborhood of
the surfaces, thus providing flux closure and pole avoidance. At the surfaces the
magnetization of such vortex walls rotates parallel to the surface (reminiscent of the
Néel mode and sometimes called a Néel cap), and the surface wall width is wider
than the width of the Bloch part in the volume that is given by Eq. (14). If two wall
segments with opposite surface rotation sense meet, a Bloch line is enforced for
topological reasons. In its core the magnetization
√ turns perpendicular to the surface
forming a swirl with a diameter of the order of A/Kd rather than a singularity.
Ferromagnetic
layer
a) Spin-orbit layer
Swirl,
vortex
Fig. 19 (a) Néel walls of the same chirality, induced by Dzyaloshinskii-Moriya interaction.
Shown is the cross section through a bilayer film. Head-on domains in an extended film (b) and
in Q 1 nanostrips of rectangular cross section with transverse (c) and vortex wall (d), seen
from the top in each case. The latter are of lower energy in wider strips and thicker films. (The
schematics in (c) and (d) are redrawn following Ref. [27])
Special walls The full development of cross-tie walls or extended Néel tails
requires sufficiently extended films. If geometrical restrictions are present, specific
wall structures may develop. A prominent example are head-to-head or tail-to-tail
walls in low-anisotropy (e.g., permalloy) film strips with sub-micrometer width,
which have been of interest in the early stages of research on current-induced
wall displacement devices (section “Current-Driven Domain Wall Motion”). If two
domains meet head-on in an extended film, a straight transversal wall would have
strongest pole concentration. By forming a zigzag shape (Fig. 19a), the pole density
decreases at the expense of wall surface, though. Depending on the film thickness,
the core of this wall may be of Néel, cross-tie, or Bloch-type, and part of the
poles are distributed in tails on both sides similar to the tails of the symmetric
Néel wall. As the zigzag amplitude and period require spatial ranges between tens
and hundreds of micrometer, zigzag walls are not possible in sub-micrometer wide
strips. Special wall types, termed transverse and vortex walls, are rather formed
(Fig. 19b, c). Their width is determined by the shape anisotropy of the wire and
thus varies approximately with the wire width. Both structures are characterized by
topological objects as marked in the figure. For details see the reviews [28, 27].
If a domain pattern is exposed to a magnetic field that favors certain domain phases
against others, a pressure acts on the domain walls which separate these phases,
and they are set in motion in order to lower the energy of one domain phase with
respect to another. The wall mobility and velocity are determined by a number of
mechanisms:
8 Magnetic Domains 421
• Domain walls may interact with inhomogeneities in the material like nonmag-
netic inclusions, grain- and phase boundaries, stress centers, etc. if the wall saves
energy when resting at these positions. For example, a nonmagnetic inclusion
exerts a pinning force to the wall as the wall saves area and thus energy when
it intersects the inclusion. The pining force is described by the balance between
the gain in Zeeman energy when the wall moves a certain distance, driven by the
field, and increase in wall energy. When some critical field, the static coercivity
Hcs , is exceeded, the wall breaks away from its pinning site and starts moving,
typically by a Barkhausen jump till it is pinned by the next obstacle. This leads
to micro-hysteresis steps that sum up to the macro-hysteresis curve. If thermally
activated creeping effects are relevant (like for the films in Fig. 3), Hcs will be
lowered with rising temperature.
• Once the wall is set in (steady) motion, it moves with a velocity v that is
proportional to the driving field Hext according to v = μw (Hext − Hcs ) where μw
is the wall mobility. It is determined by eddy currents, intrinsic damping, or other
dissipative processes, which all act like friction to the moving wall and additively
determine the overall mobility.
• One of the origins of wall friction may be thermal diffusion leading to an
induced anisotropy. If the wall moves fast enough so that the induced anisotropy
changes little when the wall moves by its width, the diffusion effects just add
to friction-like losses. If the wall rests, however, it becomes hard to move after
some time, resulting in static coercivity. In between, a fractional decrease of
wall mobility (i.e., permeability) with time under otherwise constant operation
conditions, known as disaccommodation, is the consequence. The classical
example for such a process is the diffusion of carbon in iron. In metallic materials,
disaccommodation can be avoided by removing or binding the disturbing atoms
or point defects. In high-permeability ferrites, on the other hand, electron hopping
between two- and three-valent iron ions on the same octahedral lattice sites may
lead to disaccommodation effects that are hard to suppress.
• While disaccommodation may be important for slow magnetization processes,
eddy current effects in metallic materials become more effective with increasing
frequency. For a moving domain wall, the flux change in the region swept out by
the wall induces a voltage according to Faraday’s induction law, which causes
the flow of eddy currents. They are responsible for a magnetic eddy current
field that opposes the applied field. Because the effective field acting on the
wall is consequently less than the applied field, the wall velocity is less than
if the eddy currents did not exist, i.e., the wall motion is damped. For a planar
wall oriented perpendicular to the surface of a sheet, for example, the eddy-
eddy
current-limited mobility is μw = v/H = 3 · 106 /(Ms σ D). The lower the
electrical conductivity σ and the smaller the thickness D, the more restricted are
the eddy currents and the larger the mobility. Due to eddy currents a moving
wall is retarded more at the center than at the surfaces, which may lead to drastic
wall deformations. At high velocities the walls become grossly deformed to run
mostly parallel to the surface. Eventually, magnetization processes occur mostly
in a surface-parallel sheet, a phenomenon known as the skin effect.
422 R. Schäfer
dm dm
= −γ m × H eff − α m × +τ, (16)
dt dt
where γ = μ0 gμB /h̄ is the gyromagnetic ratio in units [m/As] with μB the
Bohr magneton and g the Landé factor. The LLGS equation describes the
gyromagnetic precession of the magnetization around an effective field Heff
(first term) and its relaxation toward Heff (second term) as illustrated in Fig. 20
(for the τ -term, denoting current-induced torques, see section “Current-Driven
Domain Wall Motion” and Fig. 24c). The effective field incorporates applied and
demagnetizing fields, but also contributions from anisotropy, exchange stiffness,
etc. The second term, also called viscous-damping term, is caused by intrinsic
dissipative phenomena like the scattering of spin waves on lattice defects or the
relaxation of magnetic impurities, which are considered in the dimensionless
damping factor α. At low frequencies the loss term in the LLGS equation is
predominant, and the magnetization turns toward the effective field until both
vectors are parallel within some finite time. The gyromagnetic term has to be
taken into account only in the GHz frequency regime where it leads to strong
precessional effects on moving domain walls.
As an example let us discuss a one-dimensional Bloch wall in an extended film
with uniaxial anisotropy perpendicular to the film plane, exposed to a magnetic
field along one of the domain directions, i.e., perpendicular to the magnetization
in the center of the wall (Fig. 21a, b). If the field is slowly increasing, the damping
term in the LLGS equation dominates and the applied field exerts a direct torque
on the spins inside the wall as illustrated in (a). When the applied field is
sufficient to overcome pinning forces, the torque causes the wall to move in x-
direction. If a step-function drive field is applied to a stationary wall, however,
the wall is set in fast motion, and gyrotropic precession will become dominant
Hext
Wall velocity
Walker +
(slow) break-
down
Time
on
r
To
oti
ll m
Chaotic
x tion
Wa l mo
a) motion
na
ce ssio
Pre
H ext Conservative,
S
(fast) Hd m steady motion
N
m H ext d)
b) m Hd
z z
x
y y
Fig. 21 Torques on the magnetization vector of a 180◦ Bloch wall in case of a slowly (a) and
fast (b) changing magnetic field. The development of a Néel component in a moving Bloch wall is
illustrated in (c). The wall velocity as a function of magnetic field (d) is characterized by the three
typical regimes of steady, chaotic, and precessional motion. In the latter mode, the wall oscillates
between forward and backward motion as indicted in (e)
for the wall energy and wall width parameter. In case of dynamic equilibrium, the
Zeeman torque is cancelled by the demagnetizing torque and damping, so that the
wall translates with a constant ϑ and a fixed spin structure throughout the wall
424 R. Schäfer
As ϑ increases with rising velocity [see first term in (18)], the wall width
decreases, and the wall energy increases according to (17). From v = μw Hext
and (18), the wall mobility of a 180◦ wall is derived as μw = 4Aγ /(αγw ). The
higher the energy of a wall, the lower its mobility.
With increasing field the velocity increases up to a maximum value that is
reached when the equilibrium between damping/demagnetizing torque and drive
field torque is broken, i.e., the Zeeman torque begins to dominate. The peak
velocity vp and peak field Hp are found as [1]
vp = γ 2AQ/μ0 f (Q) and Hp = αHa f (Q) 4 1 + 1/Q (19)
√
with f (Q) = 1 + 1/Q − 1. The peak field, also called Walker field, is
obviously proportional to the anisotropy field Ha = 2Ku /(μ0 Ms ). Beyond the
peak velocity, a steady-state motion with a fixed spin structure is not possible
anymore and a transient region of “negative mobility” is found (Fig. 21d) in
which the average velocity decreases with increasing applied field. The wall
develops spatially inhomogeneous modes in that regime with parts of the wall
advancing, while other parts are lacking back in an inhomogeneous, “chaotic”
way. For the following linear regime, the wall angle ϑ undergoes a more or
less free precession with the wall magnetization cycling periodically through
Bloch and Néel wall configurations, while the wall itself oscillates back and
forth as indicated in Fig. 21e. The motion is oscillatory as the torque term is
periodic with respect to ϑ. Due to damping, the backward motion is smaller than
the forward one, resulting in a positive average displacement with a non-zero
average velocity. Anyway, domain wall motion beyond the peak velocity of the
external field has to be considered highly irregular. For this reason the maximum
velocity possible for a stationary wall motion is also called the “breakdown”
velocity, and the phenomenon is known as Walker breakdown. It determines the
maximum possible speed of devices that are based on domain wall motion. In
(thick) bubble garnet films, for instance, the peak velocity reached values of
the order of 100 m/s. Compared to extended and thick films, the Walker field
is reduced in case of confined systems like nanowires or ultrathin films due to
complex demagnetizing field effects [29].
The increase in wall energy up to the breakdown velocity can be interpreted as
if the wall exhibits an effective (not a real) mass. The wall mass becomes obvious
from the equation of motion of a vibrating wall
8 Magnetic Domains 425
d2 x dx
mw 2
+ b + ax = 2Ms (Hext − Hcd ) , (20)
dt dt
1 ∞ μ0 v 2 Ku π/2 μ0 γw0 2
γwdem = − μ0 Mx Hd dx = cos ϕdϕ = v . (21)
2 −∞ 2γ 2 A −π/2 4γ 2 A
is derived. The mass is inversely proportional to the wall width parameter Δ0w .
For a 180◦ wall in iron with γ = 2 · 105 m/As, A = 21 · 10−12 J/m, and γw0 =
4 · 10−3 J/m2 (see Fig. 14), for example, the wall mass is approx. 3 · 10−9 kg/m2 .
Conventionally, domain walls are set in motion by the pressure that acts on a
wall by an applied magnetic field according to Eq. (20). An alternative way is
wall motion driven by spin-polarized current. In small structures like magnetic
nanowires this mechanism may dominate over the effects due to the self-field of
the same current. While field-driven wall motion would be opposite for neighboring
domain walls (domains either expand or shrink in a magnetic field), all walls are
pushed in the same direction by polarized current pulses making the racetrack
memory concept [8] possible (see Fig. 7b). Current-driven domain wall motion
is based on the phenomenon of spin-transfer-torque (STT) that was predicted by
Berger and Slonczewski [32,33,34]: because of spin-dependent diffusive scattering,
an electrical current carries spin angular momentum when it travels through a
magnetic material with the majority of the electron spins being aligned along the
magnetization direction. As these spin-polarized itinerant electrons pass through a
domain wall, the electron spin precesses and changes its polarization direction due
to the exchange interaction with the localized spins of the wall. To conserve the total
spin, the change of momentum of the traversing electrons needs to be transferred to
the wall spins. The local magnetic moments in the wall thus experience a torque that
changes their direction, possibly resulting in a displacement of the wall along the
direction of the electron flow.
Phenomenologically, the SST effect is taken into account by the τ -term in the
LLGS equation of motion (16). For arbitrary current direction and wall structure,
this term is written as the sum of two spin-torque terms proportional to the gradient
of the magnetization [35]:
γ h̄Pj
τ = −(u · ∇)m + β m × [u · ∇)m] , with | u |= . (23)
2eMs μ0
The term (u · ∇)m reads u(∂m/∂x) for a current along the x direction. The vector
u scales with the current density j and represents the maximum wall velocity along
the direction of electron flow under the assumption that the conduction electron
spin moments are fully converted into wall displacement. The dimensionless
parameter P represents the spin polarization of the current with 0 < P < 1
(around 70 % for permalloy), and e is the electron charge. The larger P , the more
efficiently the STT can move a domain wall. The first and second terms in (23)
describe adiabatic and non-adiabatic STT contributions, respectively. The adiabatic
(or Berger) term is derived under the assumption of the mentioned conservation of
the spin angular momentum, i.e., the entire spin angular momentum of the injected
carriers is transferred to the magnetization. In this limit the spin of the incoming
conduction electrons follows the magnetization profile of the domain wall. This
assumption is valid for sufficiently wide walls, for which an electron as enough
“time” to adapt to the localized magnetization while precessing and exchanging
spin angular momentum with the localized moments. If the magnetization gradient
becomes large, however, the assumption of adiabatic propagation is no longer
8 Magnetic Domains 427
valid. Then the spin polarization of the current cannot follow the rapidly changing
magnetization profile anymore, i.e., the exchange of spin angular momentum
between the conduction electron and the local moment is not conservative, leading
eventually to mistracking or even reflection (domain wall scattering) of the itinerant
spin. These effects are considered in the second, non-adiabatic spin torque term
in (16) that was independently introduced in refs. [36, 35] and which describes a
torque perpendicular to the adiabatic torque. The deviation from adiabaticity of the
STT is designated by the non-adiabatic STT parameter β, the ratio between the
non-adiabatic and adiabatic torques. It considers the mentioned spin mistracking
and spin relaxation in the wall by spin-flip scattering at impurities, phonons, etc. In
general both adiabatic and non-adiabatic terms have to be considered for a given
domain wall structure.
For current-driven wall motion, similar mechanisms are predicted as for the field
torque. Their appearance depends on the relative values of the Gilbert damping
parameter α and the β parameter, which both are dimensionless. As schematically
shown in Fig. 22a, there is some threshold current density in the absence of the non-
adiabatic torque (β = 0), below which the wall does not move at all. This threshold
is intrinsic (i.e., not caused by extrinsic pinning effects) because it originates only
from magnetization changes in the wall. The relevant torques for this case are
illustrated in Fig. 22b for the example of a 180◦ Bloch wall, which is reduced
to its central vector like in Fig. 21b. The adiabatic torque τAD on this moment,
together with the resulting demagnetizing fields, leads to a Néel-like deformation
of the wall structure and to a downward torque on the central vector that effectively
compensates τAD . This compensation of torques prevents wall motion up to a critical
velocity (i.e., current density) uc = γ Δ0w Ha /2 that is proportional to the anisotropy
field Ha . Up to uc , the adiabatic torque thus acts like an applied magnetic field
transverse to the wall plane that just distorts the wall without inducing a steady
motion. Above the threshold, the internal torque is not sufficient anymore to balance
the spin transfer torque, and the wall is set in motion together with a continuous
precession of the wall magnetization.
Wall velocity
Steady Precessional
motion motion
> m AD H d,1 m
Hd
=0 H d,1 m
2
NA
d,
=
H
0 H d,2 m Hd m
a) uc u b) c)
Fig. 22 (a) Average wall velocity as a function of the effective drift velocity u of the spin current,
schematically plotted for three different non-adiabaticity coefficients β (Adapted from Ref. [35]).
The adiabatic torque leads to wall distortion and motion (b), while the non-adiabatic torque (c)
just moves the wall. Indicated are the primary STT vectors, τAD and τNA , together the following
torques due to the generated demagnetizing fields [37]
428 R. Schäfer
The non-adiabatic torque (Fig. 22c), on the other hand, causes a demagnetizing
field with a consequent downward torque that sets the wall in steady motion right
away by mimicking an easy axis field (compare Fig. 21b). According to Fig. 22a
this is true for any DC applied current if β = α, and it is true for currents smaller
than a critical current if β > α. In the steady-wall motion regime, the non-adiabatic
torque together with the damping constant α dictates the velocity v = βu/α. It is
obtained by replacing Hext in (18) by the spin transfer equivalent field βu/(γ Δw )
[29]. Beyond the critical current, the adiabatic term dominates, and the wall slows
down (v = u) due to the onset of precession and backward motion accompanied
by periodic transformations between Bloch and Néel wall. The critical current
thus corresponds to the Walker breakdown of the field-driven dynamics (compare
Fig. 21d). So the non-adiabatic spin transfer plays a crucial role in current-induced
wall motion: it allows for a non-zero mobility of the wall in a steady-state, viscous-
flow regime with the mobility proportional to β/α, resulting in the elimination of
the intrinsic threshold current even for small values of β. Any threshold current is
then only determined by extrinsic pinning.
Compared to relatively wide domain walls in in-plane magnetized nanowires
(see Fig. 19), which can readily expand to many times their equilibrium size under
current torques [38], the domain walls are of Bloch-type in nanowires with an
anisotropy perpendicular to the plane of the wire. Well studied are atomically
engineered cobalt-nickel superlattices in which interface anisotropies dominate over
the volume terms (anisotropy and magnetostatic), thus leading to the perpendicular
easy axis. With typical wall widths of some nanometers, the magnetization gradient
is large, and consequently a high non-adiabatic effect is to be expected. This makes
such materials attractive for current-induced domain wall motion as it pushes the
walls like the torque of a magnetic field with an increased STT efficiency compared
to in-plane domain walls. Wall velocities of the order of 100 m/s were measured in
such films, comparable to the speeds found for field-driven wall motion in bubble
material.
The spin transfer torques, described so far, are volume effects. Even higher
current-induced wall velocities (before Walker breakdown) in perpendicular-
anisotropy media can be achieved by making use of interface-related spin
torque effects that are obtained by depositing the magnetic stripes adjacent to a
nonmagnetic conductive layer with strong spin-orbit interaction (SO layer) like
heavy metal platinum, palladium, iridium, or tungsten films (see refs. [39, 38] for
reviews). The following current-induced SO-torques may contribute:
• Spin Hall effect (SHE): If a charge current passes the SO layer, the SHE creates a
spin current due to spin-orbit scattering of the conduction electrons. The spin
current flows in a direction perpendicular to the charge current toward each
surface of the SO layer. It may thus be seen as pure spin current, i.e., without
any charge flow in the perpendicular direction. The direction of the spin is
perpendicular to both the charge and spin currents as illustrated in Fig. 23a. The
interfacial spin accumulation is injected into the adjacent magnetic layer where
it exerts a STT [39]
8 Magnetic Domains 429
No SH Heff
Heff
Bloch
wall
SH
Heff
Heff
Néel
wall
tion
Wall mo
a) b)
Fig. 23 (a) Illustration of the Spin Hall Effect and its torque τSH . Indicated are the perpendicular
domain magnetizations and the central vectors for both rotation senses of a Bloch- (upper-) and
Néel wall (lower panel). (b) The Spin-Hall torque on a Néel wall leads to an effective magnetic
field that depends on the wall rotation sense, leading to a wall motion along or opposite to the
charge current direction. For each sketch, the spin-orbit layer is indicated as bottom layer, being in
contact with the ferromagnetic film on top
τSH ∼ m × σ × m . (24)
Here σ = j × z with j and z being the unit vectors of current and out-of-plane
direction, respectively. The spin-Hall torque τSH manipulates the magnetization
in the magnetic film as shown for domain walls in Fig. 23a. For Bloch walls of
either rotation sense, the torque vanishes, while for Néel walls a transverse torque
acts on the wall spins that points in the same direction (along the injected electron
spin direction) for both rotation senses of the wall magnetization. The resulting
demagnetizing fields finally lead to an effective magnetic field acting on a Néel
wall. As illustrated in Fig. 23b, this field is opposite for Néel walls with opposite
rotation senses. Consequently, neighboring walls will be pushed in the same
direction if they have the same chirality, i.e., opposite directions of their central
vectors. Such homochiral Néel walls can be enforced in ultrathin multilayers with
interface-induced Dzyaloshinskii-Moriya interaction; see section “Domain Wall
Types” and Fig. 19a.
• Rashba effect: This spin-orbit-related phenomenon, reviewed in Ref. [40], may
be induced by an electric field that is mediated by the symmetry breaking at
the interfaces of a typical multilayer composed of heavy-metal/ferromagnetic
metal/oxide films and that is oriented perpendicular to the film plane. When an in-
plane charge current flows in the magnetic layer, the itinerant electrons transform
the electrical field into a (Rashba) in-plane magnetic field that is experienced by
the flowing electrons and that polarizes them. By exchange interaction they can
then exert a field-like SST on the local magnetization of the magnetic film which
may result in some pressure on the domain walls [41, 39]. In contrast to the Spin
Hall effect, which is a bulk effect, the Rashba effect is an interface property.
The direction of domain wall motion and their velocity are determined by
the subtle interplay of these phenomena, which can be tuned independently by
430 R. Schäfer
varying the thickness of the SO layers and the composition of the ferromagnetic
layer. Current-induced domain wall motion with velocities of several 100 m/s
can be achieved by making use of SO effects. Still higher wall velocities of
almost 1.000 m/s were measured in nanowires that are formed from synthetic
antiferromagnets, i.e., from two antiferromagnetically coupled films via an ultrathin
nonmagnetic spacer layer [42, 38]. The high velocity is attributed to the vanishing
net magnetic moment in such film systems.
Besides the so far discussed nanowires with the current flowing in the plane,
STT [34] manifests itself also in sub-micrometer diameter pillars, composed of
magnetic multilayers and flooded by a current perpendicular to the plane. Such
pillars are the basic units of the SST-MRAM (magnetic random-access memory)
concept. Magnetically, they can be well described in the framework of a macrospin
model, meaning that the magnetic films of the pillar are assumed to move in a single-
domain state rather than by short-wavelength modes. As domains thus do not play a
role, we will touch this case just briefly here, leaving details to specialized literature
(see refs. [43, 44] for reviews).
Assume a ferromagnet/normal-metal/ferromagnet trilayer system as illustrated
in Fig. 24a, b. The two ferromagnetic layers of this spin valve-type device are
depicted as “fixed” and “free,” indicating that they are less and more susceptible,
respectively, to the STT. If unpolarized electrons are entering the fixed layer from
the left (Fig. 24a), they will undergo spin-filtering, i.e., by exchange interaction with
the magnetic moment of the fixed layer, the flowing electrons have an averaged spin
moment parallel to the magnetization of the fixed layer when emerging into the
nonmagnetic spacer film. If the spacer is thinner than the spin diffusion length, this
current will remain spin-polarized when it enters the free layer, in which the spin
components of the incoming electrons transverse to its magnetization are absorbed.
As the spin angular momentum is conserved, this lost transverse momentum of the
electrical current must be absorbed by the magnetic film, leading to a torque that
a) b) c)
Fig. 24 (a, b) Illustration of the STT in a spin-valve-type trilayer, leading to the switching of the
free layer magnetization either parallel (a) or antiparallel (b) to that of the fixed layer (starting
from an assumed perpendicular initial configuration, with the thickness of the nonmagnetic spacer
layer exaggerated for visualization purpose). The magnetization of the fixed layer is stabilized by
making it thicker than the free layer, by using a material with a larger total moment or by exchange
coupling to an antiferromagnetic layer. (c) Schematics of the STT in analogy to Fig. 20
8 Magnetic Domains 431
tends to turn the free layer magnetization toward the orientation of the incident spin
polarization. So the parallel alignment of magnetization in the fixed and free layer
is stabilized. This STT requires that the moments of the two layers are initially
non-collinear, perhaps due to thermal fluctuations (exact parallel or antiparallel
alignment would not lead to torques). If the electron flow is opposite (Fig. 24b),
the electrons will first undergo spin filtering by the free layer. They will then flow to
the fixed layer and apply a torque to that layer. This torque, however, is inefficient
as the fixed layer magnetization is held rigidly in place. However, a fraction of
the electrons will be reflected back from the interface between normal metal and
fixed layer toward the free layer. These reflected electrons have an averaged spin
polarization antiparallel to the fixed layer magnetization (the parallel spins are
readily transmitted), i.e., opposite to the case discussed before. The free layer now
feels a torque that turns the free layer moment away from the fixed layer moment,
thus destabilizing the parallel alignment of magnetization and possibly leading to
a reversal of the free layer magnetization if the current is sufficiently strong. The
fixed layer consequently serves as an electron polarizer by providing the polarized
electrons that finally act on the free layer for both current directions. This current-
induced magnetization switching between parallel and antiparallel magnetization
of free and fixed layer provides a smart alternative to magnetization switching by
magnetic field and is applied in the STT-MRAM for the writing process.
The dynamics of the free layer in the spin-valve pillar is phenomenologically
described by the LLGS equation (16), in which the τ -term reads
dmfree I
τ= = g(θ ) mfree × (mfree × mfixed ). (25)
dt A
gained from the STT are balanced over each precessional cycle. Some dynamical
equilibrium may then be reached at an intermediate angle θ , meaning that steady-
state precessional oscillations in the microwave frequency range are generated [45].
The precession, which is basically caused by a DC applied current, occurs with large
precession angles that are not accessible using magnetic field excitation alone and
which are the basis for the so-called spin-transfer oscillators that are envisaged for
applications in communication technology.
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Contents
Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
Classical Magnetoresistance in Semiconductors and Semimetals . . . . . . . . . . . . . . . . . . . . . . 440
Magnetotransport and Ferromagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
Anisotropic Magnetoresistance, Planar Hall Effect, and Two-Current Model . . . . . . . . . . . 442
Giant Magnetoresistance (GMR ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
Colossal Magnetoresistance (CMR ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
Tunneling Magnetoresistance (TMR ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
Powder Magnetoresistance (PMR ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Organic Magnetoresistance (OMAR ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Quantum Transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Exotic Tunneling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
Spin Currents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
Spin Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
Inverse Spin Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
Quantum Spin Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
Magnetoimpedance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
Abstract
M. Ziese ()
Fakultät für Physik und Geowissenschaften, Universität Leipzig, Leipzig, Germany
e-mail: [email protected]
Basics
When a static electric field E is applied to a material, it might respond with a current
flow – then it is called an electric conductor – or with a static polarization P , in
which case it is called an insulator. Conductors are characterized by Ohm’s law [1]:
When all external parameters (temperature, pressure, magnetic field . . . ) are held
constant, the current density j flowing through a conductor is proportional to the
applied electric field E:
j = σ E . (1)
The diagonal components are even under magnetic field inversion; the off-diagonal
components might have an even as well as an odd contribution. In case of isotropic
systems and cubic systems, all three diagonal components are equal and are
simply called conductivity σ . In this chapter, the material systems are restricted
to solids; according to their conductivity values, conductors might be quantitatively
further divided into metals (good conductors) and semiconductors. However, it is
more appropriate to use the temperature coefficient of resistivity (TCR) dρ/dT
to qualitatively distinguish metals (positive TCR) from semiconductors (negative
TCR). More than two thirds of the elements are metals; see Fig. 1.
If contributions from ionic motion are neglected, the current flow is carried
by electrons that are driven through the material by the applied electric field. In
a crystalline material, the electrons are found in Bloch states characterized by a
quantum number k, the wave vector, or h̄k,
the crystal momentum. The electronic
energy En (k) is a function of band index n and wave vector k, being periodic in the
9 Magnetotransport 437
Fig. 1 Left panel: Room temperature resistivities of the elements as a function of order number.
Resistivities diverge toward the r.h.s. of the periodic table (C (graphite), Si, Ge, Te). Certain
features recur periodically, such as the resistivity minima of the Cu group elements, the local
maxima of the Ti group elements, as well as a maximum at half-filling of the d-shell (Mn, Tc, Re).
Resistivity values from [3]. Right panel: Resistivity of Fe1−x Nix alloys at various temperatures [4].
The resistivity increase of the alloy is clearly seen, especially at low temperatures. The situation is
further complicated by the martensite-austenite transition that occurs along the alloying route from
iron (bcc) to nickel (fcc)
reciprocal lattice and thus forming energy bands [5]. The electron velocity vn (k)
does in general not vanish, i.e., electrons move through periodic lattices without
scattering. Electron scattering is due to imperfections in the crystal lattice, either by
static imperfections (lattice defects) or by dynamic imperfections such as phonons
or magnons. Within the Drude model , the scattering is characterized by a relaxation
time τ . The conductivity can then be expressed by the carrier density n, the effective
electron mass m∗ , the relaxation time τ , and the electron charge e as [6]
e2 nτ
σ = . (3)
m∗
When various scattering mechanisms act in the same conductor, in a first approx-
imation, the resistivities add up: ρ = ρi + ρp + . . . (Matthiessen’s rule, [7]). ρi
denotes the scattering by impurities that is mainly temperature independent, and ρp
denotes the scattering by phonons that is proportional to T 5 (Bloch T 5 law) at low
temperatures, to T 3 for umklapp processes, and to T at high temperatures [5]. The
effect of electron-electron scattering is rather small leading to a term proportional
to T 2 . As a simple rule, the resistivity of the non-ferromagnetic elements at room
temperature is proportional to the temperature, since electron-phonon scattering
dominates, whereas alloys have a nearly temperature-independent resistivity due to
438 M. Ziese
the dominance of impurity scattering. This is illustrated in the right panel of Fig. 1
showing the resistivity of Fe1−x Nix alloys for various temperatures.
A well-established model describing electron transport in the limit of weak
scattering is the semiclassical model of electron dynamics. This builds on the energy
According to Hamilton’s equations, the velocity is related to
band structure En (k).
the momentum gradient of the Hamiltonian [5]:
= 1 ∂En /∂ k .
vn (k) (4)
h̄
The time derivative of the crystal momentum is given by the Lorentz force [5]:
h̄k˙ = −e E( × B(
r , t) + vn (k) r , t) . (5)
where A(EF ) denotes the cross section of an extremal Fermi surface perpendicular
to the applied magnetic field. These effects have proven viable tools for Fermi
surface studies [5].
If the mean free path
= vF τ , where vF denotes the Fermi velocity, is of the
order of the lattice spacing a, the Mott-Ioffe-Regel limit
= a is reached and the
metal approaches insulating behaviour [9]. In the limit of strong disorder, in an alloy
or an amorphous material, the electronic wave function may become localized [10],
such that a crossover or transition to an insulating state with variable range hopping-
dominated conductivity occurs [9]. Analyzing the formation of extended wave
functions from the atomic orbitals, Mott [9] introduced the concept of a mobility
edge that separates localized states in the tails of the energy bands from extended
9 Magnetotransport 439
states within the energy band centers. In certain compounds, this limit is actually
accompanied by a resistivity saturation [11,12], but this is not a universal signature,
and the resistivity of other metals just crosses this limit without any features [13].
Electron scattering in the limit of strong disorder is determined by various scattering
length scales, and especially the phase coherence length can be much larger than
the mean free path. This leads to the possibility that an electron is strongly scattered
and retraces its original trajectory coherently, a process known as weak localization
[14]. Weak localization leads to corrections to the resistivity being logarithmic
in temperature in two-dimensional and proportional to T 1/2 in three-dimensional
systems. Furthermore, a magnetic field threading the weakly localized trajectories
destroys the phase coherence and leads to a negative magnetoresistance [14].
Spin-orbit coupling has a similar effect but leads to a positive magnetoresistance
contribution, see, e.g., the magnetoresistance of Au in Mg [15].
After discussing some of the basics of magnetotransport in metals, one might
ask what the specifics of magnetotransport in ferromagnets are. This is nicely
highlighted by a set of classic data from Gerlach and Schneiderhan [8]; see Fig. 2.
In ferromagnets, electron-magnon scattering is large and contributes another term
Fig. 2 Resistance and magnetoresistance of a nickel wire; magnetic field and current density were
applied along the wire axis. (a) The resistivity of ferromagnetic metals has a slope change at
the Curie temperature (615 K in this case, 633 K for pure Ni). (b) The magnetoresistance slope,
and therefore also the magnetoresistance in large magnetic fields has a maximum at the Curie
temperature due to critical scattering. (c) The magnetoresistance below the Curie temperature
shows an anisotropic contribution at low fields and a linear contribution from critical scattering
at high fields. (d) Above the Curie temperature, only the linear MR remains. The numbers indicate
the measurement temperatures. (After [8])
440 M. Ziese
ρ denotes the longitudinal resistivity; the Hall constant is RH = ρωc τ/B. Note that
the diagonal components of the conductivity depend on the magnetic field. If more
than one band contributes to the electron transport, the total conductivity tensor
is obtained as the sum over the conductivity tensors of all bands. In case of two
bands, this yields the following expressions for the longitudinal resistivity ρ and
Hall constant R (two-band model, the indices refer to the respective bands):
with B/ρ is expected, which is known as Kohler’s rule [20]. A nonsaturating magne-
toresistance is obtained in compensated materials with n1 +n2 = 0. These equations
form the basis for a magnetotransport analysis of semiconductors. They were also
used to describe the behavior of compensated metals such as Bismuth or zero-gap
semiconductors such as graphite. In graphite and Bi, the magnetoresistance is so
strong that a magnetic field-induced metal-insulator transition occurs, i.e., the resis-
tivity at low temperatures is larger than at high temperatures, since ωc τ is very large
at low temperatures; see Fig. 3. The resistivity and magnetoresistance can be fairly
well understood within a three-band model; see Fig. 3a and b [18]. This is somewhat
surprising, since the magnetoresistance in general depends on the form of the Fermi
surface as well as the dominant scattering mechanism [21]. Further, the semiclassi-
cal model is only an approximation and does not provide a full quantum-mechanical
description of the magnetotransport. The observation of a magnetoresistance linear
in magnetic field, e.g., in Ag2+δ Se [22] and in graphite [23] or multilayer
graphene [24], calls for a full quantum-mechanical description [25]. Early quantum
theories of galvanomagnetic effects found a scaling of the magnetoresistance in the
quantum limit with H p /T q , where the exponents p and q depend on the scattering
Spin disorder scattering near the Curie temperature was discussed in sec-
tion “Basics”. Below the Curie temperature, the magnetoresistance of a ferromagnet
depends on the relative direction between the electric current density j and the
magnetization M [28, 16, 29]. This constitutes the anisotropic magnetoresistance
(AMR ). Let ρ and ρ⊥ denote the resistivities (extrapolated to zero induction B)
in longitudinal (j M)
and transverse geometry (j ⊥ M), respectively; then the
anisotropic magnetoresistance is defined as
Δρ ρ − ρ⊥
= . (10)
ρ 1
3 ρ + 23 ρ⊥
In case of single crystalline materials, the angle dependence might be much more
complicated [29, 30, 31, 32]. As an illustration, Fig. 4 shows the anisotropic magne-
toresistance of a single crystalline SrRuO3 film as a function of angle between the
applied field of 8 T and the crystallographic axes. The complex angle dependence
is obvious. Since the magnetic anisotropy of SrRuO3 is rather strong, the angular
dependence is even further complicated, since the magnetization is not always along
the magnetic field direction; note especially the sharp magnetoresistance change at
about 30◦ from the [110] axis in the (001) plane, which is due to the crossing of a
hard magnetic axis [33].
The transverse resistivity is known as planar Hall effect . Due to the absence
of any offset in Eq. (12), this is sometimes advocated to be a much more sensitive
probe than the AMR. Especially in case of ferromagnets with rather large resistivity,
9 Magnetotransport 443
Fig. 4 Angle dependence of the AMR in a single crystal SrRuO3 film. The current density was
along the [001] orthorhombic axis; the magnetic field was rotated in the (a) (110) and (b) (001)
plane. Some crystallographic directions are indicated (After [33])
the planar Hall effect was dubbed giant [34, 35]. The planar Hall effect of
La0.84 Sr0.16 MnO3 is shown in Fig. 5.
The basis for the understanding of the AMR is Mott’s two-current model
[36, 37]. This in turn is based on the s − d model: the band structure of a 3d
transition metal might be understood as being composed of a broad free-electron-
like s-band superimposed on a narrow tight-binding-like d-band. The comparatively
high resistivity of the transition metals might be understood by scattering of mobile
s-electrons into d-states, where the latter have a considerable density of states at
the Fermi level. Spin-flip scattering events are rare, at least at low temperature,
since scattering occurs predominantly at non-magnetic scattering centers. Therefore,
electron transport can be viewed as a parallel circuit of spin-up and spin-down
conduction channels; see Fig. 6; in each channel, the resistivities ρ ↑ and ρ ↓ consist
in general of a small ss- and a large sd-scattering contribution. The spin-flip-
−1
scattering rate τ↑↓ is negligible at low temperatures. In case of strong ferromagnets,
the majority (or spin-up band) is completely filled, thus eliminating the sd-scattering
of spin-up electrons and short-circuiting carrier transport along the spin-up channel.
Historically, this model was motivated by a resistivity drop below the Curie
temperature; see Fig. 6c; note, however, data and discussion in [16].
For a measurement of ρ↓ and ρ↑ , the scattering center has to be defined. This
is usually done by alloying a ferromagnetic host metal with a few atomic percent
of particular metal impurities. The channel resistivities can then be obtained from
deviations of the measured data from Matthiessen’s rule either as a function of
temperature or in ternary alloys [16]. Figure 7 shows the channel resistivities as well
444 M. Ziese
Fig. 5 (a) AMR and (b) and (c) planar Hall effect of La0.84 Sr0.16 MnO3 at 120 K. The lines in (a)
and (b) are fits of Eqs. (11) and (12) to the data using (a) R − R⊥ = −29 Ω and (b) R − R⊥ =
−88 Ω. (After [35])
Fig. 6 Mott’s two-current model: (a) spin-up and spin-down conduction channels weakly coupled
by spin-flip scattering. (b) Short-circuiting by the spin-up channel in case of a strong ferromagnet.
(c) Similarity of the temperature dependence of the resistivities of Ni (above TC ), Pd, and Pt; for
comparison Ag
9 Magnetotransport 445
Fig. 7 (a) Channel resistivities ρ↓ (solid symbols) and ρ↑ (×ed symbols) of Ni, Co and Fe for the
specified 3d transition metal impurities. (b) Channel resistivity ratio α = ρ↓ /ρ↑ as a function of
impurity
Table 1 Channel resistivities ρ↓ and ρ↑ and α = ρ↓ /ρ↑ for Ni, Co, and Fe hosts. (From [16, 38,
39, 40, 41, 42])
ρ↓ ρ↑ α
(nΩm) (nΩm)
Impurity/host Ni Co Fe Ni Co Fe Ni Co Fe
Ti 105 110 40 56 76 105 1.9 1.4 0.4
V 67 77 13 130 77 105 0.5 1.0 0.1
Cr 65 24 28 220 73 125 0.3 0.3 0.2
Mn 75 100 17 7.5 120 130 10 0.8 0.1
Fe 60 67 4 5.4 15 12
Co 35 33 1.8 16 19 2
Ni 120 24 5
Rh 21 28 64 100 28 11 0.1 1.0 6
Re 75 77 27 260 180 87 0.3 0.4 0.3
Ir 48 38 200 280 117 22 0.2 0.3 9
Os 64 68 43 500 235 130 0.1 0.3 0.3
as their ratio α = ρ↓ /ρ↑ for the ferromagnetic hosts Ni, Co, and Fe as a function of
the 3d transition metal impurities. Table 1 contains data of the channel resistivities.
The data in Fig. 7a conform to the expectation that ρ↑ is small only for transition
metal impurities Fe, Co, and Ni. In case of the early 3d elements, the channel
resistivities are sizable, and for V and Cr that form virtual bound states at the Fermi
level of the ferromagnetic host, α is even smaller than unity. In case of Ti, rather
446 M. Ziese
large channel resistivities are found, but α, at least for the hosts Ni and Co, is larger
than unity.
The AMR is a spin-orbit interaction effect. It might be described by a model
Hamiltonian that takes the exchange interaction, the crystal-field splitting, and the
spin-orbit coupling into account [43, 44, 45]:
· S .
Ĥ = Ĥex + ĤCF + AL (13)
Spin-orbit coupling leads to a spin-admixture such that the majority carrier wave
functions acquire a small spin-down component and vice versa. The scattering
matrix element due to a spherically symmetric scatterer from an s- into a d-state
is dependent on the magnetization, i.e., spin direction, thus leading to the AMR. In
second-order perturbation theory, one obtains
Δρ
= γ (α − 1) , (14)
ρ
where α = ρ↓ /ρ↑ is the resistivity ratio between up- and down-channels and γ
sets the strength of the effect. In second-order perturbation theory γ ∝ (A/Eex )2
or γ ∝ (A/ECF )2 , depending on whether the exchange splitting Eex or crystal
field splitting ECF is larger. Figure 8 shows the anisotropic magnetoresistance as
a function of channel resistivity ratio α. Up to α 3, the data fall onto a straight
line with a slope of 0.03; shown is a linear dependence with a slope γ = 0.01 as
suggested in [46].
Fig. 8 Anisotropic magnetoresistance AMR for alloys of Ni as a function of the channel resistivity
ratio of the particular alloying element. The red line was calculated from Eq. (14) using γ = 0.01
(After [46] and [16])
carried by spin-up and spin-down currents within each layer. A multilayer can then
be modeled by a parallel circuit of layer resistances in series (CPP) or partially in
series (within a mean free path, CIP); see Fig. 10b and [52, 53, 54].
On a more fundamental basis, spin accumulation at the interfaces has to
be taken into account. The concept of spin diffusion was studied in early
work [55] with measurements of the spin diffusion length λs in Al after spin
injection from permalloy. At the interface between a ferromagnet and a normal
metal, the conversion of an unpolarized current in the normal metal into spin-
polarized currents in the ferromagnet leads to a difference in the electrochemical
potentials μ↑ and μ↓ for spin-up and spin-down electrons; see Fig. 10c; this
potential difference in turn causes an additional boundary resistance [56].
Using this concept, a quantitative theory of the GMR in CPP configuration was
developed [57].
In antiferromagnetic spintronics, the spin valve as a trilayer formed by two
ferromagnets separated by a normal metal is replaced by a ferromagnet adjacent
to an antiferromagnetic tunnel junction, e.g., in a NiFe/IrMn/MgO/Pt stack [58].
The resistance change is due to tunneling anisotropic magnetoresistance [59]. The
coupling to the external field is facilitated by the permalloy layer that rotates the
antiferromagnetic magnetic moments by the exchange-spring effect.
448 M. Ziese
Fig. 9 (a)–(f) Magnetization at 300 K (left axis) and transverse magnetoresistance at 4.5 K (right
axis) of six Ru/Co superlattices with structure Si(111)/(10 nm) Ru/[(1.6 nm) Co/tRu Ru]20 /(5 nm)
Ru and Ru layer thicknesses of 0.8, 1.1, 1.9, 2.7, 3.1, and 3.8 nm. (g) Transverse magnetoresistance
and (h) saturation magnetic field as a function of Ru layer thickness. Clear oscillations in
the saturation field and the magnetoresistance are observed: when the interlayer coupling is
antiferromagnetic with a large saturation field, the magnetoresistance is “giant” (After [51])
Fig. 10 (a) Current-in-plane (CIP) and current-perpendicular-to-plane (CPP) configurations. (b) Resistor model of GMR – upper row: carrier scattering in the
ferromagnetic and antiferromagnetic configurations (schematic); lower row, corresponding spin-dependent circuit models. (c) Spin-dependent electrochemical
potentials at a ferromagnet-normal metal interface; λsF and λsN denote the spin-diffusion lengths in the ferromagnet and normal metal ((a) and (b) after [54])
449
450 M. Ziese
Fig. 11 (a) Zero field resistivity (left axis) and magnetization (right axis) as well as magne-
toresistance ratio in a magnetic field of 1 T of La0.7 Ba0.3 MnO3 and La0.7 Ca0.3 MnO3 films.
(After [64]). (b) Magnetoresistance ratio of various manganite compounds as a function of
the Curie temperature. (After [65] and [63]). (c) Phase diagrams of La1−x Cax MnO3 and
Pr1−x Cax MnO3 with the following phases: PMI paramagnetic insulator, FMM ferromagnetic
metal, FMI ferromagnetic insulator, AFMI antiferromagnetic insulator, CO charge ordered. TC ,
TN , TP , and TCO denote the transition temperatures into the magnetically ordered and charge
ordered phases, TS denotes the temperature of the structural transition between orthorhombic and
rhombohedral phases. (After [66] and [67])
Fig. 12 (a) Crystal-field splitting of the Mn 3d-levels in an octahedral environment. The arrows
indicate the electron occupation of the levels for Mn3+ and Mn4 ions according to Hund’s rules.
The dotted arrows indicate hopping of the eg electron from Mn3+ to Mn4+ via the O 2p orbital.
This leads to the two degenerate Mn-O-Mn clusters shown. (c) Calculated band structure and
density of states of La0.7 Sr0.3 MnO3 . The band structure is shown near the Γ point in the directions
toward the X and K points (After [72])
the angle Θ between the core spins as cos(Θ/2). This conduction mechanism is
called double exchange [70,71]; see Fig. 12a; it explains the strong interdependence
between ferromagnetism and conductivity and forms the basis for understanding
colossal magnetoresistance.
The physics of manganites is really intricate, since not only charge and spin
degrees of freedom are coupled, but there is also a coupling to the orbitals and
to lattice phonons [73]. Moreover, the inherent disorder created by the doping
has to be taken into account. This has led to a variety of models for the colossal
magnetoresistance, taking electron-phonon [74], electron-polaron [75], or phase
separation [76] into account. At surfaces and interfaces, orbital reconstruction
might play a role and might lead to new effects [77]. The strong Hund’s rule
splitting leads to a half-metallic [78] band structure; see Fig. 12b [72], and in oxide
heterostructures, La0.7 Sr0.3 MnO3 is the established material for ferromagnetic elec-
trodes or spin injectors. The half-metallicity of the manganites in combination with a
breakdown of the double-exchange mechanism at extended lattice defects leads to a
significant extrinsic magnetoresistance known as grain-boundary magnetoresistance
[79, 80, 81].
AlOx barrier into a thin Al film in a large parallel field that splits the quasiparticle
density of states due to the Zeeman energy; see Fig. 13a. This technique enables
measurements of the spin polarization
D ↑ − D↓
P = . (15)
D↑ + D↓
R↑↑ and R↑↓ denote the resistance values for parallel and antiparallel magnetization
orientation; note that in the standard pessimistic MR definition used in this chapter
T MR = 2P1 P2 /(1 + P1 P2 ). High-quality ferromagnetic tunnel junctions were
reported for the first time in [89, 105]; see Fig. 13c. The junction resistance is
considerably enhanced in the magnetic field range between the coercive fields of
the two layers, when the magnetizations are antiparallel. The tunneling transport
mechanism is evidenced by the so-called Rowell-criteria [106, 90]: (i) exponential
thickness dependence of the resistance, (ii) quasi-parabolic differential conductance
vs. voltage curves, and (iii) insulator-like temperature dependence of the tunnel
resistance; see Fig. 13d. It is even possible to measure the spin-resolved density
of states using voltage-dependent TMR [107]. As seen from Eq. (16), the TMR
ratio diverges in case of half-metallic ferromagnets; see, e.g., data on LSMO [91] in
Fig. 13e. However, in case of oxide ferromagnets, the TMR ratio decreases strongly
even for temperatures far below the Curie temperature [108]. In certain single
crystalline systems, e.g., Fe/MgO/Fe, details of the band structure might enhance
the TMR ratio above the value estimated by Eq. (16) [109, 92, 110, 111]; see the
data in Fig. 13f. Large TMR ratios were also found for amorphous ferromagnets
[112].
A vast number of spin-polarization values can be found in the literature; Table 2
shows a small selection of consolidated values obtained by the transport techniques
discussed here in comparison to results from spin-polarized photoemission spec-
troscopy. The relation of the spin polarization to band structure and magnetic order
might be complex, see, e.g., CoGd alloys with compensation point [113].
9 Magnetotransport 453
Fig. 13 (a) Conductance G of a Ni/AlOx /Al junction as a function of applied voltage. The con-
ductance was normalized to the conductance GN in the normal state. T = 0.4 K. The conductance
peaks split in magnetic fields applied parallel to the Al film. In a magnetic field, the conductance
peak heights are different, since the density of states in Ni is spin dependent. (After [82]). (b)
Relative conductance ΔG/G0 = (G↑↑ − G↑↓ )/G0 of a Co/Ge/Co junction normalized to the
conductance at 0 V. T = 4.2 K. (After [88]). (c) Tunneling magnetoresistance of a CoFe/Al2 O3 /Co
junction at 295 K. (After [89]). (d) Resistance of a IrMn/NiFeCo/CoFe/AlOx /NiFeCo junction
as a function of temperature in the parallel and antiparallel magnetization state. (After [90]).
(e) Tunneling magnetoresistance of two La2/3 Sr1/3 MnO3 /SrTiO3 /La2/3 Sr1/3 MnO3 junctions
showing the strong decrease with temperature. The inset shows a resistance hysteresis loop at
4.2 K. (After [91]). (f) Tunneling magnetoresistance hysteresis loops for a Fe/MgO/Fe junction at
80 K (open symbols) and 293 K (solid symbols). (After [92])
of the TMR [116] and to investigate the surface spin chirality [117] or single
skyrmions [118].
Quantum Transport
In previous sections, transport was mainly in the diffusive regime. In case of mean
free paths being large compared to sample dimensions, i.e., in the ballistic regime,
the sample conductance does not diverge but is found to be quantized in units of
G0 = 2e2 / h = 7.74809173 × 10−5 S. The conductance can then be expressed in
the form [128]
2e2
G= Ti , (17)
h
i
9 Magnetotransport 455
where Ti denotes the transmittivity of the ith conduction channel. The quantization
can be clearly demonstrated in constrictions or nanowires, when only a few
conduction channels are available, see, e.g., [129,130]. Equation (17) is valid, when
the scattering process does not significantly depend on the spin and when states with
different spin degrees of freedom are energetically degenerate. These conditions do
not necessarily hold in ferromagnetic nanocontacts. Indeed, break junctions made
from Ni wires touching a Ni plate showed conduction with half conductance quanta
e2 / h but only in magnetic fields high enough to saturate the Ni wire magnetization
[131]; see Fig. 14a and b. This indicates that the spin structure close to the contact
is crucial in determining the conductance value.
The magnetoresistance of Ni nanocontacts and break junctions showed large
values up to 80% [132, 134]; see Fig. 14c. Although the data scatter strongly,
a clear trend toward large magnetoresistance values at small conductance values
of a few conductance quanta was observed. Similar results were found for break
junctions between various half-metallic oxides [133, 134] (see Fig. 14d) but also
for nanoconstrictions patterned in half-metallic oxide films [135]. The experimental
data on oxides differ from those on metallic ferromagnets in that the conductance
is significantly smaller than one conductance unit, such that the transport cannot
be ballistic. Domain walls in nanoconstrictions can be very sharp [136]. The
Fig. 14 Histograms of junction conductance for a variety of Ni wire-Ni plate break junctions in
applied magnetic fields of (a) 0 mT and (b) 10 mT. When the Ni wire is in magnetic saturation,
the emergence of spin-polarized half conductance quanta e2 / h was observed (After [131]).
Magnetoresistance of (c) Ni and (d) magnetite nanocontacts as a function of junction conductance.
Note that conductance in case of Ni is ballistic, whereas it is by a tunneling mechanism in case of
Fe3 O4 . (c) After [132]. (d) After [133]. The lines are guides to the eye
456 M. Ziese
Exotic Tunneling
Fig. 15 (a) TMR of Co-Al-O granular films as a function of temperature. (After [139]). (b) TMR
of a thin Co-Al-O layer in CPP geometry as a function of bias voltage. (After [139]). (c) TMR
of a Co/AlOx /NiFe spin-valve with a Cu quantum wall as a function of Cu layer thickness. (After
[140]). (d) TMR of a La0.7 Sr0.3 MnO3 /NiFe2 O4 /Au spin-filter valve. (After [141]). (e) TMR of a
Fe/BaTiO3 /La0.7 Sr0.3 MnO3 tunnel junction for two orientations of the BaTiO3 polarization. (After
[142]). (f) TMR of a La0.7 Sr0.3 MnO3 /La0.1 Bi0.9 MnO3 /Au spin-filter valve with multiferroic spin
filter. (After [143])
as a spin filter. Due to the exchange energy an electron experiences when tunneling
through the magnetically ordered insulating barrier, the barrier heights for the two
spin directions differ by 2Eex [152, 153]. A more detailed analysis shows that not
only the barrier height but also the band alignment with the electrodes plays a
role [154]. Experimentally, spin filtering was observed for ferromagnetic EuO in
Al/EuO/Y/Al junctions by conductance spectroscopy in the superconducting state
of Al [155] and ferrimagnetic NiFe2 O4 and multiferroic La0.1 Bi0.9 MnO3 by mag-
netoresistance measurements in La0.7 Sr0.3 MnO3 /NiFe2 O4 /Au [141] (see Fig. 15d)
and La0.7 Sr0.3 MnO3 /SrTiO3 /La0.1 Bi0.9 MnO3 /Au [156] tunneling junctions.
Another way of modulating the barrier height is by the use of a ferroelectric
barrier with the electric polarization along the tunneling direction. In this case,
the barrier height depends on the direction of polarization [157, 158]. This might
be due to electrostatic effects, to strain, or to detailed cation shifts at the interface
between the ferroelectric and the electrodes [157]. It is often difficult to distinguish
between a barrier height effect or extrinsic mechanisms such as resistance switching
458 M. Ziese
Hall Effect
VH d Ey ρyx 1
RH = = = =± . (18)
Ix B jx B B en
In case two bands are contributing to the carrier transport, the Hall constant was
already given in Eq. (9). The Hall angle is defined as tan ΘH = Ey /Ex = ρyx /ρxx .
A magnetic field applied to a ferromagnetic metal aligns the magnetization along
its direction; see Fig. 16a. The magnetization component M along the magnetic field
direction leads to an additional Hall effect contribution, known as extraordinary or
anomalous Hall effect. Phenomenologically, the Hall resistivity is then given by
[170]
ρyx = RH B + μ0 RA M (19)
with the anomalous Hall constant RA . Note that in ferromagnetic films the demagne-
tizing factor is close to unity and the magnetic field H within the sample is given in
terms of the applied field HA by H = HA − NM, such that the magnetic induction
is B = μ0 (H + M) = μ0 (HA + (1 − N)M) μ0 HA . Figure 16b shows the
Hall resistivity of a La0.7 Sr0.3 MnO3 film as a function of magnetic field. At low
fields, the Hall resistivity rises steeply due to the anomalous Hall contribution (see
Fig. 16c); at high fields the magnetization M is saturated, and a much smaller slope
due to the ordinary Hall effect is observed. The product μ0 RA MS is obtained by
extrapolation to B = 0 as indicated in Fig. 16b; RH is obtained from the high field
slope. The manganites are hole conductors with a negative anomalous Hall constant.
9 Magnetotransport 459
The anomalous Hall effect is due to the spin-orbit interaction; see section “Spin
Currents ”. One distinguishes between extrinsic and intrinsic contributions. Extrin-
sic contributions are due to scattering: (i) Skew-scattering is the asymmetric
scattering of an electron with respect to the plane containing its incident velocity
and the ion’s magnetic moment [170, 171, 172]. (ii) Side-jump scattering denotes
the side shift of the extrapolated trajectories before and after the scattering event
[170, 173]. Both mechanisms predict a scaling RA ∝ ρ n of the anomalous Hall
constant with the longitudinal resistivity, with n = 1 for skew scattering and n = 2
for side-jump scattering, compare to Fig. 16d.
The intrinsic contribution to the anomalous Hall effect is due to the Berry phase
electrons acquire when moving through a spin lattice [174, 175]. An example
material for this contribution might be SrRuO3 which has an intricate temperature
dependence of the anomalous Hall constant attributed to magnetic monopole-like
features at the Weyl points in momentum space [176, 177]; this is illustrated
Fig. 16 (a) Hall effect in a ferromagnet. (b) Hall resistivity ρyx measured on a 5 nm thick
La0.7 Sr0.3 MnO3 film. At higher temperature, the anomalous Hall effect is clearly seen; the
extrapolation to B = 0 to determine μ0 RA MS is indicated. (c) Initial Hall effect slopes dρyx /dB
for 300 nm thick La0.7 Ca0.3 MnO3 and La0.7 Ba0.3 MnO3 films as well as a Ni sample. (After [64]
and [167]). (d) Scaling of the Hall constant with the longitudinal resistivity for the films from
(c). Solid and dashed lines indicate the linear and quadratic scaling laws due to skew- and side-
jump scattering. (After [64]) (e) Hall resistivity of SrRuO3 illustrating the sign change of the
anomalous Hall constant. (After [168]). (f) Hall effect of a SrRuO3 /SrIrO3 bilayer decomposed
into the anomalous (AHE) and topological (THE) Hall effect contributions (After [169])
460 M. Ziese
by Fig. 16e showing the sign change of the anomalous Hall constant in SrRuO3 .
Further, Berry phase effects lead to the emergence of a topological Hall effect when
the charge carriers move through spin structures with complex topology such as
skyrmions [178,169]. Although the spin topology does not leave a direct signature in
the magnetization component M, an additional Hall resistivity ρT H E , not following
the field dependence of the magnetization, is observed. Complex spin structures
might be induced by interfacial spin-orbit coupling, as illustrated in Fig. 16f showing
the Hall effect of a SrRuO3 /SrIrO3 bilayer [169].
The Hall effect can be used for nanoscale magnetometry, since Hall bars can be
fabricated on the micro- and nanometer scale; see, e.g., magnetometry on single iron
nanoparticles [179] or the discovery of flux-line lattice melting in Bi2 Sr2 CaCu2 O8
high temperature superconductors [180].
Spin Currents
The charge current density from Eq. (1) is defined as j = (−e)n v with the electronic
charge (−e), the carrier density n, and the electronic velocity v. Taking not only
drift, but also diffusion currents into account, Eq. (1) is generalized to
∂n 1 ∂μc
ji = σ Ei + eD = σ Ei + (20)
∂xi e ∂xi
h̄
js,ik = nvi Pk . (21)
2
The units of the spin current density js,ik are chosen such that it carries angular
momentum h̄/2. Since the spin transport is coupled to the charge transport, the
spin current density is also driven by electric fields and chemical potential gradients
[182, 183]:
9 Magnetotransport 461
h̄ ∂(nPk ) h̄ 1 ∂μs,k
js,ik =− σ Ei Pk + eD =− σ Ei Pk + .
2e ∂xi 2e e ∂xi
(22)
spin drift and diffusion can be predicted. τs denotes the spin relaxation time.
New phenomena occur, when spin-orbit coupling is taken into account [182,184,
185]. It was already shown in [182] that the spin-orbit interaction couples the charge
and spin current densities in such a way that a term proportional to −(2e/h̄)ikl js,kl
is added to Eq. (20) and a term proportional to (h̄/(2e))ikl jl is added to Eq. (22).
The different signs follow from the fact that the charge current density changes sign
under both space and time inversion, whereas the spin current density changes sign
only under space inversion. This yields the equations [183, 185]:
j = σ E + eD∇n + αSH σ (E × P ) + αSH eD ∇ × (nP ) (24)
h̄ ∂(nPk ) ∂n
js,ik = − σ Ei Pk + eD − αSH σ ikl El − αSH eDikl .
2e ∂xi ∂xl
(25)
ikl denotes the totally antisymmetric tensor; αSH is the spin Hall angle defined
as the ratio of the spin Hall conductivity σs to the diagonal charge conductivity
σ : αSH = (2h̄/e)(σs /σ ); for a tabulation of αSH values, see [185].
The cross terms appearing in Eqs. (24), (25) relate to various Hall effect
phenomena. The third term on the r.h.s. of Eq. (24) yields a charge current density
proportional to both applied electric field and spin polarization, i.e., in the presence
of a finite magnetization, an applied electric field induces a Hall effect proportional
to the magnetization component perpendicular to the applied electric field. This is
exactly the anomalous Hall effect discussed in section “Hall Effect ” and described
phenomenologically by Eq. (19).
The third and fourth term on the r.h.s. of Eq. (25) lead to the spin Hall effect
[184], in which a charge current produces a perpendicular spin current that leads
to spin accumulation at the boundaries of a finite sample. Consider a narrow flat
metal or semiconductor strip of width w (−∞ < x < ∞, −w/2 ≤ y ≤ w/2,
0 ≤ z ≤ d) in an electric field E applied along the x-direction. Solving Eqs. (23),
(25) with the boundary condition of vanishing spin current density at the surface
462 M. Ziese
The fourth term on the r.h.s. of Eq. (24) leads to the inverse spin Hall effect, in
which a spin current produces a Hall voltage by the accumulation of charges at
the boundaries of a finite sample. Consider a narrow metallic or semiconducting
half-slab (−∞ < x < ∞, −w/2 ≤ y ≤ w/2, z ≤ 0). At the top surface, spins
are injected with a spin polarization along the x-axis. This leads to a nonzero spin
current density component js,zx ; solving Eqs. (25), (23) one finds a spin polarization
decreasing exponentially into the material. Since there is no charge flow through the
surfaces, the charge current generated by ∇ × P must be balanced by an induced
electric field along the y-direction: Ey = −αSH (eD)/(σ λs )(nPx0 ) exp(z/λs ); Px0
denotes the spin polarization at the top surface. The inverse spin Hall effect was
detected in Pt when spin pumping from an adjacent permalloy layer [189] or by
spin diffusion from a Cu-permalloy injector [187]; however, it does not only occur
in non-magnetic metals with strong spin-orbit interaction, but also in ferromagnetic
permalloy, after spin injection from an adjacent yttrium iron garnet (YIG) [190].
Figure 17d shows the experiment after [187]: spins are injected from a permalloy
pad into a Cu junction by driving a current through the ferromagnetic pad along one
of the Cu arms. The spin density diffuses further along the Cu arm into the Pt wire,
where it creates a Hall voltage by the inverse spin Hall effect.
The classical spin current phenomenology was extended by the discovery of the
quantum spin Hall effect in two-dimensional systems subjected to a strong magnetic
field and the realization that the spin Hall conductance σs = (h̄/(2e))αSH σ may be
quantized in units of e/(2π ) [191]. In this case, spin-up and spin-down electrons
move with opposite chirality in one-dimensional edge states around the sample,
e.g., in HgTe quantum wells [192]. A generalization of these observations leads
to the concept of the topological insulator with topologically protected conducting
surface states around insulating bulk states [193].
9 Magnetotransport
Fig. 17 Spin Hall effect [186]: (a) GaAs film with electrodes; a local Kerr effect probe measures the Kerr rotation across the sample; the Kerr rotation is
proportional to the spin polarization. (b) Kerr rotation as a function of position across the sample and magnetic field applied parallel to y. The concentration
at the sample edges and the dephasing due to the Hanle effect are clearly seen. (c) Kerr rotation as a function of position across the film. The solid line is a fit
to the sinh function derived in the text. Inverse spin Hall effect [187]: (d) Pt film connected via a Cu junction to a permalloy (Py) spin injector. A current I is
driven through permalloy and junction by the voltage Vs ; the inverse spin Hall voltage VH across the Pt strip is measured. (e) and (f) inverse spin Hall resistance
VH /I at 77 K and 300 K as a function of applied magnetic field
463
464 M. Ziese
Magnetoimpedance
(1 + i)u R
Z=R = . (26)
tanh [(1 + i)u] μac
√ the dc resistance of the ribbon and u = d/(2δ) with the skin depth
R denotes
δ = 2/(ωσ μ0 μr ). The second equation on the r.h.s. is valid for a material
with isotropic relative permeability μr . μac denotes the ac-susceptibility of the
ribbon, caused by the skin effect, when placed in an alternating magnetic field
Hac = H0 exp(iωt) along the ribbon axis. For small skin depths, d/δ 1, μac ∼
(δ/d)(1 − i), and the impedance is much larger than the dc resistance. When a static
magnetic field is applied, the relative permeability μr is substantially decreased
and the skin depth increased, thus leading to a large decrease of the impedance,
i.e., in the zeroth approximation, giant magnetoimpedance can be considered as a
magnetically controlled skin effect.
Beyond this basic approximation, various aspects have to be taken into account
[196]: in eddy current models, the role of different domain structures (circular
domains, stripe domains) on the microscopic eddy current loss was studied [197];
in domain models, the dispersion of the circumferential permeability [198] and the
different contributions from domain wall motion and magnetization rotation [199]
were clarified. Eddy current and domain models successfully explain the relevant
features of giant magnetoimpedance up to a frequency of about 100 MHz. In the
GHz range, the magnetoimpedance is dominated by ferromagnetic resonance effects
[200].
Measurements
Fig. 18 (a) Four-contact configuration for measurement of the longitudinal voltage V and the Hall
voltage VH . (b) van der Pauw geometries. (c) Corbino disk
acceptable, when the sample resistance dominates, e.g., with metallic samples and
soldered or welded contacts. CPP measurements on metallic multilayers are made
in two-contact configuration using superconducting contacts. Often, however, the
contact resistance is high or is even non-ohmic, when pn or Schottky junctions
are formed between contact material and sample. In these cases, two-contact
measurements should be avoided; care should always be taken in choosing the
appropriate contact material.
Consider first the four-contact configuration shown in Fig. 18a. When a current I
is injected through a tip into the sample, the current density j flows radially outward
from the tip and at distance r is given by
I 1 1
j = 2
r = E = − ∇Φ (27)
2π r d ρ ρ
where r is a radius vector within the plane of the sample and Φ denotes the electric
potential. The latter is found by integration; in the situation shown in Fig. 18a with
current I injected at 1 and extracted at 4, the potential difference between 2 and 3 is
given by
ρI r2
V = ln . (28)
πd r1
From this, the resistance R = V /I and the resistivity ρ might be obtained. The Hall
voltage is given by VH = ρyx I /d, where ρyx denotes the off-diagonal resistivity;
see Eq. (7). In this geometry, care has to be taken to ensure a careful alignment of the
Hall voltage contacts; any horizontal shift will lead to the addition of a longitudinal
voltage contribution to the Hall voltage.
In order to minimize the influence of contact size and placement, van der Pauw
suggested an alternative method for resistance measurements of thin homogeneous
samples with arbitrary shape [202]. Although this method is valid for arbitrarily
formed samples, the recommended shapes are shown in Fig. 18b, since these
466 M. Ziese
minimize the influence of the size and exact location of the contacts. Consider a
sample with four contacts 1, 2, 3, 4 arranged counterclockwise around its rim, see
Fig. 18b, Ikl be a current injected into contact k and extracted from contact l; in
case of dc currents eight, in case of ac currents four non-diagonal combinations
Ikl , k, l = 1, 2, 3, 4, can be defined. The voltages measured between contacts i
and j are labeled Vij . Then eight (four) voltage measurements yield eight (four)
positive resistance values: Rij,kl = Vij /Ikl . Measurement consistency requires that
Rij,kl = Rj i,lk . The reciprocity theorem [203] requires that R21,34 + R12,43 =
R43,12 + R34,21 , R32,41 + R23,14 = R14,23 + R41,32 . The sheet resistance can be
calculated from the two averaged resistances (dc case) RA = (R21,34 + R12,43 +
R43,12 + R34,21 )/4 and RB = (R32,41 + R23,14 + R14,23 + R41,32 )/4 using the van
der Pauw relation
πd πd
exp − RA + exp − RB = 1 . (29)
ρ ρ
πd
ρ= RA . (30)
ln(2)
In case of Hall measurements, the procedure is similar; with use of ac currents, the
diagonal resistances R24,13 and R13,24 are measured. The Hall resistivity loop as a
function of applied magnetic field is then obtained as
If one is only interested in the Hall constant, resistivity values for positive and
negative magnetic field should be averaged.
Hall effect measurements are only possible, when the sample has edges placed
in such a way that charges accumulate. This was the case in the configurations
discussed so far. These correspond to a vanishing current density component
perpendicular to the longitudinal current density component. Measurements in the
absence of a transverse electric field, i.e., a Hall field, can be performed in the
so-called Corbino disk configuration; see Fig. 18c. Here the conducting annulus
has contacts around the outer and inner rims. In the absence of a magnetic field,
the current density flows in radial direction; in a perpendicular magnetic field, the
current density flows in spirals. In this configuration, the conductance related to σxx
is measured.
In case of measurements of the spin accumulation, nonlocal resistivity measure-
ments are performed [55]. Usually four contacts are defined on the sample in order
to perform local four-point measurements. Further contacts are defined outside the
current path for the measurement of voltages generated by the diffusion of carriers.
Care has to be taken to define a unique ground potential in these measurements
[204].
9 Magnetotransport 467
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Magneto-optics and Laser-Induced
Dynamics of Metallic Thin Films 10
Mark L. M. Lalieu and Bert Koopmans
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478
Magneto-Optics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
Basics of Magneto-Optics from a Macroscopic Perspective . . . . . . . . . . . . . . . . . . . . . . . . . 480
Micropic Understanding of Magneto-Optics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
Measuring Magnetism Using MOKE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
Measuring Ultrafast Magnetization Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
Ultrafast Laser-Induced Magnetization Dynamics and Opto-Magnetism . . . . . . . . . . . . . . . . 502
Conceptual Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
Ultrafast Laser-Induced Loss of Magnetic Order . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
All-Optical Switching of Magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Laser-Pulse-Excited Spin Currents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 534
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537
Abstract
Optical tools have played an important role in the field of thin film magnetism,
and the spintronics that has emerged from it. Initially, the role of optics
was limited to providing sensitive and versatile magneto-optical probes of the
magnetic behavior. In the 1990s, it became clear that ultrashort laser pulses can
also be successfully used in a reverse approach to manipulate magnetic order at
down to femtosecond time scales, an approach we refer to as opto-magnetism.
This chapter provides a basic introduction and a review of developments in
both magneto-optics and opto-magnetism, as mostly applied to metallic thin
film ferri- and ferromagnetic systems. In the second part of the chapter, after a
Introduction
This chapter discusses how light can be used to unveil magnetic ordering phe-
nomena in thin film systems but also how it has become a unique tool to modify
magnetism at unprecedentedly short time scales. Key to probing magnetism is the
notion that polarized light changes its polarization state when interacting with a
magnetically ordered material. This was discovered by the English scientist Michael
Faraday in 1845. He found that the plane of polarization is rotated when light
propagates through a magnetized material [1]. The effect is nonreciprocal, i.e., it
changes sign upon reversal of the magnetization, it is cumulative in the sense that the
polarization rotation is proportional to the optical path length through the material
under investigation, and it has its origin in the different refractive index experienced
by left-handed and right-handed circularly polarized light. A similar effect occurs
when light is reflected from a magnetized material. However, in reflection it lacks
the cumulative behavior, and therefore the rotation is generally much smaller. For
this reason, it was only discovered 30 years later in 1877 by the Scottish scientist
John Kerr [2]. The effects in transmission and reflection are referred to as the
Faraday effect and the magneto-optical (MO) Kerr effect (MOKE), respectively.
Nowadays, MOKE has become one of the most versatile and widely used
characterization techniques in research on (thin film) ferromagnetic metals. Its
popularity got a strong impulse in the 1980s with the advance of thin film magnetism
that lead to the birth of spintronics.
The complementary approach, using light not to probe magnetism, but to manip-
ulate magnetic order, has a much shorter history. Among the simplest applications
is heating a ferromagnetic thin film by a focused laser spot and thereby reducing the
magnetic moment according to equilibrium thermodynamics. Since the magnetic
anisotropy has an even stronger temperature dependence than the magnetization
itself, this approach can be used for thermomagnetic writing. It was applied e.g.
in the MO recording strategies investigated in the 1990s [3]. Apart from this
technological drive, researchers were challenged by the question as to how rapidly
the magnetization could be quenched upon sudden laser heating.
The pioneering experiments on this matter were conducted by Beaurepaire and
co-workers in 1996 [4]. The authors investigated laser-induced magnetization
dynamics in the strongly nonequilibrium regime using femtosecond laser pulses.
They found that the demagnetization in ferromagnetic nickel thin films was
completed well within a picosecond, much faster than expected; see Fig. 1a. This
observation has become a benchmark in the field. Unfortunately, both the first author
of the seminal paper, Eric Beaurepaire, and his co-author Jean-Yves Bigot passed
away in 2018.
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 479
Fueled by the novel insight, a new field in magnetism emerged. Much effort is
still being devoted to understanding the ultrafast laser-induced demagnetization, but
this phenomenon turned out just to be a tip of an iceberg. Many new mechanisms
to manipulate ferromagnetic matter by short pulses of light have been discovered
since – a field that we will broadly refer to as opto-magnetism.
Among the highlights was the demonstration in 2007 that a single fs laser
pulse can be used to “write” the magnetic moment of ferrimagnetic GdFeCo
deterministically, where the final direction is merely determined by the helicity of
the circularly polarized light [5], Fig. 1b. Soon thereafter, an alternative form of
all-optical switching (AOS) of the magnetization was found, which is independent
of the laser polarization and leads to a toggle-type behavior that reverses the
magnetization at the impact of each laser pulse [6, 7]. Furthermore, while AOS
was originally restricted to ferrimagnetic alloys (materials with spin subsystems
with oppositely oriented magnetizations), very similar results have been found for
synthetic ferrimagnets [8], i.e., multilayered thin films composed of layers with
opposite magnetization and even simple ferromagnetic films with perpendicular
magnetic anisotropy, such as Pt/Co/Pt [9]. In all these cases, however, the AOS
turned out not be the result of a single fs pulse but a cumulative effect needing many
pulses.
In parallel to these discoveries, it was found that spin currents are produced
when ultrashort laser pulses are absorbed in ferromagnetic thin films [10, 11]. The
spin angular momentum carried by these currents can affect the local magnetization
dynamics [10] but can also exert a spin-transfer torque on a nearby, noncollinearly
480 M. L. M. Lalieu and B. Koopmans
Magneto-Optics
In this section, the principles of the magneto-optical Kerr effect are introduced,
both from a phenomenological and a microscopic perspective. Different schemes
for MOKE measurements on metallic thin films are explained, both for static and
ultrafast time-resolved studies. Ways to separate magnetic signal from different
layers or elements, and Kerr microscopy are addressed.
where i and j ∈ {x, y, z} and δij is the Kronecker-delta function. For isotropic
materials, ij = 0 δij . Here, is the relative permittivity or dielectric constant.
Note that in this convention is dimensionless, whereas elements of the dielectric
tensor ij have units C2 · N−1 · m−2 . The dielectric constant is related to the complex
refractive index ñ = n + iκ via = ñ2 , in which n is the refractive index and κ is
the extinction coefficient.
In order to understand the basics of magneto-optics, we consider an optically
isotropic material with uniform magnetization M. Then, the dielectric tensor reads:
⎛ ⎞
xx xy xz
= ⎝ −xy xx yz ⎠ . (3)
−xz −zy xx
482 M. L. M. Lalieu and B. Koopmans
All these tensor elements are complex parameters, with a real part (representing
an induced dielectric polarization in-phase with the driving field) and an imaginary
part (a polarization 90 degrees out of phase). Furthermore, note that whereas the
diagonal elements ii are even in M, the nonreciprocal, off-diagonal elements
ij transform antisymmetrically under reversal of the magnetization, M ↔ −M.
The latter property provides the “magnetic contrast,” being either a change of the
polarization of the light after reflection or transmission or a change of dichroic
signal, upon reversal of M. The off-diagonal element ij is related to the component
of M parallel to î×jˆ. Thus, for spatially isotropic materials carrying a magnetization
in the z-direction, the dielectric tensor reduces to
⎛ ⎞ ⎛ ⎞
xx xy 0 1 iQ 0
= ⎝ −xy xx 0 ⎠ = xx ⎝ −iQ 1 0 ⎠ , (4)
0 0 xx 0 0 1
rss rsp
, (5)
rps rpp
where the diagonal elements represent the ordinary reflection coefficients for s-
and p-polarized light. The off-diagonal elements give rise to the magneto-optical
effects. They are (generally) orders of magnitude smaller than the diagonal ones
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 483
and change sign when reversing M. Considering the incident light to be s-polarized
and normalizing all field amplitudes to the incident one, the reflected field can easily
be derived to be
rss rsp 1 1
= rss . (6)
rps rpp 0 rps /rss
+ − − = ixy . (7)
ixy
Δñ ≡ ñ+ − ñ− = = −ñQ. (8)
0 ñ
484 M. L. M. Lalieu and B. Koopmans
Due to the difference between ñ+ and ñ− and restricting ourselves to real values,
right and left circularly polarized light will experience a relative phase difference
while propagating in a direction collinear with M. Considering linearly polarized
light, which is a linear superposition of circularly polarized light with opposite
handedness,
1 1 1 1 1 1
=√ √ +√ , (9)
0 2 2 i 2 −i
This result describes a rotation of the initial polarization that is proportional with
d, which is just the Faraday effect. Similarly, it is straightforward to verify that
dissipative media with magnetic circular dichroism, i.e., Δκ = 0, generally show
both a polarization rotation and a change in ellipticity.
Of more relevance in the context of thin film magnetism is the difference in the
reflection coefficient experienced by right and left circularly polarized light, which
for normal incidence on a semi-infinitely thick material magnetized perpendicular
to the surface reads
1 − ñ±
r± = . (11)
1 + ñ±
It can be easily verified that reflected linearly polarized light will experience a
(complex) rotation of its polarization, given by
iñQ
θ̃ = , (12)
−1
which is just the MO Kerr effect at normal incidence. As stated before, at non-
normal incidence, the complex Kerr rotation depends on the polarization of the
incident light. Similar expressions for (multi)layered thin film systems and arbitrary
configurations can readily be derived using the earlier mentioned transfer matrix
method [14].
In the analysis so far, magneto-optics was described in terms of a dielectric
tensor that incorporates the magnetization implicitly. Alternatively, one may lin-
earize the M-dependence and introduce a material-dependent – but magnetization-
independent – tensor α accordingly. This description is particularly illustrative
when, in section “Ultrafast Laser-Induced Magnetization Dynamics and Opto-Mag-
netism”, we will treat the so-called inverse-Faraday effect (IFE). For a spatially
isotropic material with a finite magnetization, the induced dielectric polarization P
can be written as
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 485
P = αE × M, (13)
where α is the diagonal element of α, and E is again the amplitude of the oscillating
electric field, and M is the static magnetization vector. Equation (13) provides an
intuitive picture of both the Faraday effect and MOKE. Assuming Mẑ and incident
light with wave vector qM and polarization Ex̂, an induced oscillatory dielectric
polarization P ŷ is generated, emitting electro-magnetic radiation coherent with
the incident light but with a polarization orthogonal to it. Superposition of the
transmitted or reflected incident wave with the orthogonally polarized one is
observed as a rotation of the plane of polarization.
To complete this phenomenological introduction of MO effects, three different
configurations in which MOKE can be applied are introduced. They are distin-
guished by the orientation of the magnetization vector with respect to the sample’s
surface normal and the plane of incidence of the light; see Fig. 2c-e. In the polar
geometry, the magnetization vector is perpendicular to the magnetic thin film (or
sample surface). In the longitudinal configuration, the magnetization is parallel to
the film and lies within the plane of incidence. In this case, a non-normal incidence
of the light needs to be chosen, since a normal incidence would result in qP , for
which the MO effects vanish; see Eq. (13). This is in contrast to the polar Kerr
effect, in which case perpendicular incidence can be considered the most simple
and efficient configuration. Finally, the transverse configuration refers to the case
where the magnetization vector is parallel to the magnetic film and perpendicular
to the plane of incidence. This configuration requires p-polarized light, because the
signal vanishes for pure s-polarized light (Eq. 13). In the transverse configuration,
no change of polarization can be observed, but the Kerr effect manifests itself as a
change in intensity upon reversal of the magnetization. As a rule of thumb, the polar
effect is typically an order of magnitude stronger than the longitudinal effect.
The phenomenological analysis so far was purely based on symmetry. Aiming for a
microscopic understanding, the elements of the dielectric tensor – both the diagonal
and the off-diagonal ones – can be related to the electronic states of the material.
Within the electric dipole approximation, the interaction between light and matter
can be treated equivalently [16] using either an interaction Hamiltonian eE · r
(sometimes referred to as velocity gauge) or −(e/m)A · p (length gauge), where
e is the electron charge, m its mass, A is the vector potential, and r and p = −ih̄∇
are the position and momentum operator, respectively. For isolated atoms this leads
to the well-known dipole selection rule ΔLz = ±1, where Lz is the z-component
of the angular momentum operator, which allows for transitions between s- and
p-states, and between p- and d-states, but not between s- and d-states.
Within a single-particle description, the dielectric tensor elements can be
expanded as a sum over contributions due to “vertical” optical transitions (k n = k n ),
introducing matrix elements
486 M. L. M. Lalieu and B. Koopmans
= Ψn |pi |Ψn
,
i
Πnn (14)
where |Ψn
are single-particle electronic states with wave vector k n . Following Ref.
[17], converting equations from c.g.s. to S.I. units and expressing elements of the
dielectric tensor ij (ω) = 0 δij + iσij (ω)/ω rather than the optical conductivity
σij (ω), one obtains
e2
f (εn ) − f (εn ) Π i Π j
ij (ω) = 0 δij + n n nn
. (15)
h̄m2 V ω ωnn ω − ωnn + i/τ
n,n
Here, the summation is over all states n (n ) with energy εn (εn ) and h̄ωnn =
εn − εn . Furthermore, f (εn ) refers to the Fermi-Dirac distribution function, and
V is the volume of the crystal. Finite lifetime effects have been taken into account
in a phenomenological way, by introducing a life time τ for all transitions.
In order to capture the magneto-optics in a transparent way, the matrix elements
can be written in an alternative form that reflects transitions by circularly polarized
light, i.e., photons carrying a positive or negative quantum of angular momentum:
±
Πnn = Ψn |pi − ipj |Ψn , (16)
for light propagating in the direction î × jˆ. In this notation, the off-diagonal elements
of the dielectric tensor read [17, 18]
2 j 2
ie2
Πni n − Πn n
occ. unocc.
ij (ω) = , with i = j, (17)
2h̄m2 V ω n n
ωn2 n − ω2
where now the summation over n ranges over all occupied states and the summation
over n over all empty states. The full response including the corresponding real part
can be obtained by Kramers-Kronig transformation [18].
It can be shown that the quantity |Πn+ n |2 − |Πn− n |2 , relevant for the nonreciprocal
off-diagonal elements ij , vanishes once summed over any full set of degenerate
states if spin-orbit coupling is neglected.1 This reflects the fact that magneto-optics
probes (a weighted average of) orbital angular momentum rather than spin ordering.
Thus, although usually it is assumed that magneto-optics is sensitive to the spin
ordering, this is only true in the case of finite spin-orbit coupling and assuming
a strict correlation between spin and orbital momenta. Exact summation rules can
be derived that show that the integrated spectral weight of a certain nonreciprocal
tensor element corresponds to a component of the total orbital momentum vector
[20]. More loosely speaking, one can say that magneto-optics measures the orbital
moment, whereas the spin moment can only be derived by assuming a fixed
relation between the two. This should be kept in mind particularly when performing
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 487
a 0.8 b 4
0.6 Im 3
Im
0.4
(eV 2)
(eV 2)
2
0.2
0
0.0 1
/
/
xy
xy
Re
(h )2
(h )2
-0.2
0
-0.4
-1 Re
-0.6
-0.8 -2
0 1 2 3 4 5 6 0 1 2 3 4 5 6
h (eV) h (eV)
c 4
3 Im
(eV 2)
2
0
1
/ xy
(h )2
-1
Re
-2
0 1 2 3 4 5 6
h (eV)
Fig. 3 Experimental MO spectra showing the square of the real (black) and imaginary (red) value
of (h̄ω)2 xy /0 for (a) nickel, (b) cobalt, and (c) iron, as a function of the photon energy h̄ω. The
data points are adopted from Ref. [21], and the solid lines are guides for the eye
488 M. L. M. Lalieu and B. Koopmans
a b
Fig. 4 (a) Simplified spin-resolved density of states (up and down electrons), showing exchange
and spin-orbit split d-bands and one of the p-states out of the broad sp-band. (b) Peaks in the
imaginary part of the diagonal dielectric tensor element xx for spin-conserving transitions between
p and d states for up and down electrons, as derived from (a). (c) Similar construction of the
imaginary part of xy . The real parts, both in (b) and (c), can be obtained by Kramers-Kronig
transformations. (Figure adapted from Refs. [22, 23])
Hso = ξ L · S, (18)
Different Configurations
We consider a reflection experiment with linearly polarized light, incident on a flat
surface at a certain angle of incidence. The polarization state of the light will be
expressed as an angle θin , according to tan(θin ) = Es /Ep , where s and p refer
to the s- and p-polarized components (Fig. 2a). Upon reflection, the polarization
state may be changed, and we denote the change of rotation by θ ≡ θout − θin ,
where “in” and “out” refer to the incoming and reflected light. It should be
realized that a change of polarization state can already be induced without any
MO interaction and even from an isotropic material. This generally occurs when
the incident light is neither s- nor p-polarized. The resulting effects thereof are
widely used in ellipsometry. For the analysis of MO measurements, it is convenient
to distinguish between contributions to the total (complex) polarization rotation
that transfer symmetrically (“S”) and antisymmetrically (“A”) under reversal of the
magnetization M, θ̃T = θ̃S + θ̃A . Then, the complex Kerr rotation θ̃ = θ + i as
introduced in section “Basics of Magneto-Optics from a Macroscopic Perspective”
is obtained from
∞
θ̃ = F̃ i (z) · M i (z)dz, (20)
i 0
θ̃ = F̃ M. (21)
This provides two complementary channels to measure the same magnetic parame-
ter M, i.e., the real and imaginary part of θ̃ = θ +iε. Clearly, in order to optimize the
signal-to-noise ratio, the channel with the largest component of F should be chosen.
Moreover, optical components, such as wave plates, can be used to effectively
measure an optimal linear combination of θ and ε.
Having two complementary channels can be exploited in many ways. First of
all, in the simple case described by Eq. (21), the complementary channels can be
used to verify the assumptions that are made. For example, if reversing the in-
plane magnetization shows up differently in rotation and ellipticity in a longitudinal
MOKE experiment, it could be a signature of a perpendicular component being
mixed in due to a small misalignment of the applied magnetic field. More impor-
tantly, however, the complementary channels can be used to separately measure
different magnetic components, such as the switching of two different magnetic
layers (see section “Layer-Specific MOKE”), to differentiate between an out-of-
plane and in-plane component of the magnetization or to distinguish two different
magnetic sublattices in an alloy.
The simplest realization of a MOKE experiment exploits a crossed polarizer
configuration, as sketched in Fig. 5a. Usually, a collimated light source (often a
CW or pulsed laser) is polarized (P1) before being focused on the sample, the latter
to establish spatial resolution. The reflected light is collimated and sent through a
polarizer (P2), dubbed the analyzer, set at an angle α nearly – but not exactly –
crossed to the polarization axis of P1, i.e., α = |αP1 − αP2 | = π/2 + γ , for small
γ . For simplicity, we assume P1 to be aligned along the s- or p-polarization axis. In
that case, the intensity after the analyzer is given by
I = I0 R(γ 2 + 2γ θ + θ 2 + ε2 ), (22)
a b c
Fig. 5 Illustration of three different schemes for performing MOKE. (a) A crossed-polarizer
configuration, in which an analyzer (P2) is almost crossed with a polarizer (P1). (b) A balanced
photodiode configuration, in which a polarizing beam splitter (PBS) is adjusted so as to balance
signals of two orthogonal polarization components. (c) A polarization modulation configuration, in
which a PEM is used to establish high-frequency polarization modulation, and a lock-in amplifier
detects signals at the fundamental and second-harmonic frequency of the modulation. A quarter-
wave plate (QWP) can be inserted to select a linear combination of rotation and ellipticity
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 491
are neglected. The terms quadratic in θ and ε can usually be neglected because of
the smallness of the Kerr effect and, moreover, are symmetric under reversal of M
and thereby are difficult to distinguish from the first term. The 2γ θ term is the Kerr
rotation signal of interest. While it looks as if the sensitivity increases upon opening
the analyzer (i.e., increasing γ ), this comes at the cost of an increased background
signal, described by the first, γ 2 , term. Thus, a compromise should generally be
sought to optimize signal to noise. Finally, note that although according to Eq. (22)
the crossed-polarizer configuration seems to be insensitive to the Kerr ellipticity,
adding a quarter-wave plate (at an angle of 45◦ ) between the sample and the analyzer
reverses the role of rotation and ellipticity.
In an alternative approach, a polarizing beam splitter (PBS) is adjusted to
balance the signal from two photodiodes, measuring orthogonal polarization com-
ponents, as sketched in Fig. 5b. In this balanced photodiode scheme, with the
beam splitter set such that it splits components with polarization angles of +45◦
and −45◦ , the measured intensity simply reads (neglecting terms quadratic in
θ and ε)
I = I0 Rθ. (23)
1 0
, (24)
0 eiA0 cos(2πf t)
where A0 determines the amplitude of the oscillatory retardation between the two
orthogonal polarization components of the light. Setting A0 = π/2, the light after
the PEM oscillates between left- and right-handed circular polarization. Two simple
configurations can be distinguished. For the configuration where the main axis of
the modulator is set to 45◦ with respect to the plane of incidence of the light on
the sample, we refer to Refs. [25, 26]. Here, we will briefly discuss the simpler case
where the main axis of the modulator is set to 0◦ . The signal from the photodetector,
positioned after the analyzer that is aligned with the PEM at the p-polarization axis,
is sent to a lock-in amplifier. It can be shown [26] that dc and harmonic signals are
generated. Up to second order in the polarization modulation frequency f , they read
where Jn (A0 ) is the n-th order Bessel function. Thus, it is seen that ellipticity ε (via
the 1f -signal) and rotation θ (via the 2f -signal) – or, alternatively, complementary
linear combinations thereof when using an additional wave plate – can be measured
simultaneously.
Layer-Specific MOKE
In case of a multilayer structure including multiple magnetic layers, the measured
value of ε or θ is proportional to a weighted average of the magnetization in
the different layers, where the weighting factors depend on the details of the
structure (materials, layer thicknesses) and measurement configuration (wavelength,
polarization, and angle of incidence), c.f., Eq. (20). In this section, an extension to
the previously discussed MOKE setup will be introduced, which makes it possible to
perform layer-specific measurements in a magnetic bilayer system, i.e., individually
measuring the magnetization of one of the two magnetic layers [27, 28]. The layer-
specific technique discussed here is based on the PEM configuration of the MOKE
setup, but it is noted that it works for other MOKE configurations as well.
A phenomenological explanation of the layer-specific MOKE measurement
technique starts by representing the MO response of a single magnetic layer by a
Kerr vector θ̃ = θ + iε = Ωeiξ in the complex Kerr plane spanned by ε and θ .
The Kerr vector is described by a Kerr amplitude Ω and Kerr angle ξ , as illustrated
in Fig. 6a. Within this representation, the I1f (I2f ) signal in the ordinary MOKE
setup measures the projection of the Kerr vector on the imaginary (real) axis. In
the case of a magnetic bilayer, the Kerr vector describes the MO signal of the
complete structure and is equal to the sum of the Kerr vectors of the individual
layers, θ̃tot = θ̃1 + θ̃2 = F˜1 M1 + F˜2 M2 , as illustrated in Fig. 6b, and where we
again simplified Eq. (20). Measuring, for instance, I2f (i.e., θ ), yields the projection
a b c
Fig. 6 (a) The Kerr vector in the complex plane spanned by the Kerr ellipticity ε and the Kerr
rotation θ. It is described by a Kerr amplitude Ω and Kerr angle ξ , and represents the MO response
of a single magnetic layer. The measured values of ε or θ in the MOKE setup are the projections of
the Kerr vector on the imaginary or real axes. (b) Total Kerr vector representing the MO response
of a magnetic bilayer. The total Kerr vector θ̃tot is equal to the sum of the Kerr vectors of the
individual layers, θ̃1 and θ̃2 . Rotating the projection axis P to be perpendicular to θ̃1 causes the
MO signal of this layer to be excluded in the projection. (c) Kerr vector for different depths di of
a magnetic layer within a structure, with d1 < d2 < d3 . Burying the magnetic layer deeper into
the structure causes a rotation of the Kerr vector, as well as a decrease in its amplitude. (Figures
adapted from Ref. [27])
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 493
of θ̃tot on the real axis, also called the projection axis P , and thus includes the MO
signal of both layers. Measurement of an individual layer would be possible when
the projection axis P is rotated to be perpendicular to one of the two Kerr vectors,
e.g., θ̃1 , as illustrated in Fig. 6b. In that case, the projection of θ̃1 is zero, and the
measured signal only includes the projection of θ̃2 . This shows that by rotating the
projection axis, it is possible to individually measure the magnetization in one of
the two layers in a magnetic bilayer by removing the contribution of the other layer
to the measured MO signal.
One possible method to rotate the projection axis is by adding a quarter-wave
plate (QWP) to the MOKE setup [28]. As indicated in Fig. 5c, the QWP is placed
in between the first polarizer and the PEM. Depending on the angle of the QWP,
I1f and I2f measure linear combinations of ε and θ , corresponding to a rotation
of the projection axis. Using Jones matrix calculations [15], the first- and second-
harmonic contributions to the measured intensity of the light can be calculated to be
I1f = 2I0 R θ sin(2α) + ε cos2 (2α) J1 (A0 )
(28)
I2f = 2I0 R θ cos2 (2α) − ε sin(2α) J2 (A0 ),
in which α is the angle of the QWP. It can be seen that for both I1f and I2f , there
are certain angles of the QWP α = α0 at which the MO signal disappears (i.e.,
I1f/2f (α0 ) = 0).
When the Kerr vectors of the two magnetic layers (i = 1, 2) in a magnetic bilayer
have different Kerr angles ξi , as is the case in Fig. 6b, the MO signal of the individual
layers will disappear at different angles α0,i . When the QWP angle is set to α0,i
of layer i, only the magnetization of the other layer is measured, resulting in a
layer-specific measurement. One way to assure different Kerr angles is by using
two magnetic layers made of different materials. This was used in Ref. [28], in
which the magnetization dynamics of the individual Ni and Fe layers in a Fe/Ru/Ni
multilayer were measured separately at different angles of the QWP (α0,Ni = α0,Fe ).
An additional advantage of this technique over other element-specific measure-
ment techniques is the ability to perform layer-specific measurements on magnetic
bilayers containing two identical magnetic layers. This is made possible by a depth
dependence of the MO signal [27, 29], as illustrated in Fig. 6c. The figure illustrates
the Kerr vector of a (single) magnetic layer for different depths di within a structure,
with d1 < d2 < d3 . Burying the magnetic layer deeper into the structure causes a
rotation of the Kerr vector, as well as a decrease in its amplitude. The rotation of
the Kerr vector with depth causes the Kerr angle of two identical magnetic layers in
a magnetic bilayer to be (slightly) different, resulting in a different α0 for the two
layers and making it possible to perform a layer-specific measurement.
An experimental demonstration of the depth dependence of α0 for a single out-
of-plane magnetized Co layer buried in Pt is presented in Fig. 7a. In this figure,
the I2f signal coming from the magnetization in the Co layer is measured as a
function of the QWP angle, for different thicknesses of the Pt capping layer. The I2f
494 M. L. M. Lalieu and B. Koopmans
b 1.0
0.5
0.0
MOKE Signal (norm.)
-0.5
-1.0
1.0
0.5
0.0
-0.5
-1.0
1.0
0.5
0.0
-0.5
-1.0
-250 -200 -150 -100 -50 0 50 100 150 200 250
Field (mT)
Fig. 7 (a) Measurement of the I2f signal coming from the magnetization in the Co layer
as a function of the QWP angle, for different thicknesses of the Pt capping layer. The inset
highlights the shift in α0 when the Co layer is buried under an increasing amount of Pt. The
solid lines are fits to the data using Eq. (28). (b) Layer-specific measurement performed on a
Ta/Pt/Co/Pt/Ru/Pt/Co/AlOx (bottom to top) multilayer, showing three hysteresis loops measured
at three different angles α of the QWP. The top panel shows the hysteresis curve in which both
Co layers are visible, in which the outer (inner) switches correspond to the magnetization in the
bottom (top) Co layer. The middle and bottom curves show layer-specific measurements, in which
the signal of one of the two layers is excluded from the measurement
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 495
signal is determined from the height of the hysteresis curve measured using polar
MOKE. The solid lines are fits using Eq. (28), showing a very good agreement.
It can be seen that for each curve there are two angles of the QWP at which the
I2f signal is zero. These angles correspond to the α0 angles of the Co layer. More
importantly, highlighted in the inset, a clear shift in α0 of about 0.4 ◦ nm−1 is seen
when the Co layer is buried under an increasing amount of Pt. This shift correlates
to the rotation of the Kerr vector, as illustrated in Fig. 6c, whereas the decrease in
the signal amplitude with increasing Pt thickness corresponds to the decrease of the
Kerr amplitude.
The prediction that the small shift in α0 allows for a layer-specific measure-
ment in a magnetic bilayer containing two magnetic layers made from the same
material is demonstrated in Fig. 7b. The presented measurement is performed on
a Ta(2)/Pt(10)/Co(1)/Pt(0.4)/Ru(1)/Pt(0.4)/Co(1.3)/AlOx (2.0) (bottom to top and
thickness in nanometer) multilayer, containing two out-of-plane magnetized Co
layers that are antiferromagnetically coupled by a thin Pt/Ru/Pt spacer. At α = 3.57◦
(middle panel), a sensitivity to only the top layer is achieved, resulting in a single-
component hysteresis curve. Similarly, at α = 5.01◦ (bottom panel), only the
bottom layer is seen, while at arbitrary angle (top panel), both layers show up.
This measurement clearly demonstrates that although the difference in α0 for the
two Co layers is quite small (1.44◦ ), a layer-specific measurement is possible,
even when the two magnetic layers are made of the same material, which is not
possible with element-specific measurement techniques such as X-ray magnetic
circular dichroism, discussed in the next section. For completeness, it is noted that
the difference in α0 for the two layers may not only be due to their different depth
but may also be partially ascribed to subtle differences in their electronic and optical
properties due to different neighboring layers.
MO Spectroscopy
Another approach to disentangle magnetic information in more complex systems is
provided by selecting appropriate wavelengths. While most MOKE setups operate
with a single laser or LED operating in the visible or near-infrared, a complete MO
spectrum can be measured using either a broadband light source in combination
with a spectrometer or a wavelength-tunable laser system. Clearly, as with ordinary
ellipsometry, a more complete deconvolution of the MO response in multilayer
systems is possible from such a spectrum, provided enough information about the
wavelength-dependent diagonal and off-diagonal elements of the dielectric tensor
of the different layers is known. More specifically, in some alloys it is known
that different elements contribute to different parts of the MO spectrum. As an
example, in rare-earth transition-metal ferrimagnetic alloys, it is known that the
high-wavelength part (600 nm) is most sensitive to the transition-metal atoms
(and their magnetic moments) and the (ultra)violet part to the rare-earth atoms.
This has been used e.g. to disentangle the different response of the sublattices after
femtosecond laser heating [30].
Extending our scope to sources well outside the visible range, X-ray techniques
are known to be extremely powerful. In fact, X-ray magnetic circular dichroism
496 M. L. M. Lalieu and B. Koopmans
MOKE Microscopy
One of the advantages of using MOKE as a magnetometry tool is its spatial
resolution. Even with long-focal-length lenses, a resolution of a couple of tens of
micrometer resolution is easily achieved in a very simple setup. Such resolution
allows local magnetization measurements on thin film samples where one (or more)
of the layers has been given a position-dependent thickness via a “wedge growth”
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 497
a
~16 fps
CCD camera
Longitudinal
Polar Longitudinal with transverse Transverse Transverse
sensitivity
Tube lens
Analyzer
Collector Field
Aperture Compensator
Diaphragm
diaphragm
Xe arc (centered) Polarizer
lamp
Back
focal plane
Objective lens
sample sample
50 mm
Fig. 8 (a) Schematic drawing of a wide-field Kerr microscope. Figure adapted from Ref. [39]. (b)
Example of Kerr microscopy, showing a domain pattern in a permalloy patterned film element
of 240 nm thickness, imaged in longitudinal sensitivities with light incidence from different
directions. (Figure adapted from Ref. [40] Reproduced from [40], with the permission of AIP
Publishing)
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 499
probe scheme using two laser pulses, i.e., the first pulse is used to excite (pump) the
magnetization dynamics and the second (mechanically time-delayed) pulse is used
to probe it. The ultimate time resolution is achieved by using two pulses derived
from the same laser source to avoid electronic jitter. To obtain a high sensitivity, a
stroboscopic scheme can be employed, in which a train of high-repetition-rate laser
pulses is focused on the sample. In such cases, the approach is commonly referred
to as time-resolved MOKE (TR-MOKE).
Linearizing Eq. (21) for a simple system in which the MO signal depends solely
on a single magnetization component, it is simple to see that the pump-pulse-
induced complex Kerr rotation can be written as
where F0 and M0 are the generalized Fresnel coefficient and the magnetization in the
absence of a pump pulse. This equation carries an important warning. The first term
on the right-hand side is proportional to the laser-induced change in magnetization,
ΔM(t), and is the targeted signal reflecting the genuine magnetization dynamics.
The second term, however, does not. It is due to a pump-induced modification of
the proportionality factor, ΔF (t). We will return to this issue in section “Ultrafast
Laser-Induced Loss of Magnetic Order”, but the message here is that one should
always be aware of the occurrence of possible “artifacts.”
An implementation of TR-MOKE based on the polarization modulation scheme
is sketched in Fig. 9 and will be explained later. A simpler realization exploits the
crossed-polarizer configuration, which was introduced in Fig. 5a. Both the pump
and probe pulses can be derived from the same laser source using a beam splitter
(BS) or frequency converter by a nonlinear crystal. Collimated probe pulses are
polarized before being passed along a mechanical delay line to adjust the time delay
between the two pulses, whereafter they are directed to the sample. Pump and probe
pulses are focused to (at least partially) overlapping spots on the sample. It can be
of advantage to use a probe spot that is smaller than the pump spot, in order to
probe a region where the change in magnetization is more or less homogeneous.
The influence of the pump beam on the polarization state of the reflected probe
pulse is measured using an analyzer and any type of photodetector. To measure
the pump-induced changes to the magnetization, measurements of θ̃(t) with and
without pump-pulse excitation are compared. Often, to enhance the sensitivity, a
mechanical chopper is placed in the pump beam that periodically blocks the pump
pulses (see Fig. 9), and a lock-in amplifier is used to directly measure Δθ̃ (t).
From Eq. (22), it is easy to derive that the pump-induced change in output signal
is described in lowest order of θ̃ by [26]:
where R0 and ΔR(t) are the reflectivity and pump-induced transient thereof. Care
has to be taken to rule out artificial signals due to a ΔR(t) of nonmagnetic origin.
The term γ 2 ΔR(t) transforms symmetrically under reversal of M, and can as such
500 M. L. M. Lalieu and B. Koopmans
Fig. 9 Schematic overview of the TR-MOKE setup in a polarization modulation scheme. Using
a delay line to alter the path length of the probe pulse, the magnetization can be measured as a
function of time after the pump-pulse excitation by adjusting the pump-probe time delay (Δt)
ΔI1f (t)
= 2J1 (A0 )Δε(t), (33)
Idc
ΔI2f (t)
= 2J2 (A0 )Δθ (t). (34)
Idc
probe time delay. The figure displays both the fast demagnetization dynamics in the
first few picoseconds and a laser-induced magnetization precession at a longer time
scale, which is discussed in the following section. The top panel shows the dynamics
measured for the two opposite magnetization directions (black), set by the external
field applied almost perpendicular to the sample surface (H = ±160 kA/m).
The pure magnetic response to the laser-pulse excitation is calculated using the
difference of the two curves (Eq. 19) and is shown by the open dots in the bottom
panel (red). The solid symbols (blue) represent the laser-pulse-induced changes in
the optical signal due to “nonmagnetic” contributions, which is calculated using
the sum of the measured data for the two opposite magnetization directions and
arises e.g. due to state-filling that can occur during pump-probe overlap (see
section “Experimental Demonstration of Laser-Induced Demagnetization”). In this
specific measurement, it only shows some small features around zero pump-probe
delay, but in other cases these nonmagnetic contributions to the signal can become
more prominent, or even dominant.
The setup as displayed in Fig. 9 can be considered as a basic or standard TR-
MOKE arrangement. A simple extension can be made in order to reduce the
nonmagnetic contributions by using a two-color scheme, in which the pump and
502 M. L. M. Lalieu and B. Koopmans
probe pulses have different wavelengths. This can be accomplished, for instance, by
sending the probe beam through a frequency doubler. Also, the previously discussed
layer-specific MOKE technique can be used by adding a QWP to the setup, as was
shown for the static MOKE in Fig. 5c and which allows to individually measure
the magnetization dynamics in one of the two layers in a magnetic bilayer, e.g., see
Refs. [28, 46].
Analogous to the TR-MOKE setup, time-resolved MCD measurements
can be performed by using fs X-ray or XUV pulses for the probe beam,
allowing element-specific and spin-orbit-resolved MCD measurements of the
laser-induced magnetization dynamics. An example of such time-resolved element-
specific XMCD measurement, performed to investigate the laser-pulse-induced
magnetization reversal in a GdFeCo alloy, is discussed in section “All-Optical
Switching of Magnetization”. Lastly, time-resolved MSHG measurements can be
achieved by recording the probe-pulse-induced second-harmonic generation as a
function of the pump-probe delay time [47].
Conceptual Introduction
The 1990s saw an entirely new development, facilitated by the commercial avail-
ability of fs pulsed laser sources, which began to be used to explore the ultimate
limits of magnetization dynamics. A major outcome of these studies is that we no
longer see optics as merely a powerful tool to read the magnetic state but also as
a very efficient tool to manipulate it. As such, a new field of opto-magnetism has
emerged, in which magnetic ordering is affected by the light.
Opto-magnetism provides a method to control the magnetic state beyond the
traditional precessional dynamics as described most conveniently by the Landau-
Lifshitz-Gilbert equation of motion [48]
dM α dM
= −γ μ0 (M × Heff ) + M× . (35)
dt M dt
Here, an effective field H eff is introduced that applies a precessional torque on the
magnetization M as described by the first term on the right-hand side, where γ is
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 503
the (positive) gyromagnetic ratio and μ0 the vacuum permeability. The second term
describes a phenomenological damping via the Gilbert damping parameter α, which
allows the system to dissipate energy and thereby converge to the lowest energy
state, in which M is aligned with H eff . The precessional dynamics in ferromagnets
proceed at frequencies of up to 10s of GHz for applied magnetic fields not exceeding
1 MA/m (μ0 H ∼ 1 Tesla) and conserves the magnitude of the local magnetization.
Opto-magnetism provides a route to change not only the orientation but also the
magnitude of M, and it does so on a time scale that is typically up to three orders of
magnitude faster.
A first (basic) mechanism to exploit pulsed lasers to manipulate ferromagnetic
order is laser heating. Pulsed lasers have enough energy per pulse to heat up a
ferromagnetic thin film of any material and with a thickness comparable to the skin
depth of the light, to well above its Curie temperature. Increasing the temperature
will lower the equilibrium magnetization, and the system will strive to re-establish
thermal equilibrium between the spin- and other degrees of freedom, lowering its
magnetization. Finding the relevant time scale associated with losing magnetic
order was one of the fundamental quests that inspired researchers in the 1990s.
Beaurepaire and co-workers were the first to find that the relevant time scale was
well below a picosecond [4]. This rapid loss of magnetization was referred to as
ultrafast demagnetization.
Effects of laser heating can be even more spectacular if they provoke a transition
between contrasting magnetic phases. A trivial example is laser heating through the
Curie temperature, driving a system from the ferromagnetic to the paramagnetic
state. Then, the magnetization can regrow in the opposite direction upon cooling
down when a static reversed magnetic field is applied [49], as is shown in Fig. 11a.
A more interesting situation occurs for materials like FeRh, which can be grown
Fig. 11 (a) Recovery of the magnetization of GdFeCo alloy after a full laser-induced demagneti-
zation in the presence of a applied magnetic field in the original direction (triangles up), zero field
(squares), and reverse field (triangles down). (Figure taken from Ref. [49]. with kind permission
of APS) (b) Laser-induced growth of magnetization in FeRh as measured by TR-MOKE (filled
symbols), compared to the transient reflectivity ΔR. (Figure taken from Ref. [50] with kind
permission from APS)
504 M. L. M. Lalieu and B. Koopmans
M = αE × E ∗ , (36)
where E is the amplitude of the oscillating (optical) electrical field as defined before,
E ∗ its complex conjugate, and α a material constant characterizing the size of
the IFE in the material. It should be emphasized that the cross product E × E ∗
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 505
vanishes for linearly polarized light. For circularly polarized light, we see that the
induced magnetization reverses upon reversal of the helicity. Furthermore, it should
be stressed that the induced M is coherent in the sense that it is setup by the laser-
field and decays within a decoherence time. It has been suggested that the IFE
may be of relevance for HD-AOS of metallic ferrimagnets, which is discussed in
section “All-Optical Switching of Magnetization”.
Laser excitation has been demonstrated to be a source of laser-induced spin
currents – whether by spin-polarized ballistic electrons, of “superdiffusive”
nature, or driven by the demagnetization or thermal gradients. These spin
currents trigger a variety of magnetization dynamics, further elaborated on in
section “Laser-Pulse-Excited Spin Currents”.
a b
gep
Te Tp
Ce Cp
ges gsp
Ts
Cs
Fig. 12 (a) Induced MSHG signal as a function of pump-probe delay time at different laser
fluences measured for nickel. Displayed fluences normalized to 1.00 ≈ 6 mJ/cm2 . (Figure taken
from Ref. [47]. with kind permission from APS) (b) Schematic diagram of the evolution of Te (t)
(red), Tp (t) (blue), and Ts (t) (green), as well as the corresponding M(t)/Msat (green, top panel),
after pulsed laser excitation at delay 0, calculated using the 3TM (Eqs. 41 and 42), and setting
gsp = 0. Demagnetization time τM and e-p equilibration time τE are indicated. Note that a peak
in Ts (t) corresponds to a dip in M(t). (c) The 3TM, showing the three interacting reservoirs
with temperature Ti and heat capacity Ci and that exchange heat via a coupling constant gi,j
(i, j = e, p, s), see discussion Eq. (42)
their spins, and the lattice (phonons). To each of them, a temperature is assigned
(discussed in more detail later). In terms of this model, the laser pulse causes
an ultrafast rise of the electron temperature, which subsequently cools down by
exchanging heat with the lattice as mediated by electron-phonon coupling. The
electron-phonon equilibration time is denoted by τE (see Fig. 12b) and is typically
of the order of ∼0.5 − 1.0 ps. In parallel, the spin system is heated up by interaction
with the electrons and the lattice, causing the rapid loss of magnetization with a
demagnetization time τM , and finally equilibrates with both of them. The surprising
outcome was that the spin temperature follows the electron temperature faster
than the lattice does. It hereby reaches a peak – corresponding to a dip in the
magnetization – after approximately half a picosecond. Successively, the spins cool
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 507
Fig. 13 (a) Normalized rotation (filled diamonds) and ellipticity (open circles) channels measured
by TR-MOKE for a Ni thin film, showing clear differences during the first few hundred fs. (Figure
taken from Ref. [67] with kind permission from APS). (b) Similar results on CoPt3 ; rotation (open
diamonds) and ellipticity (filled circles). (Figure taken from Ref. [70] with kind permission from
APS). (c) Calculated dichroic bleaching for nickel at a similar excitation density fexc (defined as
the number of optically excited electrons per atom) as used in the measurements in (a). The vertical
dashed lines indicate the photon energy used in the experiment. (Figure taken from Ref. [71])
508 M. L. M. Lalieu and B. Koopmans
(a)
0.8
(b)
Spin and orbital moments ( ħ per atom)
Sz
0.6 th = 280 ± 20 fs
0.4 –55%
Lz
2.5 mJ/cm2
3.0 mJ/cm2
0.2 = 220 ± 20 fs 3.5 mJ/cm2
th
4.0 mJ/cm2
4.5 mJ/cm2
–67% 5.0 mJ/cm2
0.0
0 1 2
Dela y (ps)
(c)
Fig. 14 (a) Spin (Sz , red) and orbital (Lz , blue) magnetic moments as a function of the delay time
between the laser pump and the X-ray probe pulses, extracted using sum rules. The measurement
is performed on a ferromagnetic Co0.5 Pd0.5 thin film using the Co L2,3 absorption edges. (Figure
taken from Ref. [84] with kind permission from APS). (b) Fluence dependence of the laser-induced
sub-ps demagnetization of a 15 nm Ni film at room temperature. Figure taken from Ref. [85]. (c)
Time-resolved magnetization following single-cycle THz pumping of a 5 nm CoFeB film. Inset:
CoFeB demagnetization amplitude as a function of the THz peak field. (Figure taken from [86])
ps electrical current pulse [92]. These experiments are indicative that neither the
photon field nor hot electrons with eV energies are an essential ingredient for sub-
ps demagnetization. A similar conclusion can be drawn from a TR-MOKE study by
Roth et al. on a Ni thin film at different pump laser fluences [85], shown in Fig. 14b.
The demagnetization slows down at increasing laser fluence. At the highest fluence,
a rather continuous demagnetization takes place up to a ps, well after the driving
laser field has decayed and electrons have thermalized (both typically 50–100 fs).
Yet another way of exciting sub-ps demagnetization is by using single-cycle THz
pulses. Bonetti and co-workers performed THz-pump MOKE-probe experiments on
crystalline Fe and amorphous CoFeB [86]. Although the amount of demagnetization
was very small, typically 0.1%, the drop in magnetization followed quite accurately
the dissipated power as expressed by the THz driven current J (t) and the THz
electric field E(t); see Fig. 14c.
Although the foregoing results seem to favor a local and thermodynamic picture,
there is growing evidence that this is not the whole story. The community has
become aware of the role of optically induced spin transport, first demonstrated by
Malinowski et al. [10]. There is growing evidence that the demagnetization process
proceeds faster for ultrathin films on top of a metallic substrate as compared to
insulting substrates, due to spin angular momentum being efficiently transported
out of the ferromagnetic layer [46]. Yet, even when confining the metallic system in
a nonconductive environment to prevent spin transport, ultrafast demagnetization at
a 100 fs timescale is consistently being seen [93].
where we separated the electron contribution into an orbital and a spin part, Le and
S e , Llat is the angular momentum provided by the lattice, and J EM is the angular
momentum in the photon field.
A fundamental bottleneck in ultrafast changes of the magnetization is provided
by the need to conserve the total J while changing the magnetic moment:
μ = μB (Le + gS e ). (38)
For the materials considered here, g ≈ 2. In the ground state, the magnetic moment
is strongly dominated by Se , since the orbital momentum is significantly quenched
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 511
beating between the m = 2 and m = −2 state. The apparent conclusion is that the
angular momentum is not conserved! This is due to the torque applied by the crystal
field on the d-orbitals, while we neglected in our Hamiltonian the back action on
the neighboring nuclei. If we would have included the motion of the nuclei in our
Hamiltonian, the total angular momentum would have been exactly conserved by
compensating contributions from the electron and the nuclei.
Extending this picture to laser-induced demagnetization requires many additional
interactions to be included in our Hamiltonian, including spin-orbit coupling as an
essential ingredient. Upon laser heating, the original angular momentum associated
with the magnetic ordering is transferred to a local twist of the crystal within an
area comparable to the size of the laser spot. This local twist will propagate radially
outward as a torsional shockwave. Ultimately, this leads to a final (though minute)
rotation of the crystal, c.q. its holder, cq., the optical table, etc., in a fashion similar
to a picture sketched by Fähnle et al. [98].
With the notion in mind that our Hamiltonian generally does not necessarily
conserves angular momentum, we analyze the possible underlying elementary
scattering processes. A relevant one is the Elliott-Yafet spin-flip scattering, in which
electrons have a finite chance to flip their spin upon scattering at impurity sites or by
emission or absorption of a phonon (in a e-p scattering process) [99]. The resulting
spin-flip probability is a consequence of the fact that spin (nor J ) is not a good
quantum number in our crystals. Thereby, eigenstates of our Hamiltonian are of a
mixed spin character of the type
for σ =↑, ↓ and where labeling is chosen such that for all states b < 0.5. Then, a
spin-mixing parameter < b2 > can be calculated after weighing it over all possible
scattering processes. This spin-mixing parameter scales with Z 4 , where Z is the
ionic charge in units of e, and typically b2 << 1 for materials under consideration.
If an electron scatters from a state k to k , the spin can generally not be conserved,
which finally leads to a spin-flip probability asf of the order of the bk2 after a weighted
averaged over the Brillouin zone. We emphasize that it is an incorrect picture to state
that (all) spin angular momentum associated with the electronic spin-flip process is
transferred to the specific phonon emitted or absorbed.
Interestingly, this process of EY type of scattering with phonons can be trivially
extended to the process of electron-electron (e-e) scattering. Also, in this case, the
process can be quantified by a finite spin-flip probability during the e-e scattering
event – an approach adapted e.g. by Steil et al. [97] and further elaborated on in
the next section. Similar to the phonon-mediated Elliott-Yafet process, the angular
momentum will be dumped in the rotational degrees of freedom of the crystal.
τ0 ∝ (E − EF )−2 . (40)
Typically, life times are just a few fs for energies of more than an eV above EF .
Electrons kick out other electrons from the Fermi sea via Coulomb scattering,
starting a cascade of increasingly more excited electrons while conserving the total
excess energy. After a typical thermalization time of τT = 100 fs, the occupation
of electronic states resembles a Fermi-Dirac distribution again, a process that can
be followed by time-resolved photoemission [82,100]. For ferromagnetic materials,
the life time for majority and minority carriers can be significantly different due to
the different phase space for spin-conserving Coulomb scattering, as first measured
by Aeschlimann et al. by spin-dependent two-photon photoemission in 1997 [101].
This spin-dependent lifetime is of crucial relevance for superdiffusive spin transport,
discussed in section “Laser-Pulse-Excited Spin Currents”.
After thermalization of the electron system, a two-temperature model can be
used to describe the dynamics of the heated electron system in contact with the
cooler lattice. Thermal reservoirs are introduced for the electrons and the lattice
(phonons), as in the 3TM sketched in Fig. 12c. Each bath is assumed to be in
full internal equilibrium, and a temperature, Te and Tp , respectively, is assigned
to it. Furthermore, both baths are assigned a heat capacity, Ce and Cp , and a
coupling constant gep is introduced to account for heat exchange, microscopically
mediated by electron-phonon (e-p) scattering processes. Thus, a simple set of
coupled differential equations is derived, including a source term that describes the
heating of the electrons by the laser pulse. The solution describes a process in which
initially the electrons are heated, after which electrons and lattice equilibrate at a
time scale τE ∼ 0.5 ps for the ferromagnetic transition metals.
For a phenomenological description of laser-induced demagnetization, Beaure-
paire et al. used an extension of the two-temperature model, which has been dubbed
the three-temperature model (3TM) [4]. Like the electron and lattice system, the
spin system is assumed to be in full thermal equilibrium and is assigned a “spin
temperature.” Although not a trivial concept, it can most easily be defined by
relating the instantaneous magnetization M(t) at certain time t to the equilibrium
magnetization at temperature at T:
dTe
Ce = gep (Tp − Te ) + ges (Ts − Te ) + P (t),
dt
dTp
Cp = gep (Te − Tp ) + gsp (Ts − Tp ),
dt
dTs
Cs = ges (Te − Ts ) + gsp (Tp − Ts ), (42)
dt
514 M. L. M. Lalieu and B. Koopmans
where Cs is the spin specific heat, diverging at TC , ges and gsp are the electron-
spin and spin-lattice coupling constants, respectively, and P (t) is the source term.
In the limit of low laser fluence and zero pulse length, i.e., instantaneous heating
of the electron gas, and neglecting the spin specific heat, an analytical expression
for the time evolution of the magnetization ΔM(t) has been derived in terms of τE
and τM [102, 45]. This expression can be conveniently used to fit and parameterize
experimental data sets [103]. Despite its use for phenomenological understanding
and as a quantitative fitting tool, the 3TM does not provide any microscopic insight.
Next, we will discuss theoretical approaches that have tried to pinpoint the key
microscopic mechanism of sub-ps demagnetization.
As briefly introduced before, it has been suggested that the photon field might
play a crucial role. A first mechanism is a direct effect, in which the magnetic
moment in the excited state after optical absorption of a photon differs from
the one in the ground state. However, effects will be relatively small in the
prototype transition-metal (TM) ferromagnets since the orbital magnetic moments
are quenched. Moreover, it has been argued that the number of photons in
typical experiments is far too small to account for the observed magnetization
dynamics [67].
In 2000, it was argued that a laser field in combination with electron correlation
and spin-orbit coupling could lead to an ultrafast demagnetization at tens of fs
[104, 105, 106]. Later, Bigot et al. conjectured that the material polarization induced
by the photon field may interact coherently with the spins, corresponding to a
mechanism that has its origin in relativistic electrodynamics [59]. In passing, it
should be mentioned that the latter results have been criticized in Ref. [107].
Moreover, the experimental effects reported in [59] were only seen during the
presence of the laser pulse and left no imprint on the magnetization afterward.
As mentioned in the previous section, spin-orbit coupling leads to spin-mixing in
the electronic eigen states, which is a source of spin-flip scattering when electrons
scatter with other quasi particles. Koopmans and co-workers have proposed a
theoretical framework to incorporate Elliott-Yafet type of spin-flip scattering with
phonons [55, 103] or impurities [55] into the earlier mentioned 3TM. Within this
microscopic three-temperature model (M3TM), a simple model Hamiltonian is used
to derive three coupled differential equations for the time evolution of Te , Tp , and the
normalized magnetization m = M/Ms (directly related to Ts according to Eq. (41)).
The model is schematically depicted in Fig. 15a.
In the M3TM, the electron system is described by spinless free electrons, with
a constant density of states near the Fermi level (DF ), leading to Ce = γ Te with
the constant γ ∝ DF . Phonons are described within the Einstein model, or mapped
on a Debye model, in both cases described by the Debye (phonon) energy ED ,
and the phonon number of modes per atom Np . The phonon heat capacity Cp
is assumed to be independent of T , a reasonable approximation near and above
the Debye temperature. Finally, spin excitations are treated using a spin S = 1/2
mean-field Weiss model, introducing the atomic magnetic moment μat and the Curie
temperature TC , directly related to the mean-field exchange parameter J . The spin
specific heat is neglected, Cs = 0, so that the evolution of Te and Tp does not
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 515
(a) (b)
E (½ + n) h p
+½ e
EF kTe
ex
-½ asf p
DOS e
Electrons Spins Phonons
Fig. 15 Schematic diagram of the M3TM. (a) Representation of the electron, phonon, and spin
system, including a scattering event in which an electron loses kinetic energy, a phonon is emitted,
and a spin is flipped to reduce the magnetization, while conserving energy. (b) Elliott-Yafet spin-
flip mechanism, in which a spin is flipped during an e-p scattering event
Thus, a compact equation for the evolution of the magnetization dynamics m(t) is
found, in which the rate of demagnetization is described by the parameter
(in units of s−1 ), where Vat is the atomic volume, and gep ∝ λ2ep can be expressed in
elementary model parameters (see Supplementary Information of Ref. [103] for
details). The parameter asf is proportional to < b2 > in Eq. (39), highlighting
the importance of spin-orbit interaction. One readily sees that no magnetization
dynamics occurs, i.e., dm/dt = 0, if asf = 0, as expected.
Two other approaches, although rather contrasting at first sight, reproduce
magnetization dynamics very similar to the M3TM. Firstly, the Landau-Lifshitz
Bloch (LLB) equations provide an extension of the LLG equation, by adding
516 M. L. M. Lalieu and B. Koopmans
h̄ 1
τM ≈ c0 , (45)
k B TC α
using the calculated ab initio value, whereas Schellekens et al. argue that close
agreement with experimental results is obtained by implementing them in the Weiss
or Heisenberg picture (in which the magnetization dynamics is due to thermally
disordered orientation of fixed atomic moments) [112].
The basic M3TM makes use of severe approximations that can be lifted when
desired. One can implement a more realistic electronic density of states, phonon
dispersion, or extensions from S = 1/2 to arbitrary spin multiplets. Also, the
description of itinerant magnetism in a pure Weiss picture may be considered
inadequate. The s-d model applied to ultrafast magnetization dynamics in Ref. [113]
provides an interesting step beyond.
We treated phonon-mediated Elliott-Yafet spin-flip scattering in quite some
detail. Spin-flip e-e scattering is another possibly relevant scattering mechanism, in
which one of the two mutually scattering electrons flips its spin. Although it could be
argued that this process does not conserve angular moment, we highlighted before
that it will be facilitated by the non-spin-conserving character of the Hamiltonian
and will lead to a dump of angular momentum in the rotational degrees of motion of
the crystal. Steil et al. included this type of Coulomb scattering, without the need of
referring to a phononic spin bath [97, 114]. They implemented this in a Stoner-
like description in which electrons are scattering between different spin bands.
Reasonable agreement with experiments was found assuming spin-flip probabilities
of 0.15 and 0.30, for Co and Ni. From this, a μT -model emerged, in which
dynamics is described in terms of equilibration of temperatures and chemical
potentials of the electron subsystems simultaneously [115]. This approach bares
some similarities with the s-d model of Ref. [113].
Finally, the increase of computational power and refinement of codes have fueled
activities on many-body theory and ab initio calculations. Ultimately, this would
enable to trace the angular momentum transfer from a microscopic perspective.
Töws and Pastor performed small-cluster calculations distinguishing local and
itinerant electrons and exploring the interplay between spin-orbit interactions and
interatomic hopping, as well as the role of the photon field [96]. Realistic time
scales of demagnetization of typically 100 fs were obtained. Although the lattice
degree of freedom was not included in this work, the authors stated that the leaking
angular momentum would manifest itself as a global rotation of the rigid lattice if it
were explicitly included in the calculation.
Fully ab initio calculations of laser-induced magnetization dynamics have been
reported by Sharma and co-workers [116, 117]. They employed time-dependent
density functional theory in an all-electron solid-state code for the case of uncon-
strained noncollinear spins, as driven by short pulses of electro-magnetic radiation.
Despite the fact that the amount of demagnetization observed was at least an order
of magnitude smaller than realistic experiments would show and the phonons were
not included yet, this field is rapidly making progress.
(a) (b)
(c)
1.0
0.9
0.8
M/M0
0.7
0.6
0.5
original work [63], fs-XMCD studies revealed an initial much more rapid decay
within the first ps that accounts for only a part of the total demagnetization [75];
see Fig. 16c. As mentioned before, this behavior has been denoted as type-II, in
contrast to ordinary type-I behavior with a single continuous decay as observed for,
e.g., Ni and Co [103]. A similar two-step demagnetization was also observed in the
fs-XMCD for ferromagnetic Tb films, with an identical 1 ps initial decay, but the
slower decay being a factor of 5 faster than for Gd. The initial faster component
was assigned to the presence of hot electrons that speed up spin-lattice interaction
during the first ps, in line with the 1 ps that is needed in both materials to equilibrate
the electron and phonon system. The differences between Gd and Tb were assigned
to the different orbital momenta in their respective ground state, being L = 0 and
L = 3, respectively.
The peculiar type-II behavior observed for Gd has also been addressed in the
context of the M3TM in Ref. [103]. Surprisingly, in that work it was found that
type-II dynamics is a natural outcome whenever τM becomes larger than τE . In
such a case, a single scattering mechanism naturally provides a two-step decay with
two different time constants. The first rapid decay occurs as long as the electron
temperature is still (far) above the lattice temperature. Once the electron and phonon
520 M. L. M. Lalieu and B. Koopmans
system, we know that this may be a poor approximation at a 100 fs time scale.
Indeed, experiments using time- and energy-resolved photoelectron spectroscopy
have resolved that at ultimate short time scales, one cannot treat the spin polarization
of the conduction band as a uniformly varying rigid system any longer [127].
However, whether such nonequilibrium effects significantly affect the main channel
of angular momentum transfer is yet unknown.
(a) (b)
100
–50
Fe
–100
–1 0 1 2 3
Pump–probe delay (ps)
In the years that followed, the importance of both the laser-induced heating
and helicity effects for the AOS was under debate [130, 131, 132, 133, 134, 135].
Macrospin Landau-Lifshitz-Bloch [132] and atomistic Landau-Lifshitz-Gilbert
[134] calculations showed that AOS could indeed be achieved via a laser-induced
effective-field pulse (in combination with the demagnetization). However, apart
from the high amplitude of the magnetic field pulse needed for the switch (≈20 T),
the induced magnetic field needed to persist in the material for a much longer time
than the duration of the laser pulse itself. This resulted in the notion of some kind
of helicity memory mechanism in the RE-TM system [133, 135].
More clarity came when it was observed that the magnetization in GdFeCo can be
switched using single linearly polarized laser pulses [7], proving the (single-pulse)
switching mechanism to be a purely thermal process, which was simultaneously
established theoretically as well [136]. Moreover, it was demonstrated that the
helicity dependence presented in Fig. 17a was the result of magnetic circular dichro-
ism (MCD) [137], which describes the difference in absorption for left and right
circularly polarized light in magnetic materials (section “Basics of Magneto-Optics
from a Macroscopic Perspective”). In the case of AOS, there is a minimum amount
of energy that needs to be absorbed for the switch. Therefore, the MCD opens up a
fluence window where the AOS is helicity-dependent.
Insight into the thermal single-pulse switching mechanism was actually already
observed earlier using time-resolved XMCD measurements [6] (section “MO
Spectroscopy”). In these measurements, the magnetizations of the individual Gd
and Fe sublattices in a GdFeCo thin film were measured in time after fs laser-
pulse excitation and in the presence of an external magnetic field. The result of
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 523
the measurement is presented in Fig. 17b, where the normalized XMCD signal of
both magnetic sublattices is plotted as a function of pump-probe delay. The observed
behavior is typically divided into three subsequent phases: (i) the magnetization of
both sublattices rapidly demagnetizes after the laser-pulse excitation. The magneti-
zations on the two sublattices quench at different rates, with the Fe magnetization
demagnetizing much faster and reaching zero while the Gd is still demagnetizing.
(ii) As a result of exchange scattering, angular momentum is transferred from the
demagnetizing Gd to the Fe sublattice, resulting in a buildup of Fe magnetization
along the Gd magnetization direction. This results in a transient ferromagnetic-like
state in the ferrimagnet. (iii) Finally, the system cools down on a longer time scale.
With the relatively large magnetization buildup in the Fe, the antiferromagnetic
exchange coupling drives the switch of the Gd magnetization. Eventually, the system
recovers to the ferrimagnetic state, having its magnetization reversed with respect
to the initial state and demonstrating the AOS.
Soon it was concluded that – in agreement with the previous scenario – there are
three key ingredients necessary to facilitate the AOS: (i) two magnetic sublattices;
(ii) an antiferromagnetic exchange interaction between the two sublattices, resulting
in an antiparallel alignment of the sublattice magnetizations; and (iii) a difference
in demagnetization rate for the two sublattices. This was verified theoretically by
introducing these ingredients in various models, including a general theoretical
framework [136], atomistic spin models [6,7,138,139], and the M3TM [140], which
all demonstrated the capability of thermal single-pulse switching. Experimentally,
the range of materials for which AOS was found rapidly expanded, including
different RE-TM alloys, multilayers, heterostructures, and RE free synthetic-
ferrimagnetic heterostructures [141, 8, 142]. The common features in all these
material systems are the previously mentioned needed ingredients, supporting their
necessity. The importance of the helicity of the light, however, was not elucidated
for some of the systems.
The inconsistency between the AOS mechanism resolved for the GdFeCo alloys
and the observation of AOS in ferromagnetic systems was reconciled by the
discovery that there are two different AOS mechanisms at play [145]. For the
GdFeCo system, it was confirmed that the AOS is indeed a single-pulse helicity-
independent switch, corresponding to the earlier discussed thermal single-pulse
switching mechanism. For both a ferromagnetic Pt/Co/Pt multilayer and a ferrimag-
netic TbCo alloy, however, no single-pulse AOS was found. For these systems, a
helicity-dependent multiple-pulse mechanism was revealed. A measurement of this
switching mechanism in the Pt/Co/Pt multilayer is shown in Fig. 18a. The figure
(a)
(b) -
M
1 Hz M 15 µm
No pulse 100 pulses 600 pulses 3,600 pulses
Fig. 18 (a) Measurement of the multiple-pulse AOS switching mechanism in a Pt/Co/Pt sample,
showing the normalized magnetization (measured as the anomalous Hall voltage VHall ) as a
function of time, while simultaneously the structure is exposed to femtosecond laser pulses which
are either left circular (σ − ), right circular (σ + ), or linearly (π ) polarized. (Figure taken from
Ref. [145] with kind permission from APS) (b) Measurement demonstrating the helicity-dependent
laser-pulse-induced domain wall motion. The direction of the domain wall motion is set by the
helicity of the laser pulses, causing either the up (light) or down (dark) magnetized domain to grow
in size. (Figure taken from Ref. [146])
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 525
system for which the single-pulse AOS mechanism was found, which is needed
for fast future spintronics. Realizing that the AOS is a purely thermal process,
it was found that the switch could also be obtained using ultrafast hot-electron
pulses [154, 155] (analogous to the hot-electron pulse-induced demagnetization
discussed in section “Key Observations in Laser-Induced fs Demagnetization”).
These hot-electron pulses were generated by laser-pulse excitation of the Pt layer
in a Pt/NM/GdFeCo multilayer, whereafter the hot-electron pulse flows through the
thick nonmagnetic conductive spacer (NM) toward the GdFeCo layer. There, the
hot-electron pulse will deposit its energy and induce the magnetization reversal.
Later, using a photoconductive switch, it was demonstrated that the fast switch can
also be induced by a picosecond charge-current pulse [156].
Alongside the investigation on the different modes of stimuli for the thermal
AOS, research was done trying to achieve the single-pulse AOS in other material
systems that are more relevant for spintronic applications. For instance, it was
demonstrated that a ferromagnetic layer can be switched using single laser pulses
when it is deposited on top of a GdFeCo layer, in which case the ferromagnet
switches along with the GdFeCo alloy due to the exchange coupling between the
two layers [157]. A similar mutual AOS can be achieved when the GdFeCo layer
and the ferromagnet (FM) are separated by a nonmagnetic (NM) spacer layer to
create a GdFeCo/NM/FM spin-valve structure. In this case, the single-pulse AOS in
the GdFeCo alloy can be transferred to the ferromagnet by the spin current generated
by the Gd sublattice upon laser-pulse excitation [158, 159].
A different approach was taken, both theoretically [162] and experimentally
[160], by using a synthetic-ferrimagnetic multilayer which mimics the earlier
discussed properties of the GdFeCo alloy that are needed for the thermal single-
pulse AOS. Figure 19a shows the magnetization of a Pt/Co/Gd stack, toggling up
(light) and down (dark) upon excitation with subsequent fs laser pulses [160]. This
toggling behavior is characteristic for the thermal single-pulse AOS. The use of
such synthetic-ferrimagnetic multilayer allows for easy fabrication and (interface)
engineering. Moreover, the specific Pt/Co/Gd stack possesses a perpendicular
magnetic anisotropy (PMA) [160], large spin-orbit torques (spin Hall effect), and
a sizable interfacial Dzyaloshinskii-Moriya interaction (iDMI) resulting in chiral
Neél domain walls [161], making the structure an ideal candidate to facilitate the
integration of AOS with spintronic devices such as the racetrack memory [163]. The
potential of the stack for spintronic integration is demonstrated in Fig. 19c, showing
field-free “on-the-fly” AOS in a Pt/Co/Gd (micron-sized) racetrack [161]. The figure
shows the normalized anomalous Hall signal (∝ Mz ) measured in the Hall cross
located at one end of the racetrack, as illustrated in Fig. 19b. The measured signal
registers magnetic domains passing the cross shortly after they are written at the
other side of the racetrack using thermal single-pulse AOS (red dotted lines). The
domains are transported through the wire as soon as they are written by an electrical
current that is sent continuously through the wire, combining the spin Hall effect in
the heavy-metal Pt seed layer, the PMA in the magnetic layer, and the chiral Neél
walls for coherent and efficient domain wall motion.
Additionally, recent experiments have demonstrated that the DW velocity
in synthetic-antiferromagnetic [164] and (synthetic) ferrimagnetic [165, 166]
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 527
0.5
0.0
-0.5
-1.0
0 5 10 15 20 25 30 35 40 45 50 55 60
(c) Time (s)
Around the same time of the first observation of all-optical switching, it was also
discovered that the fs laser-pulse excitation of ferromagnetic layers can induce a
nonlocal transfer of angular momentum [10]. In other words, it was demonstrated
that a current of spin polarized electrons, i.e., a spin current, can be generated upon
fs laser-pulse excitation of a ferromagnetic thin film. As was the case for all-optical
switching, part of the excitement over the observation derived from its potential use
in future spintronic applications. Within the field of spintronics, spin currents are
heavily used to manipulate magnetic information in (future) data storage devices,
e.g., to write data in magnetic random access memory [167] or transport data in
the earlier introduced magnetic racetrack memory [163]. Conventionally, these spin
currents are generated electronically on a nanosecond time scale. The manipulation
of the magnetization can be pushed to the ultrafast time scale by using the optically
528 M. L. M. Lalieu and B. Koopmans
generated spin currents, which operate at the sub-picosecond time scale. On a more
fundamental level, the discovery of the fs laser-pulse-excited spin current sparked
a debate about the underlying mechanism of ultrafast demagnetization, discussing
the importance of both local and nonlocal dissipation of angular momentum. In the
following, a selected overview of the research performed on the optically generated
spin currents and their ability to control the magnetization in magnetic thin films is
given.
(a) (b)
t Ru = 0.4 nm
Normalized Δθ/θ
(c) H probe
pump Fe Au AP
P
MgO(001)
0 0.5 1.0
M mSHG Delay (ps)
Fig. 20 (a) Illustration of the magnetic collinear bilayer used to demonstrate the presence of laser-
pulse-excited spin currents. (b) Demagnetization traces measured with the magnetic bilayer in the
parallel (P) and antiparallel (AP) configuration, showing an increase in demagnetization speed and
amplitude for the AP alignment with respect to the P alignment. ((a,b) Figure taken from Ref.
[10] with kind permission of Springer Nature) (c) Illustration of the second-harmonic generation
pump-probe measurement on a Fe/Au bilayer, directly measuring the laser-induced spin current
injected from the Fe layer into the nonmagnetic Au layer. (Figure taken from Ref. [168] with kind
permission from APS)
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 529
shown in Fig. 20b, which indeed shows that both the speed and amplitude of the
demagnetization is increased for the antiparallel alignment with respect to the
parallel alignment. Performing similar measurements on a bilayer with an insulating
spacer showed no difference in the demagnetization for the parallel and antiparallel
configurations, confirming the presence of angular momentum exchange by the
laser-pulse-excited spin currents in the case of the conducting spacer.
Soon after the discovery, a first model on the generation mechanism of the
optically excited spin current was developed [11, 169]. In this model, a spin current
is generated as a result of spin-dependent lifetimes and velocities of the excited
hot electrons. As a specific example, the hot majority electrons in Ni have a longer
inelastic lifetime as compared to minority electrons [τ0,↑ > τ0,↓ , Eq. (40)], and
thereby will dominate the spin current. The spin current is considered to propagate in
the “superdiffusive” regime, starting in the ballistic regime just after excitation and
relaxing to normal diffusion on a longer time scale. Moreover, it was claimed that
the demagnetization measured in thin nickel films could be explained purely based
on this nonlocal transfer of angular momentum away from the probed area, starting
the discussion on the local versus nonlocal dissipation of angular momentum as the
driving force of fs laser-induced demagnetization.
Even though the occurrence of optically induced spin currents was demonstrated
in experiments such as shown in Fig. 20a, b, determining their relative contribution
to sub-ps demagnetization as compared to local dissipation of angular momentum
turned out to be a challenge. While some experiments were explained using the
optically excited spin current as the dominant source of demagnetization [170, 171,
172, 173], other demagnetization studies showed no sign of its contribution [93].
An increasing amount of experiments, however, demonstrated that both the local
and nonlocal angular momentum dissipation mechanisms are of importance and
that the relative contribution of either is dependent on the precise material system
[34,29,174,46]. Using element-specific XMCD measurements, even a laser-induced
enhancement of the Fe magnetization in a Fe/Ru/Ni multilayer was claimed [170,
33, 34]. The enhancement to values up to 10% above the saturation magnetization
was attributed to the spin current generated in the (parallel) Ni layer being absorbed
in the Fe layer. This observation, however, could not be reproduced using different
measurement techniques, i.e., by XMCD measurements at a different absorption
edge of the Fe and Ni [174], or using the earlier discussed layer-specific MOKE
technique [28] (see section “Layer-Specific MOKE”).
The first direct detection of the optically excited spin current was done using a
Fe/Au bilayer [168]. An illustration of the measurement is shown in Fig. 20c. A spin
current was generated in the Fe layer by laser-pulse excitation at the Fe side, which
was injected into the (thick) nonmagnetic Au layer and propagated toward the outer
Au surface. Using a probe pulse incident from the Au side, the spin current was
measured at the Au surface via magnetization-induced second-harmonic generation
(MSHG) (see section “MO Spectroscopy”). Later, the spin accumulation resulting
from this laser-pulse-excited spin-current injection into the nonmagnetic layer in a
FM/NM bilayer was also measured using time-resolved MOKE [13, 175] and using
the layer-specific MOKE technique [46].
530 M. L. M. Lalieu and B. Koopmans
With the increasing amount of research on the optically excited spin currents,
more mechanisms for spin current generation were proposed. At least four different
mechanisms have been identified. (i) As conjectured in the original work by
Malinowski [10], an optically generated spin-polarized distribution of ballistic (hot)
electrons can act as a source of spin current. (ii) Adding inelastic scattering events,
one arrives at the earlier discussed superdiffusive spin current model [11, 169]. (iii)
Beyond the superdiffusive mechanism, assuming all electrons to be thermalized,
a laser-induced temperature gradient across a ferromagnetic layer may still result
in a longer-lived spin current generation at the FM/NM interface due to the spin-
dependent Seebeck effect [176]. This concept was extended to the nonthermal
regime in Ref. [177]. (iv) Also the rapid change of M itself has been proposed
as a source. More specifically, the angular momentum conservation of the electron-
magnon coupling causes the demagnetization to generate spin-polarized electrons
at a rate of −dM/dt, which propagate into the neighboring layers. This process was
modeled in the diffusive regime by Choi et al. [13]. Strongly related, but within
the perspective of an s-d model, sudden laser-driven demagnetization will induce a
temporal splitting of the s-electron chemical potential, which also act as a source of
spin current into neighboring layers [113].
Heat current
M spin current M
(b) 0.2
0.1
(mdeg)
0.0
–0.1
0.1
Δ Kerr
0.0
–0.1
0 250 500 750 1,000
Delay (ps)
(c) 8
6
Efficiency (%)
0
0 1 2 3 4 5 6
Co thickness (nm)
Fig. 21 (a) Illustration of a noncollinear bilayers used to measure the laser-induced spin-transfer
torque. (Figure taken from Ref. [13] with kind permission from Springer Nature) (b) Time-resolved
measurements of the out-of-plane component of the magnetization for two different configurations
of the noncollinear bilayer. (Figure adapted from Ref. [12] with kind permission from Springer
Nature) (c) Efficiency as a function of the collector layer thickness, with the efficiency defined as
the ratio of spins absorbed by the collector to the spins lost during demagnetization in the emitter.
(Figure taken from Ref. [179] with kind permission from APS)
532 M. L. M. Lalieu and B. Koopmans
anisotropy [12, 56] (as discussed in section “Conceptual Introduction”). The red
curve, however, corresponds to the precession of the in-plane magnetization in the
Co collector (red arrow) and is driven by the optical STT mechanism demonstrated
in Fig. 21a. Comparing the dynamics for the two different configurations shows that
the phase of the magnetization precession in the collector is set by the orientation of
the magnetization in the emitter (i.e., the polarization of the generated spin current),
as is expected for the laser-induced STT mechanism.
This laser-induced STT in the noncollinear bilayer can be used as a tool to probe
the optically excited spin current and has been used to investigate the transport of
the laser-pulse-excited spin current through different spacer layers [12], the optical
excitation of spin currents in ferrimagnetic alloys [159], and the dependence of the
optical spin current generation on the emitter thickness [179]. The latter showed that
the full thickness of the emitter (an out-of-plane magnetized [Co/Ni]N multilayer)
contributes to the generated spin current (at least up to 3.4 nm), which is consistent
with recently performed theoretical calculations using an extended superdiffusive
spin current model [181] but contradicts an earlier observed optical spin-emission
region in Fe of ≈1 nm [182]. Additionally, the absorption of the optically excited
spin current in the collector was investigated using a wedge-shaped collector layer.
The result of this measurement is presented in Fig. 21c. The figure shows the
efficiency as a function of the Co collector thickness, with the efficiency defined as
the ratio of spins absorbed by the collector to the spins lost during demagnetization
in the [Co/Ni]4 emitter. It can be seen that the spin current is absorbed very locally
near the injection interface, i.e., 90 % of the transverse spins are absorbed within
the first ≈2 nm of the collector layer.
(a) 4.0
3.5
MOKE signal (arb. unit.)
3.0
2.5
1.0
0.5
0.0
10.23 GHz
-0.5
0 5 20 40 60 80 100 120 140 160 180 200
Delay (ps)
(b) 1.2
(c)
×20 n =4
n =3
Frequency (THz)
0.8 n =2
n =1
n =0
0.4
panel shows the Fourier spectrum of the magnetization dynamics measured in the
collector after laser-pulse excitation. The right panel displays the calculated spin
wave dispersion, in which the dots represent the frequencies corresponding to the
534 M. L. M. Lalieu and B. Koopmans
At the end of this chapter, we briefly highlight some of the exciting trends in the
field and sketch promising routes for future research.
Magneto-optics is known for almost two centuries, and experimental approaches
including Kerr microscopy have well matured. Nevertheless, applications to new
systems and phenomena keep introducing new demands and opportunities. The
rise of thin film magnetism and the birth of spintronics in the last two decades
of the previous century have pushed applications of the magneto-optic Kerr effect
enormously. A similar boost has come from recent trends in spintronics, such as
novel device architectures based on magnetic domain walls that are driven by spin-
orbit torques, which has caused a revival of Kerr microscopy.
Another trigger pushing methodological developments has come from the new
field of opto-magnetism, requiring magneto-optical techniques with femtosecond
resolution. In many cases this can be easily established by pump-probe configura-
tions and measuring in a stroboscopic manner. But such an approach is of limited
value if stochasticity plays a role. This faces new challenges, in particular when
aiming at microscopy. Developments of single-shot wide-field magneto-optical
microscopy and other experimental approaches with combined spatial resolution
down to the nanometer scale and sub-ps time resolution are emerging and will most
probably grow in importance. An interesting case is provided by establishing depth
resolution, which could certainly be pushed beyond todays achievements.
As briefly discussed in this chapter, together with experimental progress in
using visible and near-infrared (laser) light for magneto-optical and opto-magnetic
experiments, rapid developments using other parts of the electromagnetic spectrum
have been witnessed. In this sense X-ray techniques are particularly noteworthy
because of their element specificity, as well as distinguishing spin and orbital
magnetism. Table-top implementations using high-harmonic generation will enable
much more widespread use and possibly new spectroscopic approaches. Finally, a
rapid growth of THz studies is being seen. They provide access to ac conductivity
of electrons and a complementary view on sub-ps magnetization dynamics and spin
currents.
10 Magneto-optics and Laser-Induced Dynamics of Metallic Thin Films 535
Notes
1 An exception is provided by topological MO effects for crystals with a specific magnetic point
group symmetry with a chiral spin ordering [19].
2 Note that in the presence of spin-orbit coupling S and L are no good quantum numbers either, but
we might have expected the total J to be still conserved, but this is apparently not the case.
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Further Reading
1. Qiu, Z.Q., Bader, S.D.: Surface magneto-optic kerr effect. [37]
2. Soldatov, I.V., Schäfer, R.: Advances in quantitative Kerr microscopy. Phys. Rev. B 95, 014426 (2017)
3. Oppeneer, P.M.: Magneto-optical Kerr spectra. [17]
4. Hellman, F., et al.: Chapter IV in “Interface-induced phenomena in magnetism”. [184]
5. Kirilyuk, A., et al.: Ultrafast optical manipulation of magnetic order. [185]
6. Koopmans, B.: Laser-induced magnetization dynamics. [26]
7. Koopmans, B.: Time-resolved Kerr-effect and Spin Dynamics in Itinerant Ferromagnets. [186]
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
Classification of Magnetoelastic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
Anisotropic Magnetostriction (Joule Magnetostriction) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
Magnetovolume Effects, Spontaneous Magnetostriction, Forced
Magnetostriction, and Invar Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 552
Villari Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 553
E Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 553
Magnetomechanical Damping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 555
Wiedemann Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
Matteucci Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
Magnetic Field-Induced Strain Phenomena, Which Differ from Joule
Magnetostriction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
Magnetoelasticity and Joule Magnetostriction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 560
Derivation of the Magnetostrictive Strain Tensor: Cubic Case . . . . . . . . . . . . . . . . . . . . . . . 560
Magnetostriction of Polycrystalline Cubic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
Derivation of the Magnetostrictive Strain Tensor: Hexagonal Case . . . . . . . . . . . . . . . . . . . 565
Magnetostriction of Polycrystalline Hexagonal Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 566
Magnetostriction and Stress-Induced Magnetic Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
Magnetoelastic Effects in Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
Experimental Determination of Magnetostriction and Magnetoelastic Coupling . . . . . . . . . . 570
Magnetoelastic Coupling in Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
Magnetostriction and Magnetoelasticity: Physical Origin and Insights from Theory . . . . . . . 574
Compilation of Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
Magnetoelastic and Elasticity Data for Bulk Transition Metals . . . . . . . . . . . . . . . . . . . . . . 577
Theoretical and Experimental Values of Magnetoelastic Coupling
Coefficients and Their Strain Dependence (Table 4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
Magnetostriction Data of Amorphous Fe Alloys (Table 5) . . . . . . . . . . . . . . . . . . . . . . . . . . 579
D. Sander ()
Max Planck Institute of Microstructure Physics, Halle, Germany
e-mail: [email protected]
Abstract
Introduction
λ >0
M = Ms
H
λ <0
T < TC
ω>0
T > TC Mavg = 0
H=0
temperature dependence α(T ) shows distinct variations near the magnetic ordering
temperature [4, 23]. This is also true for antiferromagnets and other types of
magnetic order.
The spontaneous volume magnetostriction of a metal can be slightly altered
by applying a large external magnetic field, and this gives rise to forced volume
magnetostriction [24].
The spontaneous volume magnetostriction, if positive, can produce a lattice
expansion to compensate or cancel the usual contraction of lattice spacing with
deceasing temperature, leading to vanishingly small or even negative thermal
expansion – lattice expansion upon cooling. The former effect is found in invar
alloys such as Fe64 Ni36 [25] and the latter in Mn3 (Cu(1−x) Gex )N [26] alloys. Invar
generally refers to a material with a vanishingly small thermal expansion near room
temperature due to its large positive spontaneous volume magnetostriction [27, 28].
Elinvar refers to a material with a vanishingly small temperature variation of its
elastic properties with temperature. For further discussion of magnetovolume and
invar effects, see [23, 25, 29, 28, 30].
Villari Effect
The Villari effect describes a change of magnetic susceptibility due to straining the
sample [31] by an external stress. It is easier to magnetize a material with positive
magnetostriction in the direction of a tensile stress. The stress-induced lattice strain
induces a change of the magnetic configuration such that those domains grow in
size which have their local magnetization oriented parallel with the lattice strain.
This change of domain configuration affects the susceptibility and the magnetization
curve below saturation. The impact of stress on the magnetic anisotropy of a sample
is discussed in section “Magnetostriction and Stress-Induced Magnetic Anisotropy”.
The stress-induced change of domain configuration is schematically illustrated in
Fig. 8.
E Effect
positive magnetostrictive strain λ⊥ still appears along the stress direction, and the
material appears again softer. Thus, irrespective of the sign of magnetostriction, a
magnetic material with domains that are non-collinear with the applied stress in zero
field always appears elastically softer during a magnetization process as compared
to a sample which is magnetically saturated. This variation of elasticity is termed
E effect.
Figure 2 presents an example of the E effect for Ni [32]. The Young modulus
E is affected by the magnetization state of Ni below the Curie temperature of TC =
360 ◦ C. The demagnetized sample shows a considerably reduced Young modulus of
178 GPa below TC , as compared to the magnetically saturated sample with 211 GPa.
Here, a relative reduction of the Young modulus of (Esat − Emagn=0 /Emagn=0 =
0.185) is observed.
The magnitude of the E effect depends on numerous factors. The crystal-
lographic orientation of the sample, its magnetic domain structure, magnitude
and orientation of the applied strain (stress), and the direction and magnitude
of an applied magnetic field need to be considered for a quantitative description
of the effect [32, 4, 10]. The resulting complexity is alleviated by considering
approximations such as a magnetic domain orientation orthogonal to the stress
direction, isotropic elastic and magnetic properties, and minute strains in the
realm of acoustic vibrations. Under these assumptions, the reduction of the Young
modulus due to magnetostrictive contributions to strain is approximated by [10]
Eel − Eλ 9λ2S H 2
= Eel . (1)
Eλ μMS HS3
demagnetized sample
(M = 0, lower curve (red))
[32]. The Young modulus of 200
the demagnetized sample is
smaller than that of the fully
190
magnetized sample below the
Curie temperature TC of Ni of
360 ◦ C 180 M=0
100 200 300 400
temperature (oC)
11 Magnetostriction and Magnetoelasticity 555
(Eel-Eλ)/Eλ
applied field is oriented along
the length of the reed. The
strain induced by the flexural
0.4
vibration leads to a stronger
reduction of elasticity for
transversal domain
orientation 0.2
longitudinal
0
0 1 2
applied field (mT)
Magnetomechanical Damping
There is a loss of energy associated with any elastic vibration of a sample. Exper-
iments show that this loss is larger for ferromagnetic than for non-ferromagnetic
samples [4, 6]. The reason is that vibrations lead to flexural strains which interact
with the magnetic configuration via magnetoelastic coupling. This link to mag-
netization opens a further loss channel, and a stronger damping results. This is
advantageous for applications where a strong intrinsic damping is required to avoid
catastrophic vibrational amplitudes near resonance, such as in turbines, but it is
556 D. Sander
Wiedemann Effect
The Wiedemann effect [37] is the torsional twist observed in a sample upon
the application of an helical magnetic field. The helical field results from the
superposition of an axial magnetic field produced by a surrounding coil and a
circular field produced by a current passing through a wire-shaped or thin-walled
tube sample. The situation is schematically illustrated in Fig. 5, and the resulting
sample torsion γ is indicated. The effect is the basis of a most sensitive measurement
of magnetostriction, as the method can be applied in resonance with a torsional
Iwire
γ
Icoil
Fig. 5 Schematic of the Wiedemann effect. A coil surrounding the sample gives an axial magnetic
field along the sample axis. The current through the wire (sample) produces a radial field, which in
conjunction with the axial field results in an helical magnetization of the sample. Magnetostriction
in the sample causes a sample twist, which induces a torsion γ , as depicted in the schematic of the
cross section
Matteucci Effect
The converse to the Wiedemann effect is the Matteucci effect, the appearance of a
helical magnetization component at the end of a twisted sample upon changing the
axial sample magnetization [39]. The effect has been exploited in micro-fluxgate
sensors, where a helical magnetization is imposed on an amorphous Fe77.5 Ni7.5 B15
wire of 0.125 mm diameter. A field sensitivity of order 100 nT has been reported
[40].
cubic
T > Tm
cooling heating
T < Tm T > Tm
H
εH
H=0 applying
a field H
Fig. 6 Illustration of the ferromagnetic shape-memory effect. The parent material is cubic above
the martensitic temperature Tm . A martensitic phase transition occurs upon cooling below Tm . A
lattice strain of order 1% is observed, which is accompanied by the creation of a twin structure
with two variants. The application of a magnetic field H drives the growth of one variant, and a
field-induced strain H is observed. Heating above Tm restores the material to its cubic phase. The
white arrows indicate the magnetization direction within the variants
11 Magnetostriction and Magnetoelasticity 559
The effect is observed in the Heusler alloy Ni2 MnGa. This material has a
martensitic transition between a high-temperature cubic phase and low-temperature
tetragonal phase. The transition temperature is near Tmart = 276 K. The dominant
mechanism of this first-order phase transition is the occurrence of shear strains in
the low-temperature phase. The tetragonal phase is characterized by a huge lattice
strain along the c-axis of order −7%, whereas the lateral strain along a and b is only
of order +1.3% with respect to the parent cubic phase.
It is possible to move the phase transition temperature Tmart to higher values by
modifying the electron-per-atom ratio by alloying [11]. Strains of up to 10% are
achieved for the transition into a orthorhombic phase [44].
It has been found that the temperature dependence of the Ni 3d states plays a
crucial role in the electronic origin of the ferromagnetic shape-memory effect [45].
This supports the view that the martensitic instability can be described as a Jahn-
Teller effect [45].
The ferromagnetic shape-memory effect differs from Joule magnetostriction due
to its different physical origin; no strain dependence of the magnetic anisotropy
is necessary. Also, the effect shows a threshold field, below which no strain is
observed. In addition, the magnetic field-induced strain shows a large hysteresis,
whereas magnetostriction in hard axis magnetization is an anhysteretic process. The
field-induced strain in FSMAs is usually observed only in a narrow temperature
range below Tmart and above a lower cutoff temperature [11].
Magnetostriction in Superconductors
The application of a magnetic field along the c-axis of the high Tc superconductor
Bi2 Sr2 CaCu2 O8 in its superconducting state at 5 K leads to a transverse magne-
tostriction in the a, b plane of −2 × 10−4 at 6 T [48]. The negative sample strain
in the plane perpendicular to the field direction is ascribed to a compressive stress,
exerted by pinned Abrikosov vortices which are pushed together by an increasing
field.
After this overview of effects due to magnetoelastic coupling and magnetic field-
induced strain, we now focus on Joule magnetostriction. Relations useful for the
description and measurement of magnetostriction and magnetoelastic coupling in
cubic and hexagonal bulk samples and films are derived in the following sections.
560 D. Sander
We start from the expressions for the elastic fel and the magnetoelastic energy
density fme for a sample with a cubic lattice. These expressions can be found in
many textbooks [7, 8, 10, 12] and reviews [2, 17]. We use the tensor notation for the
lattice strain ij [49]. Confusion is possible because there are different conventions
for representing strain. The contracted Voigt notation and engineering strains are
alternative descriptions, but they give different expressions for the off-diagonal
strain. The different conventions are discussed in the Appendix.
The magnetoelastic strain tensor me gives the three-dimensional strain state of a
sample upon saturation magnetization along the direction (α1 , α2 , α3 ), where the
αi are the direction cosines of the magnetization with respect to the cubic axes.
The magnetization-induced strain always refers to a reference state of zero net
magnetization, as given by a demagnetized sample. This demagnetized reference
state is formally implemented by assuming a random orientation of the magnetiza-
tion. By convention, this reference state is characterized by zero magnetostrictive
strain. This convention gives rise to terms of −1/3 in the expression of the αi2 ,
reflecting the average of cos2 (ϑ) over the unit sphere (see Eq. (17)). Note that such
a demagnetized reference state may be hard to realize experimentally. Irrespective
of this, the resulting expressions can be used also for calculating the change of strain
between two well-defined magnetization directions as outlined below. The role of
the reference state for magnetostriction measurements is illustrated in Fig. 7. The
elastic energy density
1
fel = 2
c11 (11 +22
2
+33
2
)+c12 (11 22 +11 33 +22 33 )+2c44 (23
2
+13
2
+12
2
)...
2
(2)
and the magneto elastic energy density
1 1 1
fme = B1 (11 (α12 − ) + 22 (α22 − ) + 33 (α32 − )
3 3 3
+2B2 (23 α2 α3 + 13 α1 α3 + 12 α1 α3 ) . . . (3)
are given in second and first order in strain , respectively [17]. The coefficients
of the rank two strain tensor are ij . The elastic stiffness constants are given by cij
(units N/m2 ), and the magnetoelastic coupling coefficients are given by Bi (units
J/m3 ). Note that this equation is given in a short-hand notation for the cij which
disguises that the elastic stiffness is described by a rank four tensor. Appropriate
tensor transformations need to be applied for the study of directional dependencies
[17]. The dots indicate that higher-order terms are omitted, but may be important
11 Magnetostriction and Magnetoelasticity 561
(a) εII ε
εII
εT
3λ
Mavg=0 M=MS 2 S
0
H=0 H=HS ε T
0 HS H II εII
(b) εII 1 Δε 2
ε
T
Mavg=0 M=MS
H=0 H=HS
Fig. 7 (a) Starting from a demagnetized state with a random magnetization configuration, satura-
tion along the field direction gives the lattice strain along that direction and ⊥ perpendicular to
it. (b) Note that a demagnetized state with a collinear domain orientation along the field direction
does not show any magnetostrictive strain change upon saturation. To avoid the impact of the
often undefined reference state at zero field, a strain measurement during the reorientation of
the magnetization direction between two saturated states 1 (vertical) and 2 (horizontal) gives the
change of strain as = 32 λS
[17, 50]. This will be discussed below for fme , where the Bi are found to be strain
dependent.
We also note that an alternative description exists within the symmetry-invariant
notation [10]. Here, the free energy expression is expanded in a set of orthogonal
harmonic functions. For a thorough discussion, see [51, 52, 8].
The components of the magnetoelastic strain tensor are obtained by calculating
the strain derivatives of the total energy density ∂f/∂ij with f = fel + fme ,
setting the expressions to zero, and solving the resulting six equations for ij . Some
simplification is possible by exploiting α12 + α22 + α32 = 1, and the following
magnetoelastic strain tensor results:
⎛ ⎞
B1 α12 − 13
⎜ − c11 −c12 − B22cα44
1 α2
− B22cα44
1 α3
⎟
⎜ ⎟
⎜ B1 α22 − 13 ⎟
me = ⎜ − B2 α1 α2 − B2 α2 α3 ⎟ .
− 2c44 ⎟ (4)
⎜ 2c44 c11 −c12
⎝ B1 α32 − 13
⎠
B2 α1 α3
− 2c44 − B22cα44
2 α3
− c11 −c12
562 D. Sander
3 3
= βi βj meij (5)
i=1 j =1
B1 1 1 1
=− α12 − β12 + α22 − β22 + α32 − β32
c11 − c12 3 3 3
B2
− (α1 α2 β1 β2 + α1 α3 β1 β3 + α2 α3 β2 β3 ) . (6)
c44
This equation gives zero strain for a state with random magnetization direction.
We calculate the magnetostrictive strains δ for different magnetization and strain
measurement directions. This defines recipes for extracting the tabulated magne-
tostrictive coefficients λ100 and λ111 . We refrain from calling the λ constants, as
their value may be changed due to lattice strain, or in the monolayer thickness range
[53,54,55,56,17,57,58,50]. The first remark refers to a potential strain dependence
of the magnetoelastic coupling coefficients Bi and the second to the contributions
of interface effects to Bi in atomically thin samples.
Magnetization Along [100]; Strain Measurement Along [100]
This defines a procedure to measure λ100 , starting from the demagnetized state with
random domain orientation. With α = (1, 0, 0) and β = (1, 0, 0), we obtain
δ 2B1
= λ100 = − . (7)
3(c11 − c12 )
δ B2
= λ111 = − . (8)
3c44
δ
We can now express the magnetostrictive strain in terms of the magnetostriction
coefficients λ.
3
= βi βj λij (10)
i=1 j =1
1
3
= λ100 α12 β12 + α22 β22 + α32 β32 −
2 3
+3λ111 (α1 β1 α2 β2 + α1 β1 α3 β3 + α2 β2 α3 β3 ) (11)
We apply this expression first to derive the difference between longitudinal and
transversal magnetostrictive strain, namely, strain along the magnetization direction
100 − 100
and perpendicular to it. To this end, we calculate the difference of strain 100 010
for a fixed magnetization direction along [100] and strain measurements along [100]
and along the perpendicular direction [010].
Magnetization Along [100]; Strain Measurement Along [100] and [010]
We introduce superscripts and subscripts to identify the magnetization direction and
the strain measurement direction, respectively.
1 3
100
100 = λ100 ; 010
100
= − λ100 ; 100
100
− 010
100
= λ100 (12)
2 2
It follows that λ100 can be derived from two strain measurements along and
perpendicular to the saturation magnetization direction, irrespective of a reference
state with unknown magnetization distribution. We also see that the transversal
magnetostrictive strain is opposite in sign and half in magnitude of the longitudinal
magnetostrictive strain. The same result is obtained for the strain along [001]. Thus,
the sample volume, given by the trace of the strain tensor, remains constant.
The values for λ111 are accessible from measurement along other directions.
Magnetization Along [110]; Strain Measurement Along [110] and [1–10]
1 3 1 3 3
110
110 = λ100 + λ111 ; 1−10
110
= λ100 − λ111 ; 110
110
− 1−10
110
= λ111 (13)
4 4 4 4 2
564 D. Sander
The angle ϑ is measured between the magnetization direction and the strain
measurement direction. The reference to the crystal axes is lost.
Determination of the Isotropic Magnetostriction
A strain measurement along the direction of magnetization, λ , and perpendicular
to it, λ⊥ , gives
3
λ − λ⊥ = λs , (15)
2
The directional dependence is given by terms cos2 (ϑ), cos4 (ϑ), and cos2 (ϑ)
sin2 (ϑ). A random orientation of crystallites, which is the basis of the isotropic
sample described here, is considered by averaging the directional dependence over
the unit sphere. We calculate the respective averages
2π
π 1
cos (ϑ)avg =
2
cos2 (ϑ) sin(ϑ)dϑdϕ/(4π ) =
0 0 3
2π
π 1
cos4 (ϑ)avg = cos4 (ϑ) sin(ϑ)dϑdϕ/(4π ) =
0 0 5
2π
π 2
cos2 (ϑ) sin2 (ϑ)avg = cos2 (ϑ) sin3 (ϑ)dϑdϕ/(4π ) = (17)
0 0 15
11 Magnetostriction and Magnetoelasticity 565
2 3
λs = λ100 + λ111 . (18)
5 5
This expression was first presented by Akulov [59] and was later criticized
for neglecting elastic anisotropy [60], which leads to a correction, which can be
negligible or sizable, depending on the material [60].
We follow the same procedure as for the cubic case above. We start from the
following expressions for the elastic and the magnetoelastic energy density [17].
We choose a coordinate system where the z-axis coincides with the c-axis and the
x-axis with one of the unit vectors of the basal plane. The reference state is ascribed
to magnetization parallel to the c-axis ( α3 = 1, α1 = α2 = 0).
1 1
fel = 2
c11 (11 + 22
2
) + c33 33
2
+ c12 11 22 + c13 (11 33 + 22 33 )
2 2
+ 2c44 (23
2
+ 13
2
+ (c11 − c12 )12
2
+ ... (19)
fme = B1 (11 α12 + 212 α1 α2 + 22 α22 ) + B2 (1 − α32 )33
+ B3 (1 − α32 )(11 + 22 ) + 2B4 (23 α2 α3 + 13 α1 α3 ) + . . . (20)
We calculate the strain derivative of the total energy density, set it to zero, and
solve for the ij . We then calculate the magnetostrictive strain for four different
magnetization states [61, 62] and obtain the following definitions for the Bi :
3 3
= hex
βi βj λij (23)
i=1 j =1
Here, ϑ is the angle between the magnetization direction and the c-axis. With
the calculated averages of the trigonometric functions from Eq. (17) and with
(sin4 (ϑ))avg = 15
8
, we get
2 8
λ = λA + λD . (27)
5 15
1
λ⊥ = (2λA + 5λB + 5λC − 4λD ). (30)
15
Inspection of Eqs. (3) and (20) reveals that magnetoelasticity is intimately linked to
magnetic anisotropy insofar as it involves terms which depend on the direction of
magnetization. Consequently, the application of stress τ induces a lattice strain ,
and this strain contributes via the magnetoelastic coupling coefficients Bi to the
energy density. It is important to note that it is the stress-induced strain which
drives the corresponding change of magnetic anisotropy. This impact of an imposed
lattice strain on magnetic anisotropy is often referred to as inverse magnetostrictive
effect. Theory exploits the link between lattice strain and magnetoelastic effects
by identifying magnetoelasticity as the derivative of magnetic anisotropy with
respect to strain [63, 64]. This aspect is elucidated in section “Magnetostriction and
Magnetoelasticity: Physical Origin and Insights from Theory”. Here, we briefly note
that for 3d metals the corresponding physics is due to the spin-orbit interaction. Its
dependence on lattice strain is a daunting topic. This is also due to the small energy
scales, which typically are in the μeV per atom range. Reliable calculations with
the required numerical accuracy remain challenging.
Thus, phenomenological pictures are still used to describe stress-induced mag-
netic anisotropy. Here, we focus on illustrative examples to provide a basic
description of the matter for a cubic system. We calculate the stress-induced lattice
strain and insert the obtained strain in the equation of the magnetoelastic energy
density fel of Eq. (3). Then, the orientational dependence of the expression is
analyzed.
The stress-strain relation is derived from the expression of the elastic energy
density of Eq. 2 by exploiting τij = ∂fme /∂ij . In the following, we neglect shear
stress by setting τij = 0 for i = j and focus on the cubic system. We obtain
and solve these equations for ii to derive the stress-induced lattice strain.
568 D. Sander
Isotropic Stress
An isotropic stress τ = τii gives rise to an isotropic strain of magnitude = ii =
τ/(c11 + 2c12 ). An isotropic contribution to fel of magnitude B1 τ/(c11 + 2c12 )
results. Thus, the magnetic anisotropy, defined as energy difference between two
magnetization directions, remains unaffected.
Uniaxial Stress
We assume an uniaxial stress τ11 = τ, τ22 = τ33 = 0. A three-dimensional strain
state results, where the lattice strain differs along the direction of applied stress from
its value in the plane perpendicular to the stress direction. We obtain
c11 + c12
11 = τ
(c11 − c12 )(c11 + 2c12 )
c12
22 = 33 = −τ . (32)
(c11 − c12 )(c11 + 2c12 )
The ratio −22 /11 = −33 /11 defines the Poisson ratio ν = c12 /(c11 + c12 ).
Insertion into Eq. 3 and omitting isotropic terms give the stress contribution to
magnetic anisotropy as
B1
τ
fme =τ α2
c11 − c12 1
3
= − τ λ100 cos2 (ϑ), (33)
2
where ϑ gives the angle between the direction of stress and magnetization. Thus, an
uniaxial magnetic anisotropy results.
How large are stress-induced magnetic anisotropies? Can they potentially change
the easy magnetization direction as given by the magnetocrystalline anisotropy?
Stress-induced magnetic anisotropies scale as Bi . Typical values for B are of order
several MJ/m3 . The strain in bulk samples is certainly always below 0.01, and thus
the stress contribution in a bulk sample can reach 0.1 MJ/m3 . This is a sizable
contribution to magnetic anisotropy in comparison to K1 = 0.05 MJ/m3 of bulk
Fe [17, 65, 58]. For systems with smaller magnetocrystalline anisotropy, such as
Ni or amorphous metals, stress-induced magnetic anisotropy is often the dominant
source. In epitaxial ultrathin films, much larger strains of up to several percent may
prevail, and stress-induced anisotropy should always be considered [17, 65].
In view of the impact of magnetoelasticity on anisotropy, it is important to realize
that terms B, Bτ, τ λ contribute. Thus, the application of a tensile stress τ > 0 to
a sample with positive magnetostriction (λ > 0, B < 0) has the same impact on
anisotropy as the application of a compressive stress (τ < 0) to a sample with
negative magnetostriction. If λ is positive, then it is easier to magnetize the material
in the direction of a tensile stress. This link between stress and magnetic anisotropy
plays a role for the domain distribution in stressed materials and for the approach to
11 Magnetostriction and Magnetoelasticity 569
(a) λ>0
τII τII
MII
τII, λ>0
MS
V(MII)>V(M ) τII, λ<0
τ=0
T
(b) λ<0
Mavg=0
τII τII
τ=0 0
V(M )>V(MII)
T
0 H II τ
Fig. 8 The impact of stress on the magnetization curve of a magnetostrictive material. (a) Tensile
stress favors a longitudinal domain configuration in a material with positive magnetostriction. (b)
A transversal domain configuration is favored for negative magnetostriction. Magnetization along
the tensile stress direction gives a reduced effective anisotropy in (a) (red curve) and a larger
anisotropy in (b) (blue curve)
(a) (b)
Fig. 9 (a) Magnetostriction in bulk samples is accessible from the magnetization-induced change
of the lattice strain λ , λ⊥ . (b) Magnetization of a film induces a biaxial magnetoelastic stress,
which is related to the magnetoelastic coupling coefficients Bi . A thin substrate undergoes a
anticlastic curvature with radii of curvature of opposite sign along and perpendicular to the
magnetization direction. Curvature measurements give Bi ; see Eq. (36)
11 Magnetostriction and Magnetoelasticity 571
sample shape. Thus, for magnetostatic reasons alone, a magnetized sample tends
to elongate along the magnetization direction, thereby lowering its demagnetizing
energy. This leads to the superposition of the form effect-driven lattice strain with
the magnetostrictive lattice strain. When λ is small, both can be of comparable
magnitude, and corresponding corrections are required [91].
The Wiedemann Effect: Magnetization-Induced Sample Twist
Alternatively, the Wiedemann effect can be applied to deduce magnetostriction from
a magnetization-induced sample twist (Fig. 5). The helical twist is straightforwardly
measured with high sensitivity by reflecting a laser beam from the sample onto a
position-sensitive detector. This method is extremely useful for samples in the form
of thin ribbons and wires [92,38], where strain measurements are otherwise difficult
to implement. Quantitative analysis reveals [92] a non-monotonic dependence of the
torsion per unit sample length ξ on the magnetic field produced by coil and current.
The maximum torsion per length is related to the isotropic magnetostriction constant
λs via
2.2λs
ξmax = , (35)
a
The indirect methods described above may also be used to study magnetoelastic
effects in thin films. However, they lack the direct link between the experimental
572 D. Sander
Fig. 10 (a) Sketch of an ultrahigh vacuum chamber for in situ film growth with magnets for
magnetoelasticity studies. (b) Optical curvature measurement. The optics is mounted outside of the
vacuum chamber, and the sample is in the vacuum chamber. 1: sample manipulator, 2: substrate
with film (3) on front surface, 4: laser diode with optics, 5: beam splitter, 6: mirrors, 7: piezo
transducer, 8: split photodiode. (c) Schematic curvature change upon an in-plane magnetization
reorientation of a film-substrate composite with positive Beff
11 Magnetostriction and Magnetoelasticity 573
flange of the vacuum chamber for in situ stress measurements during film growth
and during magnetization processes. The experiment involves a measurement of the
change of substrate curvature upon an in-plane reorientation of the magnetization
direction [17, 65, 99]. The curvature along the sample length is measured for mag-
netization along its length and magnetization along its width. The magnetoelastic
stress produces an anticlastic curvature of the sample.
Let us assume a cubic (100)-film with negative B1 (λ100 > 0). The sample
length is along [100]. Magnetization along [100] induces a compressive stress along
[100], as the film has the tendency to expand along its magnetization direction.
This induces a negative curvature along the sample length. A tensile stress results
along the perpendicular in-plane direction. Magnetization along the film width [010]
rotates the compressive stress to the film width, and a tensile stress along the
film length results. An anticlastic curvature results in both magnetization states.
The sample changes its curvature from curved downward to curved upward upon
magnetization reorientation. This situation is schematically shown in Fig. 10c.
This curvature change is directly linked to the effective magnetoelastic coupling
coefficient Beff [17]
Es ts2 1 length 1 width
Beff = − . (36)
6(1 + νs )tf Rx Rx
Note that the elastic properties of the substrate enter via the Young modulus
Es and the Poisson ratio νs . Substrate and film thickness are given by ts and tf ,
respectively. The superscripts give the magnetization direction.
Different magnetoelastic coupling coefficients Bi can be measured depending on
the crystallographic orientation of the film. Table 1 gives an overview of the required
experiments to measure Bi [99].
The quantitative analysis of magnetoelastic curvature measurements needs to
take crystalline anisotropy and substrate clamping into account [100, 99]. The
use of substrates with a length-to-width ration larger than three minimizes the
Table 1 Effective magnetoelastic coupling coefficient Beff for films with the given symmetry and
orientation for an in-plane reorientation of the magnetization. The Bi are defined in Eq. (20). x1
and x2 denote the direction along film length and film width, respectively
Film structure Beff
Cubic, film axes along x1 , x2 B1
Cubic, film axes rotated by 45◦ with respect to x1 B2
Hexagonal, c-axis in-plane,
2 domains parallel to x1 , x2 1
2 (B1 − B2 + B3 )
Hexagonal, c-axis in-plane,
2 domains rotated by 45◦ with respect to x1 B4
Hexagonal, c-axis in-plane,
3 domains rotated by 120◦ with respect to x1 1
4 (B1 − B2 + B3 ) + 12 B4
574 D. Sander
energy (μeV/atom)
Note the small energy scale
of order 100 neV or 1 mK per -0.15
atom
-0.25 tetragonal
λ100
-200 -100
distortion (10-6)
Ab initio calculations offer some insights into the physical origin at the electronic
level of the strain dependence of the magnetocrystalline anisotropy [115]. Figure 12
shows the calculated change of the density of states upon uniaxial compression
of bulk Fe. This tetragonal strain shifts and broadens electronic bands. As a
consequence, the spin-orbit coupling between bands of different symmetry near
the Fermi energy is changed, and this drives a strain-induced change of magnetic
anisotropy [115].
Recent measurements of magnetoelastic coupling in atomic layers have revealed
that film strain may modify the magnetoelastic coupling coefficients in a way that
can be described by higher-order strain contributions to the magnetoelastic energy
density [50]. Calculations [71, 70, 76, 74, 75, 77] support the phenomenological
introduction of strain-modified magnetoelasticity, as discussed in section “Magne-
toelastic Effects in Films”.
576 D. Sander
Compilation of Data
Table 2 Room temperature values of λ and B [17]. Note that Eq. (3.4) in [17] should read B4 =
c44 (λA + λC − 4λD ). The Bi are calculated from the λi . The required elasticity data are in Table 3.
The values for fcc Co are extrapolated from data for PdCo alloys [17]
Element B1 B2 λ100 λ111 B3 B4 λA λB λC λD
zbcc Fe −3.43 7.83 24.1 −22.7
fcc Co −9.2 7.7 75 −20
fcc Ni 9.38 10 −64.5 −28.3
hcp Co −8.1 −29 28.2 37.4 −50 −107 126 −105
578 D. Sander
Table 3 Elastic stiffness constants cij , Young modulus E in GPa. The latter is calculated for the
(0001) and (100) orientation for hcp and cubic elements, respectively. The Poisson ratio is given
by ν. (Data from [17])
Element c11 c12 c44 c13 c33 E ν
hcp Co 307 165 75.5 103 358 211 0.49
fcc Co 242 160 128 114 0.40
bcc Fe 229 134 115 131 0.37
fcc Ni 249 152 118 133 0.38
Table 4 (continued)
B1 D1 B2 2D2 B3 B4 D4
GGA [133] −4.1 – – –
GGA [73, 74] −2.4 383 −3.9 18
GGA [113] −4.8 – – –
Exp. film Fe/MgO(100) and −3.4 1100 7.8 −365
Fe/Cr/MgO(100) [57]
Fe/Ir(100) [58] −3.6 155 – –
Fe/W(100) [17] −1.2 200 – –
hcp Co
Exp. bulk [17] −8.1 – −29 – 28.2 37.4
Exp. film Co/W(001) [135] 3.4 1346
Magnetostrictive and elastic data of these binary and ternary alloys [136] have
been measured and compiled for different alloy compositions with high resolution
on the composition scale [91]. Table 6 presents specific examples of those alloy
compositions where magnetostriction is much larger or smaller than that of pure Fe.
Note that a tenfold increase of magnetostriction of Fe71.2 Ga28.8 as compared
to Fe is observed, although the magnetoelastic coupling coefficient is only twice
as large as that of Fe. This indicates a contribution of elastic softening to the
remarkably large magnetostrictive strain in this alloy. Equation 7 shows that a
small value of (c11 − c12 ) leads to a large magnetostriction λ100 for a given
magnetoelastic coupling B1 . Ultrasound spectroscopy revealed a decrease of the
tetragonal shear modulus 0.5(c11 − c12 ) from the Fe bulk value of 48 to 6.8 GPa
for a Ga content of 27.2% at room temperature [137]. In addition to lattice
softening, density functional theory has revealed the atomic arrangement of Ga in
Fe-Ga alloys as a further important aspect. The Ga-induced change of electronic
structure is of key importance for the understanding of large magnetostriction
in these alloys [138, 139]. A structural origin of large magnetostriction, due
to nanoscale precipitates of different crystallographic order, has been proposed
[140, 141, 142, 143], but this could not be supported by theory [139].
580 D. Sander
The decrease of λ100 with increasing Ge content, leading to negative λ100 above
14% Ge content [91], has been tackled by theory [120], which finds that at small
Ge content a Ge-induced softening of the tetragonal shear modulus contributes to a
large magnetostriction. The calculated softening of the tetragonal shear modulus is
in qualitative agreement with experimental results [91]. At higher Ge content, the
availability of eg holes above the Fermi energy induces a negative magnetostriction
[120]. It has been predicted that the addition of Cu (Fe79.7 Ga18.7 Cu1.6 ) should lead
to an enhanced magnetostriction of λ100 = 550 × 10−6 [116], but this is not
observed. However, doping melt-spun Fe83 Ga17 with 0.23 atomic % Tb has been
reported to lead to a four times increased magnetostriction as compared to the
binary alloy [144]. This increase has been ascribed to a localized increased spin-
orbit interaction in proximity to Tb [144] (Fig. 13).
alloy with roughly 80% Ni and small additions of other metals such as Cu, Cr,
Mo, balance Fe); sendust (Fe alloy with 10 weight % Si and 5% Al); Fe-Si
alloys, MnZn and NiZn ferrites, and amorphous (FeCo)B alloys; and nanocrystalline
Fe-based alloys, which find widespread applications in magnetic sensors, trans-
formers, electrical motors, and magnetic shielding [145, 146, 10]. Achieving
these material properties is innately linked with the demand for vanishingly
small magnetic anisotropy. An important contribution to magnetic anisotropy is
magnetoelastic coupling, and consequently small magnetostriction is required.
This reduces the strain-induced magnetic anisotropy, which arises inevitably in
manufacturing and shaping (bending) the material for use in applications. Thermal
annealing after manufacturing, often in an H2 atmosphere, may relax strain and is
often performed to obtain ultra-soft magnets.
Amorphous and nanocrystalline materials can be of high interest in correspond-
ing applications, as their effective magnetocrystalline anisotropy may average out
to zero, provided that the crystallographic grain size is smaller than the magnetic
domain size. One example is the alloy Fe73.5 Cu1 Nb3 Si13.5 B9 with a suppressed
magnetocrystalline anisotropy and zero magnetostriction [147].
In the quest for low magnetic anisotropy, one can exploit that different elements
contribute to magnetic anisotropy with opposing signs, leading to zero net magnetic
anisotropy. This venue is followed for permalloy, where the composition Ni78 Fe22
shows almost zero magnetocrystalline anisotropy and almost zero magnetostriction.
Bringing both properties to zero at exactly the same composition can be achieved
by adding further elements such as Mo and Cu. This is the material of choice when
highest initial permeability of up to 106 μ0 is required [10].
A critical aspect for application is that permalloy films show a magnetostrictive
behavior which depends on film thickness [56]. Figure 14 reveals that zero
magnetostriction is only observed for films thicker than 7 nm, whereas thinner films
nonzero magnetostriction.
-1.0
(Adapted from [56])
-1.5
-2.0
-2.5
-3.0
0 5 10 15 20 25 30 35
thickness (nm)
582 D. Sander
exhibit magnetostriction of −2.5 × 10−6 at 3 nm. This suggests that other effects,
such as sample roughness, film strain, and electronic hybridization between film and
substrate, may lead to a qualitatively different magnetoelastic behavior in atomically
thin films as compared to bulk [17, 65, 50].
Magnetostriction of the rare earth metals Tb, Dy, and Ho is large at cryogenic
temperature with strains of order 10−3 [152, 153]. These elements show different
magnetic order with increasing temperature, but none at room temperature.
(a) x10-3 Tb
3.2 78.7 K, λb
2.4
1.6 224.3 K, λc
0.8
224.5 K, λb
λ
0
79.7 K, λc
-0.8
c 225.4 K, λa
-1.6 a
-2.4 Hb
79.6 K, λa
c 20 K, λc 0 45 K, λb
λ
-1 a c
H a 77 K, λb
-2 b -1 77 K, λa
144 K, λb Hb 4.2 K, λa
-3 -2 45 K, λa
85 K, λb
-4 20 K, λb 0 0.5 1 1.5 2 2.5
0 0.5 1 1.5 2 2.5 H(T)
H(T)
Fig. 15 Magnetostrictive strain for (a) Tb, (b) Dy, and (c) Ho measured along different directions
with the field along the a and b direction for Dy and Tb and Ho, respectively. (Adapted from
[152, 153])
584 D. Sander
The Laves phase alloys TbFe2 (Terfenol) and DyFe2 show a large magnetostriction
also at room temperature; see Fig. 16. Large magnetic fields are required to reach
saturation magnetostriction close to 1.3 × 10−3 of the isotropic polycrystal. The
necessity of high fields for saturation has been ascribed to the pronounced magnetic
anisotropy of the material. SmFe2 shows a comparable magnitude of magnetostric-
tion, although with opposite sign [21]. Curiously, the different magnetostrictive
coefficients differ vastly, λ111 λ100 , and crystals with predominant (111)
orientation give the largest strain [21].
Tb and Dy lead to fourth-order cubic magnetic anisotropy of opposite sign in
the respective rare earth-Fe2 compound. Thus, the alloy composition of Tb-Dy-
Fe can be tuned such as to minimize the magnetic anisotropy, still preserving a
large room temperature magnetostriction. The material has been named Terfenol-D
(Tb27 Dy73 Fe2 ). It reaches a saturation magnetostriction of order 2.2 × 10−3 at room
temperature in moderate fields of 0.3 T [21]. Alloying of Terfenol-D with other
elements has not lead to higher magnetostriction, but specific material properties
may be tuned by alloying [156].
x 10-3 x 10-3
1.0 295 K λll 3.5 TbFe2 (H= 8)
0.8
TbFe2
3.0
0.6
2.5 TbFe2 (2.5 T)
0.4 DyFe2
λll
0.2 2.0
3/2 λS
λ
0 1.5
-0.2 DyFe2
λ T
1.0
-0.4
TbFe2 0.5
-0.6 DyFe2 (2.5 T)
λ T
-0.8 0
0 1.0 2.0 3.0 0 50 100 150 200 250 300
H(T) T(K)
Exchange interactions in oxides are usually antiferromagnetic, but they can lead to
ferromagnetic order in structures such as spinel or garnet. Some values are listed
in Table 8. Values for cobalt-containing are large on account of the large spin-orbit
interaction for the Co2+ cation.
Appendix
There are different conventions for the definition of strain, and it is mandatory
essential to distinguish between tensor strain ij and engineering strain γij [49,17].
The two conventions differ by a factor of two for the off-diagonal elements such
that 2ij = γij for i = j . Note that the use of the tensor strain is required if it
is transformed according to the tensor transformation rules to account for rotated
coordinate systems [49]. Throughout this contribution, all strain expressions are
given by the tensor strain. For completeness, we note that also the contracted Voigt
notation is often used. Starting from the tensor strain, the replacement rule given
in Table 9 applies to combine two subscripts into one. Note that factors of two
are inserted for the components with subscripts 4, 5, and6 to get 4 = 223 , 5 =
213 , and6 = 212 .
586 D. Sander
Table 9 Subscript replacement rule for the contracted Voigt notation. Note that factors of two are
inserted for the components with subscripts 4, 5, and6 to get 4 = 223 , 5 = 213 , and6 = 212
Convention Subscripts
Tensor notation: 11 22 33 23, 32 31, 13 12, 21
Contracted Voigt notation: 1 2 3 4 5 6
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11 Magnetostriction and Magnetoelasticity 593
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Dirk Sander received his PhD from RWTH Aachen in 1992 and
worked at the IBM T.J. Watson Research Center at Yorktown
Heights, New York, before he joined the Max Planck Institute of
Microstructure Physics, Halle, in 1993. He received his Habilita-
tion from Halle University in 2000. His research interests include
surface and film stress, magnetoelasticity, and spin-dependent
phenomena and superconductivity on the nanoscale.
Magnetoelectrics and Multiferroics
12
Jia-Mian Hu and Long-Qing Chen
Contents
Magnetoelectrics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596
Multiferroics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
The Evolving Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
Electric Field Switching of Magnetization in Multiferroic BiFeO3 :
Status and Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
Composite Multiferroics and Magnetoelectrics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
Terminology and Exiting Reviews . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
Mechanisms and Application of Magnetoelectric Effects and
Experimental Data of Magnetoelectric Coefficients in Composite Magnetoelectrics . . . . . 609
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
Abstract
J.-M. Hu ()
Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison,
WI, USA
e-mail: [email protected]
L.-Q. Chen
Materials Research Institute, and Department of Materials Science and Engineering,
The Pennsylvania State University, University Park, PA, USA
e-mail: [email protected]
are discussed. Experimental data showing the basic magnetic and ferroelectric
properties of different types of single-phase multiferroics are collected. For
composite magnetoelectrics, a relatively comprehensive experimental dataset of
both the direct and inverse magnetoelectric coefficients is compiled.
Magnetoelectrics
can become appreciable. The data measured on the same sample indicates αijH <3 × 10−11 when
H < 23 T
e Ni B O I can also display a nonlinear magnetoelectric effect: its spontaneous polarization
3 7 13
(0.076 μC cm−2 ) changes signs sharply at H ∼ ±0.6 T
Multiferroics
Multiferroics are a family of materials that “have two or more primary ferroic
properties in the same phase,” based on Schmid’s definition [24] (Fig. 2a). The
term ferroic was first introduced in 1970 by Aizu [35], who suggested that a
ferroic crystal should have two or more orientation states in the absence of a
magnetic field, electric field, or mechanical stress and can be switched from one
orientation state to another by a magnetic field, an electric field, a mechanical stress,
12 Magnetoelectrics and Multiferroics 599
Fig. 2 The evolving terminology of multiferroics. The original definition by Schmid [24] requires
the coexistence of two or all three primary ferroic order parameters, including spontaneous
magnetization Ms , spontaneous polarization Ps , and spontaneous strain εs , as shown in (a)
Eerenstein et al. [31] later suggested excluding the ferroelasticity. The present use of multiferroics
has been broadened to include antiferroic order (as stated in Refs. [32, 33]). (b) The Venn diagram,
drawn based on similar diagrams in Refs. [31, 34]. Some representative single-phase materials
are also listed. Magnetically (electrically) polarizable materials also include antiferromagnetic
(antiferroelectric) and other magnetically (electrically) ordered materials
is induced by magnetic order. Note that hexaferrites such as Ba0.5 Sr1.5 Zn2 Fe12 O22
[46] are not multiferroic, because they do not exhibit a spontaneous polarization
although a polarization on the order of 0.02 μC cm−2 can be induced and then
rotated by an applied magnetic field. Yet, these hexaferrites are magnetoelectric
because both magnetic field-controlled polarization [46–50] and electric field-
controlled magnetization [27, 51–54] have been experimentally demonstrated. More
information can be found in a topical review [55].
Ferroelectric Ferromagnets
Ferroelectric ferromagnets have remained rare in nature (notably in oxide per-
ovskites [56]), partly because ferromagnets are usually good electron conductors
while ferroelectrics are generally electron insulators. To our knowledge, in all
ferroelectric ferromagnets discovered so far, the ferroelectricity and magnetic order
arise independently (Type I multiferroics). For example, in the Ni3 B7 O13 I bulk
crystal, which was the first ferroelectric ferromagnet to be discovered [15], the
ferromagnetism arises from the transition metal Ni while the ferroelectricity arises
from the distorted I-O octahedron. In BiMnO3 (reported in both ceramics [57–
59] and thin films [58, 60]) and LaBiMnO3 thin films [61], ferroelectricity arises
from the 6 s lone pair of the Bi3+ , while the ferromagnetism arises from the Mn
cations. A special example is EuTiO3 : it is a paraelectric antiferromagnet in the form
of unstrained bulk crystal [62], yet can transform into the strongest ferroelectric
ferromagnet under a large (>1.2%) biaxial compressive strain in thin-film form [63,
64]. Table 2 summarizes the spontaneous/saturation polarization , magnetization,
and the onset temperatures for the ferroelectric order (TFE ) and ferromagnetic order
(TC ) of these ferroelectric ferromagnets.
Ferroelectric Antiferromagnets
Ferroelectric antiferromagnets are the most commonly reported single-phase mul-
tiferroics. These materials are grouped by their different origins of ferroelectricity
[32, 33], as follows:
• Solid solutions where the ferroelectric polarization arises from the 6 s lone pair of
the A-site atom (A = Bi, Pb) in the ABO3 structure that distorts the unit cell (viz.,
lone pair-driven ferroelectricity). Examples include Pb(Fe1/2 Nb1/2 )O3 that was
the first discovered material of this kind [68], and BiFeO3 (Sect. “Electric Field
Switching of Magnetization in Multiferroic BiFeO3 : Status and Perspective”),
the best known [69].
• Compounds where the ferroelectric polarization arises from the polar tilts and
rotations of the anionic sublattice (viz., geometrically driven ferroelectricity),
including hexagonal (h-) manganites RMnO3 (R = Sc, Y, In, or Dy-Lu, see, e.g.,
[70]), hexagonal LuFeO3 thin films [71], and some fluorides such as BaMF4
(M = Ni, Mn, Fe, Co, see, e.g., [72–74] and a review [75]).
• Compounds where the ferroelectricity polarization is induced by spin ordering
(viz., spin-driven ferroelectricity, see reviews [76–78]). Specifically, the polar-
ization can arise from:
(i) The noncollinear spin ordering through the inverse Dzyaloshinskii-Moriya
interaction (asymmetric exchange coupling) [79, 80]. Examples include
Cr2 BeO4 (the first material of this kind to be discovered) [81], orthorhombic
(o-) rare earth (RE) manganites REMnO3 with a cycloidal spin spiral
(Fig. 3a) (e.g., TbMnO3 [29]), and the CaMn7 O12 with a helical spin spiral
(Fig. 3b) [82, 83].
(ii) The collinear spin ordering through Heisenberg (symmetric) exchange
coupling [84, 85]. Examples include o-REMn2 O5 (e.g., TbMn2 O5 , the first
material of this kind to be discovered [30]), GdMn2 O5 [86], and SmMn2 O5
[87]), and the Ising chain magnet Ca3 Co2-x Mnx O6 [88]. Note that ferro-
electric polarization arising from such collinear spin ordering is generally
larger than that those from noncollinear spin ordering. For example, the
cycloidal spin spiral in o-TbMnO3 can be transformed into collinear spin
ordering by applying pressure, leading to an order of magnitude increase in
the spontaneous polarization [89].
(iii) The spin-dependent orbital hybridization between the 3d orbitals of mag-
netic transition metal (Co, Fe, Cr) and the 2p orbitals of ligand (O) via
spin-orbit coupling [90]. Examples include triangular-lattice antiferromag-
nets such as CuFeO2 [91] and CuCrO2 [92] and a staggered antiferromagnet
Ba2 CoGe2 O7 [93].
Ferroelectric Ferrimagnets
Ferroelectric ferrimagnets mainly include Fe3 O4 [103, 104], LuFe2 O4 [105], and
Pr1-x Cax MnO3 [106]. In these materials, ferroelectricity was thought to arise from
charge ordering ([107] is a brief review on this topic), which has been hotly debated.
For example, reports have suggested that the LuFe2 O4 , a prototypical example
of charge-ordering-driven ferroelectricity [105] with ferrimagnetic ordering, is
not ferroelectric [108–110]. However, in a (LuFeO3 )9 /(LuFe2 O4 )1 superlattice,
robust ferroelectricity has been demonstrated by out-of-plane piezoreponse force
microscopy at room temperature, while an evident magnetic hysteresis loop has
been directly recorded [111] at 250 K. Combining high-resolution transmission
electron microscopy imaging with first-principles calculations led to the suggestion
that the key ingredient for ferroelectricity is the severe rumpling imposed by the
neighboring LuFeO3 . It is such rumpling that drives the ferrimagnetic LuFe2 O4 into
a simultaneous ferroelectric state. Table 4 summarizes the spontaneous/saturation
polarization, magnetization, and the onset temperature for the ferroelectric order
(TFE ) and ferrimagnetism (TC ).
Table 3 (continued)
Type I
or II
multi- Origin of fer- Spontaneous
Material ferroics roelectricity polarization TFE TAFM Reference
TbMnO3 Type II Spin-driven 1 μC cm−2 20 K 20 K [89]
under (collinear spin @5 K @ (TE-AFM )f
high ordering) 5.2 GPa in bulk
pressure single crystals
(> 5 GPa)
CuCrO2 Type II Spin-driven 0.03 μC cm−2 24 K 24 K [92]
(p-d orbital @5 K @ 30
hybridization) MV/md in bulk
single crystals
a Estimated from structural analyses, not through direct measurement
b Will experience a second phase transition to weak ferromagnetism via spin canting below 100 K,
the TWFM
c Below T
CYCL , the sinusoidal AFM ordering (emerging when TCYCL < T < TN ) will transform into
a cycloidal spin spiral ordering. The latter induces ferroelectricity
d Thus it does not represent spontaneous polarization, unlike others
e It is still under debate whether CaMn O indeed exhibits such a surprisingly large spontaneous
7 12
polarization
f Under high pressure (>5 GPa), the sinusoidal AFM ordering will transform into a collinear E-type
AFM ordering, instead of transforming into the cycloidal spiral mentioned above (see temperature-
pressure phase diagram in Ref. [89])
(ZrO2 )0.905 (Y2 O3 )0.095 (or 9.5 mol% yttria-stabilized zirconia, YSZ) substrates
multiferroic material. Since a famous 2003 Science paper [96] that reports a large
spontaneous polarization and an arguably large [113] spontaneous magnetization
in BiFeO3 thin films, research efforts into BiFeO3 have remained the center stage
for multiferroics and magnetoelectrics. In fact, there exist no less than seven (2006–
2018) comprehensive review articles that specifically discuss BiFeO3 [69, 114–120]
including some very comprehensive ones [118–120]. Here we provide a briefing of
12 Magnetoelectrics and Multiferroics 605
some of the seminal research efforts on the electric field control of magnetization in
BiFeO3 .
Fig. 4 (a) Schematic of an antiferromagnetic spin cycloid. The canted antiferromagnetic spins
(blue and green, representing two sublattices) rotate within the plane defined by the polarization
P and the cycloidal propagation vector Q. They also induce a net magnetic moment Mc (orange)
which is also within that plane and averaged out to zero over one cycloid period of λ = 64 nm.
(b) Schematic of the magnetic easy plane (antiferromagnetic plane) containing the rotating
spins (double-headed arrows), the P, and the Q in BiFeO3 bulk crystals. (c) Schematic of G-
type antiferromagnetism (left) and the 3D view of the Mc induced by canted antiferromagnetic
spins via Dzyaloshinskii-Moriya interaction. (d) Relationship between the P, the Mc , and the
antiferromagnetic vector L (parallel to the magnetic easy plane) in BiFeO3 epitaxial thin films in
which the spin cycloid is destroyed by epitaxial strains or/and reduced thickness. (a, b), Redrawn
based on Ref. [123]. (c) Redrawn based on Ref. [124]
606 J.-M. Hu and L.-Q. Chen
magnetic easy plane also rotates (Fig. 4b), as demonstrated experimentally by two
different research groups [128, 129]. If decorating the BiFeO3 single crystal with a
soft magnetic thin film (such as Permalloy), the electric field-induced reorientation
of magnetic easy plane can further switch the magnetic anisotropy of the soft
magnetic thin film [128].
Electric Field Control of Spin Cycloid in BiFeO3 Thin Films: From the Control
of Collinear Magnetism to Noncollinear Magnetism
Electric field control of spin cycloid (and magnetic easy plane) has been experi-
mentally demonstrated in BiFeO3 bulk crystals [123] but not yet in BiFeO3 thin
films, although epitaxial strain-induced switching of spin cycloid in BiFeO3 thin
films has been experimentally demonstrated [134]. The coupling among the oxygen
octahedral tilts, polarization, and the spin cycloid, which has been discussed with
phenomenological approaches [142, 143], awaits experimental investigation.
Fig. 5 (a) Classifying composite magnetoelectrics based on the functionality of the constituent
dielectric material, along with representative dielectric materials. The solid ellipses suggest the
corresponding mechanisms of inverse magnetoelectric effects. EC, exchange coupling; FE-AF,
ferroelectric antiferromagnet; ME-AF, magnetoelectric antiferromagnet. Redrawn based on Ref.
[151] http://creativecommons.org/licenses/by/4.0/. (b) Relationship between composite multifer-
roics and composite magnetoelectrics by a loose definition, see discussion in the main text
Fig. 6 Complied experimental datasets showing the direct magnetoelectric voltage coefficientα HV
as a function of (a), the frequency of the driving AC magnetic field, and (b), the magnitude of
the bias magnetic field, both of which are necessary for the experimental measurement of α HV .
Available data in both bulk and thin-film composites of different phase connectivity are compiled.
Adapted from Ref. [151] http://creativecommons.org/licenses/by/4.0/. PC, particulate composites;
HC, horizontal composites; VC, vertical composites (see schematics in (c))
write magnetic-read memories [140, 177–179] and logic [180–184], electric field
tunable radiofrequency or microwave devices [158], etc. For example, electric field-
driven magnetization switching in the free layer of a magnetic tunnel junction (MTJ)
allows us to electrically toggle the electrical resistance of the entire junction between
high and low value, representing the bit information “1” and “0,” respectively.
The inverse magnetoelectric effect in composites magnetoelectrics may occur
through different mechanisms, depending on the functionality of the constituent
dielectric materials. Below we briefly discuss these mechanisms in composite
magnetoelectrics with a “plain” dielectric, piezoelectric, ferroelectric, ferroelectric
antiferromagnet, or a magnetoelectric antiferromagnet, respectively. We use a
layered magnetoelectric (Fig. 7) for discussion.
Plain Dielectric (Oxygen Ion Insulator). In the case of a “plain” dielectric
with low concentration of ion-conducting defects (such as MgO and HfO2 , see
Fig. 5a for representative materials), the inverse magnetoelectric effect typically
occurs through the modulation of spin-polarized charge densities (ns ≈ nη)
at the magnetic/dielectric interface as voltage is applied. Here n = ε0 εr E is
the change of the screened charges densities with ε0 and εr denoting the vacuum
and relative permittivity, respectively. The electric field-induced change of interface
12 Magnetoelectrics and Multiferroics 611
charge densities will shift the Fermi level at the interface, further changing the
interfacial spin polarization P = (D↑ − D↓ )/(D↑ + D↓ ), where D↑ (D↓ ) indicates
the densities of states for the spin-up (down) electrons, as schematically shown in
Fig. 7a. Notably, inverse magnetoelectric effect through such mechanism, which
we term as charge densities, can be directly observed [185–188] in a magnetic
tunnel junction such as CoFeB(pinned layer)/MgO/CoFeB (free layer) without
integrating additional dielectric materials. This is an important advantage for device
applications. However, such charge density-mediated inverse magnetoelectric effect
is generally very weak (see our compiled experimental dataset in Fig. 8a) and
usually causes an electric field-controlled interface magnetic anisotropy of less than
0.1 pJ/m2 per unit electric field (1 V/m), which is too small to switch a magnetization
with a sufficiently high thermal stability (>40 kB T) [189].
612 J.-M. Hu and L.-Q. Chen
Fig. 8 (a) Compiled experimental datasets showing the inverse magnetoelectric coefficient α E
(the slope) in magnetoelectric heterostructures, where the horizontal and vertical axes represent the
driving electric field and the electrically induced change of magnetization, respectively. The data
are classified by the corresponding mechanisms of inverse magnetoelectric effects as discussed
in Fig. 7, including charge densities (CD), interfacial oxidation (IO), exchange coupling (EC),
and strain transfer (ST). (b) Corresponding thickness of the constituent magnetic layer in a
chronological order. (a–b) Reprinted with permission from Ref. [151] http://creativecommons.org/
licenses/by/4.0/
Plain Dielectric (Oxygen Ion Conductor). If the dielectric layer is a good oxygen
ion conductor (such as GdOx ) and if the magnetic layer (M = Co, Fe, CoFe)
has a perpendicular magnetic anisotropy (PMA) that is sensitive to the degree of
interface oxidation (i.e., the x in an interfacial MOx layer), it is then possible to
tune the PMA by applying a voltage to tune the O2− concentration at the interface
and hence the degree of interface oxidation. The inverse magnetoelectric effect
through such mechanism, which we term as interfacial oxidation (see schematic
in Fig. 7b), has been observed mainly in Co/GdOx heterostructures [190–193],
and it can enable a giant electric field-controlled interface magnetic anisotropy of
more than 10 pJ V−1 m−1 , over 100 times larger than that in the case of charge
densities mechanism. This can be also seen from the approximately 100 times
larger inverse magnetoelectric coefficient as shown in our complied experimental
dataset (10−8 s/m vs. 10−10 s/m, see Fig. 8a). However, the speed of the inverse
magnetoelectric effect through such an interfacial oxidation mechanism may be low
compared to that through the charge density mechanism, because of intrinsically
slow oxygen ion migration. In addition, the back-and-forth oxygen-ion migration
between the upper and lower surfaces of the dielectric may accelerate dielectric
degradation. Thus, the potential device application of such interface oxidation
mechanism remains an open question.
Piezoelectric or Ferroelectric Dielectric. If the dielectric layer is piezoelectric ,
magnetism can be tuned, through magnetoelastic coupling, by strain imparted by
the piezoelectric layer as voltage is applied (see schematic in Fig. 7c), but it can
12 Magnetoelectrics and Multiferroics 613
also be tuned through the charge density mechanism mentioned previously. If the
piezoelectric layer is also ferroelectric, it is possible to obtain larger strains through
ferroelectric domain switching or a structural phase transition and larger electrically
induced change of interfacial charge densities due to the larger relative permittivity
εr in the ferroelectric. Both will lead to larger inverse magnetoelectric effects.
Furthermore, strain-mediated electric field-driven full magnetization reversal [194,
195] and unidirectional magnetic domain-wall motion [196] have recently been
computationally demonstrated at room temperature, providing exciting application
potential for electric-write magnetic-read memories. However, microfabrication of
some piezoelectric or ferroelectric materials may not be compatible with Si CMOS
(complementary metal-oxide-semiconductor) processing, and the fatigue problem
of ferroelectrics is also a potential issue.
Ferroelectric (or Magnetoelectric) Antiferromagnet. If the ferroelectric is also
antiferromagnetic such as BiFeO3 , the modulation of magnetism in the magnetic
layer can also be achieved, through Heisenberg-type exchange coupling, by elec-
trically tuning the antiferromagnetic order through reorientation of the magnetic
easy plane or/and the canted magnetization (see details in Sect. “Electric Field
Switching of Magnetization in Multiferroic BiFeO3 : Status and Perspective”).
Notably, exchange coupling-mediated electric field-driven 180◦ net magnetization
reversal has been experimentally demonstrated at room temperature [138]. However,
the high leakage current of BiFeO3 as well as its incompatibility with Si CMOS
processing in terms of microfabrication (e.g., specific oxide substrates must be
used for film deposition) undermines the application potential of BiFeO3 -based
magnetoelectric heterostructures. Such an exchange coupling mechanism has also
been observed in Cr2 O3 -based magnetoelectric heterostructures at room tempera-
ture [197]. Cr2 O3 is a magnetoelectric antiferromagnet, where the antiferromagnetic
domains as well as the uncompensated surface magnetic moment can be reversed by
applying an electric field (see schematic in Fig. 7d). Thus, the interfacial magnetic
moments in the overlaid magnet can be tuned through exchange coupling. Cr2 O3
has excellent dielectric properties with high dielectric breakdown field of 109 V/m
at room temperature, which is an advantage for potential device application,
although it remains a challenge to achieve such dielectric properties in Cr2 O3
thin films. Moreover, the electric field switching of antiferromagnetic domains in
Cr2 O3 requires simultaneous application of a static magnetic field to lift the time-
reversal symmetry. This will be a potential disadvantage for high-density device
applications, as it could complicate the device design by increasing the noise level
and possibly causing cross talk among neighboring device units.
Among the different mechanisms discussed above, only the strain-magnetization
coupling is long-range, while all the others are interface effects, consistent with our
complied experimental dataset showing the thickness of the constituent magnetic
layer in the case of different mechanisms (see Fig. 8b). Such long-range strain-
magnetization coupling partially leads to the fact that strain-mediated inverse
magnetoelectric effect is generally larger than the other types of effects, consistent
with the experimental data shown in Fig. 8a. For more detailed discussions on these
different mechanisms as well as remaining open questions, see He et al. [151].
614 J.-M. Hu and L.-Q. Chen
Acknowledgments This work was supported by a start-up fund from the University of Wisconsin-
Madison (J.-M.H.) and partially by the National Science Foundation under the grant no. DMR-
1744213 (Chen) and partially by the Army Research Office under the grant number W911NF-17-
1-0462 (J.-M.H. and L.-Q.C.). The authors acknowledge Xin Zou for helping draw some of the
schematics.
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Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
Paramagnetic Limit and Nonuniform FFLO Superconducting State . . . . . . . . . . . . . . . . . . . . 628
Interplay of Zeeman Field and Spin-Orbit Interaction: Spinless Fermions
and a Route Towards Topological Superconductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
Ising Superconductors: Interplay of Magnetic Field and Spin-Triplet Channels . . . . . . . . . . . 638
Superconductivity in the Presence of Antiferromagnetic Order . . . . . . . . . . . . . . . . . . . . . . . . 640
Phenomenological Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
Microscopic Consideration: Important Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 643
Ferromagnetic Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 648
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 652
Abstract
I. M. Eremin ()
Institut für Theoretische Physik III, Ruhr-Universität Bochum, Bochum, Germany
e-mail: [email protected]
J. Knolle
Blackett Laboratory, Imperial College London, London, UK
e-mail: [email protected]
R. Moessner
Max-Planck Institut für Physik komplexer Systeme, Dresden, Germany
e-mail: [email protected]
matter physics. In this short review, we have aimed to provide some introduction
to this exciting field of research.
Introduction
To gain an understanding of the paramagnetic effect, observe that the critical field
to destroy the superconducting state, Hp , at zero temperature may be found from a
comparison of two energy scales, the superconducting condensation energy, ΔEs ,
and the energy gain due to the spin polarization of electrons in the normal state,
ΔEp . The spin polarization of the electron gas changes its energy in the magnetic
field in the normal state by
H2
ΔEp = −χp , (1)
2
where χp = 2μ2B N(0) is the paramagnetic (Pauli) spin susceptibility of the normal
metal, μB is the Bohr magneton, N(0) is the density of electron states at the Fermi
level, and the electron g-factor is equal to 2. At the same time, the spin polarization
is absent in a spin-singlet superconductor, and the BCS condensation energy is given
by
Δ20
ΔEs = −N(0) , (2)
2
where Δ0 is the superconducting gap at zero temperature (in the BCS theory,
its value is given by 1.76kB Tc ). Comparing the two energy scales, one finds the
13 Magnetism and Superconductivity 629
Δ0
Hp (0) = √ . (3)
2μB
Note that this field would represent a first-order phase transition from a normal
to a superconducting state. However, Fulde and Ferrell [6] and Larkin and
Ovchinnikov [5] predicted the appearance of the nonuniform superconducting state
with a sinusoidal modulation of the superconducting order parameter at the scale
of the superconducting coherence length, ξs , which is now called FFLO state. In
this FFLO state, the Cooper pairs have a finite momentum compared with zero
momentum in conventional superconductors. The critical field of the second-order
transition into the FFLO state appears above the first-order transition line into
a uniform superconducting state [3]. At T = 0, it is H F F LO = 0.755Δ0 /μB ,
whereas Hp ∼ 0.7Δ0 /μB . The FFLO state only appears in the temperature interval
0 < T < T + (see Fig. 1) and is sensitive to impurities as it is a state with finite
momentum [25]. In real situations, the paramagnetic effect has to be considered in
addition to the orbital effects induced by the magnetic field. The relative importance
of the orbital and paramagnetic effects in the suppression of the superconductivity
is described by the Maki parameter [3]
√ Hc2
orb (0)
m ∗ Δ0
α= 2 ≈ , (4)
Hp (0) m0 εF
where m∗ is the effective mass of the conduction electron and m0 is the free electron
mass. Gruenberg and Gunther examined the stability of the FFLO state against
the orbital effect for the spin-singlet three-dimensional superconductors [26]. The
FFLO state can exist at finite temperatures if α is larger than 1.8 and its region
narrows considerably from that in the absence of the orbital effect. The typical phase
diagram indicating the formation of the nonuniform FFLO state is shown in Fig. 1.
The appearance of a modulation in the superconducting order parameter is related
to the Zeeman splitting of the electron’s energy level under a magnetic field (or
exchange field if we are talking about ferromagnets) as illustrated in Fig. 2. In
the absence of the Zeeman field, a Cooper pair is formed by two electrons with
opposite momenta and spins, +kF ⇑ and −kF , ⇓. The resulting momentum of the
Cooper pair will be 0. Because of the Zeeman splitting, the Fermi momentum of the
electron with spin ↑ will shift from kF to k↑ = kF + δkF , where δkF = −μB H /vF
and vF is the Fermi velocity. Similarly, the Fermi momentum of an electron with
spin ↓ will shift from −kF to k↓ = −kF + δkF . The resulting momentum of
the Cooper pair will then be given by k↑ + k↓ = 2δkF , which implies that the
space modulation of the superconducting order parameter has a resulting wave
vector q = 2δkF . In contrast to one dimension, it is not possible to choose the single
wave vector δkF in two- [27] and three-dimensional superconductors [6, 5], which
compensates the Zeeman splitting for all electrons on the Fermi surface, as δkF
depends on the direction of vF , which yields the existence of the paramagnetic limit,
which is absent in one dimension. Observe that the critical field for a nonuniform
state at T = 0 is always higher than a uniform one. When T > μB H , at finite
temperature, the smearing of the electron distribution function near the Fermi energy
decreases the difference of energies between nonuniform and uniform states. From
microscopic calculations, at T > T + = 0.56Tc , the uniform superconducting phase
(a) (b) q
ky
ky
kx kx
Fig. 2 Schematic illustration of the pairing states in two dimensions. (a) BCS pairing state (k, ↑;
−k, ↓). (b) FFLO pairing state (k, ↑; −k + q, ↓) with q = 2δkF . The inner and outer circles
represent the Fermi surface of the spin-down and spin-up bands, respectively. The dashed circle
represents the initial Fermi surface
13 Magnetism and Superconductivity 631
is always favored [3]. Observe that in real systems the Maki parameter is usually
much less than unity; thus, the influence of the paramagnetic effect is negligibly
small in most superconductors. However, in quasi-2D layered superconductors (for
parallel fields) and heavy-fermion superconductors such as CeCoIn5 , αM is largely
enhanced owing to large m∗ /m0 values, and thus the superconductivity may be
limited by the Pauli paramagnetic effect. We discuss this in more detail below. It
should be stressed that in superconductors with small Fermi energies, a large Δ0 /εF
leads to the enhancement of αM , as was recently argued in some of the iron-based
superconductors such as KFe2 As2 [28] and FeSe [45].
The formation of the FFLO phase can be also described in the framework of the
generalized Ginzburg-Landau expansion [19]
b
F = a|ψ|2 + γ |∇ψ|2 + |ψ|4 , (5)
2
η(H, T ) 2 2 b(H, T ) 4
F = a(H, T )|ψ|2 + γ (H, T )|∇ψ|2 + |∇ ψ| + |ψ| . (6)
2 2
Its minimization results in the equation that determines the critical temperature
of the second-order phase transition into a superconducting state
η 2
aψ − γ Δψ + Δ ψ = 0, (7)
2
η 4
a = −γ q 2 − q . (8)
2
Observe that for γ < 0, the maximum critical temperature corresponds to the
finite value of the modulation vector q02 = −γ /η and the corresponding transition
632 I. M. Eremin et al.
temperature
F F LO into the nonuniform
FFLO state TcF F LO (H ) with the coefficient a =
α Tc (H ) − Tc (H ) = γ /2η. This temperature is higher than the critical
2
Finally, we note that some of the iron-based superconductors such as KFe2 As2
and FeSe can be an interesting platform for studying peculiar multiband features
of the FFLO phases, as both have Maki parameters larger than 1.85 and a very
large Ginzburg-Landau parameter, κ = 15, necessary conditions for the FFLO state
to be observed. In addition, in both systems, there are several bands crossing the
Fermi energy with relatively low EF . Especially in FeSe, an estimate gives Δ/εF ∼
0.1 − 0.3 for the hole band and an even larger Δ/εF for the electron band [44].
In KFe2 As2 , a clear double transition for the field strictly aligned in the ab-plane
and a characteristic upturn of the upper critical field line far beyond the Pauli limit
was observed in magnetotorque and specific heat measurements [28] as shown in
Fig. 4. In FeSe, it has also been discussed that the high-field phase for H
ab can
be associated with an FFLO phase: in the H -T phase diagram shown in Fig. 4b, the
steep enhancement of Hc2 ab at low temperatures and the first-order phase transition
Fig. 4 (a) H − T phase diagram of KFe2 As2 inferred from the magnetic torque and the specific
heat measurements; the data points are taken from Ref. [28]. The upper transition curve separates
the FFLO state from the normal paramagnetic (PM) state. The additional lines represent the Hc2
lines predicted for a purely Pauli-limited superconductor [46] and for an in-plane isotropic s-wave
and a d-wave superconductor with the FFLO state [47]. (b) High-field phase diagram of FeSe
for H
(ab)-plane. Figure taken with permission from [45]. Copyright 2020 by the American
Physical Society. Blue circles and green crosses show Hirr and Hp determined by resistivity
measurements. Above the first-order phase transition field, a distinct field-induced superconducting
FFLO phase emerges at low temperatures
13 Magnetism and Superconductivity 635
H = Hwire + HΔ , (9)
where
∂x2
Hwire = dx ψσ† − − μ − iασ ∂x + hσ ψσ
y z
(10)
2m
and
HΔ = dx Δ ψ↑ ψ↓ + h.c. . (11)
Here, ψσ† creates an electron with effective mass m, chemical potential μ, and
spin σ in the wire, while α > 0 denotes the strength of the spin-orbit coupling
and h ≥ 0 is the Zeeman energy arising from a magnetic field applied in the z-
direction. Overall, Hwire refers to an electron-doped semiconducting wire such as
InAs or InSb with strong Rashba spin-orbit coupling, in the limit where only the
lowest transverse subband is relevant. The pairing term HΔ models the proximity
effect arising from the adjacent s-wave superconductor like Nb or Al.
The red and blue curves in Fig. 5a illustrate the band structure of Hwire for h = 0.
Due to spin-orbit coupling, the blue and red parabolae respectively correspond to
electronic states whose spin aligns along y and −y. The magnetic field lifts the
crossing between these parabolae at k = 0, producing band energies
636 I. M. Eremin et al.
Fig. 5 (a) Electronic band structure for the interface between a wire and a conventional s-wave
superconductor, shown in the inset, without (red and blue curves) and with external magnetic field
(black curves). (b) Shows the kinetic energy in the Kitaev toy model with spinless fermions. The
superconducting gap opens a bulk gap except at the chemical potential values μ = ±t. For |μ| < t,
the system forms a topological weak-pairing phase. In this case, the model, written in terms of
Majorana fermions, couples at adjacent lattice sites, leaving two “unpaired” Majorana degrees of
freedom at the ends of the chain. Figures taken with permission from [20]. Copyright 2012 by IOP
Publishing Ltd.
k2
± (k) = − μ ± (αk)2 + h2 (12)
2m
1 †
Ebulk (k) = εk2 + |Δ̃k |2 (14)
where εk = −t cos k − μ is the kinetic energy and Δ̃k = −iΔeiφ sin k is the pairing
amplitude in momentum space.
Ebulk (k) allows gapless bulk excitations when the chemical potential is fine-
tuned to μ = t or −t where the Fermi level respectively coincides with the top and
bottom of the conduction band. The gap closure at these isolated μ values reflects the
p-wave nature of the pairing required by the Pauli exclusion principle. In particular,
Δ̃k is an odd function of k, and Cooper pairing at k = 0 or k = ±π is prohibited,
thereby leaving the system gapless at the Fermi level when μ = ±t (see Fig. 5).
The physics of the chain is different in the two gapped regimes with |μ| > t
and |μ| < t. The first case connects smoothly to the trivial vacuum (upon taking
μ → ∞) where no fermions are present. By contrast, in the latter, a partially filled
band acquires a gap due to p-wave pairing. The new physics associated with this
state can be most simply accessed by decomposing the spinless fermion operators
cx in the original Kitaev Hamiltonian in terms of two Majorana fermions via
e−iφ/2
cx = γB,x + iγA,x , (15)
2
†
where the γ operators obey the Majorana fermion relation γα,x = γα,x . In this basis,
the Hamiltonian, HKitaev , reads
μ
N
HKitaev = − 1 + iγB,x γA,x
2
x=1
N −1
i
− (Δ + t) γB,x γA,x+1 + (Δ − t) γA,x γB,x+1 . (16)
4
x=1
N −1
it
HKitaev = − γB,x γA,x+1 (17)
2
x=1
which couples Majorana fermions only at adjacent lattice sites. However, as there
are two Majorana fermions per site, the ends of the chain (for the open boundary
conditions) now support “unpaired” zero-energy Majorana modes γ1 = γA,1 and
γ2 = γB,N . These can be combined into an ordinary – although highly nonlocal –
fermion that costs zero energy and therefore produces a twofold ground-state
degeneracy. Note the stark difference from conventional gapped superconductors,
638 I. M. Eremin et al.
where typically there exists a unique ground state with even parity so that all
electrons can form Cooper pairs.
The appearance of localized zero-energy Majorana end states and the associated
ground-state degeneracy arise because the chain forms a topological phase while the
vacuum bordering the chain is trivial. For the purpose of our review, it is important
that the fermions have to be spinless. This property ensures that a single zero-
energy Majorana mode resides at each end of the chain in its topological phase.
Suppose that instead spinful fermions, initially without spin-orbit interactions, form
a p-wave superconductor. In this case, spin merely doubles the degeneracy for
every eigenstate of the Hamiltonian, so that when |μ| < t, each end supports two
Majorana zero modes, or equivalently one ordinary fermionic zero mode. Unless
special symmetries are present, these ordinary fermionic states will move away from
zero energy upon including perturbations such as spin-orbit coupling.
Note that despite the intense search for intrinsic topological superconductors, the
practical realization of Majorana fermions appears to be easiest in the heterostruc-
ture described above with recent significant advances towards their experimental
realizations [53, 54, 55, 56, 57, 58]. This promises further exciting developments
on the interplay of magnetism and superconductivity in the field of topological
superconductors. To study the subject of topological superconductivity in depth,
the reader is invited to look into special reviews on the subject [20, 22, 53].
Apart from inducing singlet-triplet mixing, the SOC makes the superconducting
state robust against the in-plane Zeeman field B. Because of the negligible thickness
of the monolayer, orbital-limiting effects do not contribute, and the only way
a magnetic field can affect the electronic states is via the paramagnetic effect,
discussed above. The large SOC enhances the critical in-plane field Bc well beyond
the Pauli limit. This has been studied theoretically [66, 65, 67, 68, 69, 70, 71] and
demonstrated experimentally [60, 72, 73, 61, 74, 75, 76, 62].
Till now, theoretical analyses of the superconducting pairing mechanism in
monolayer NbSe2 [71, 77] have relied on model descriptions of superconductivity
in materials that lack inversion symmetry based on the band structure calculated
from first principles. There is also a lack of consistency between first-principles
descriptions of superconductivity in bulk NbSe2 and experimental results. For exam-
ple, first-principles calculations overestimate Tc in bulk NbSe2 and isostructural
NbS2 and the zero-temperature gap [78]. Most recently, it was demonstrated that
bulk and monolayer NbSe2 are close to a magnetic instability [79], and repulsive
as well as spin-fluctuation-induced interactions cannot be most likely neglected
when addressing superconductivity in NbSe2 [80]. This perspective on the role of
magnetism in monolayer NbSe2 will also be crucial to un- derstand and control
the superconducting properties of monolayer NbSe2 in the presence of an external
magnetic field or with heterostructures between monolayer NbSe2 and magnetic
materials.
640 I. M. Eremin et al.
Phenomenological Description
Similar to the case of the FFLO state, the competition between superconductivity
and antiferromagnetism near their finite-temperature phase transitions can be
described in terms of a Ginzburg-Landau theory of coupled order parameters
without referring to microscopic details; see, for example, [16]. The free energy
functional in the spatially homogeneous case is given by
as bs δ am 2 bm 4
FAF +SC (ψ, M) = |ψ|2 + |ψ|4 + |ψ|2 M2 + M + M , (18)
2 4 2 2 4
δ
g=√ −1 . (19)
bm bs
√
For g < 0 (0 < δ < bm bs ), (p∗ , T ∗ ) is a tetra-critical point where the two
second-order phase lines cross, leading to a regime in the phase diagram where
simultaneous AFM and SC orders coexist homogeneously. This is shown in Fig. 7a;
both phases compete but do not exclude √ each other.
On the other hand, if g > 0 (δ > bm bs ), the competition between two phases
is sufficiently strong such that both phases are separated by a first-order transition
that terminates at the bi-critical point (p∗ , T ∗ ). Notice that if the parameter p jumps
13 Magnetism and Superconductivity 641
Fig. 7 Schematic phase diagrams (p, T ) for competing AFM and SC orders, after [16]. Here,
p is a generic physical parameter and T is temperature. Solid and dashed lines denote second-
order or first-order phase transitions. For g < 0, there is a tetra-critical point and a region of
homogeneous coexistence (a). For g > 0, there is a bi-critical point, shown in (b) and (c). If p
changes discontinuously across the first-order transition, there will be a region of heterogeneous
coexistence for p1 < p < p2 (b), while its conjugate variable hp changes continuously and the
phase diagram has only one first-order line (c). Figure taken with permission from [16]. Copyright
2010 by the American Physical Society
where θ is a relative phase between the SC order parameters of the two Fermi
surface sheets. Once the phase difference is π (i.e., the superconducting gaps have
opposite phases), this term contributes to the reduction of the generally positive
value of δ in Eq. (18). Therefore, the situation of Fig. 7a appears more likely for
these unconventional superconductors.
13 Magnetism and Superconductivity 643
The interplay between AFM and SC has been investigated in many contexts and
has a long history [83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 16, 94, 95, 96, 97, 98]. In
the following, we are not going to review these works in detail but concentrate on
exposing the most important aspects.
The first important aspect of superconductivity in the presence of translational
symmetry breaking AFM order is the folding of the electronic structure and
formation of new bands below TN , as illustrated in Fig. 8. The details depend on
the particular model under consideration, but the main features can be clarified for
the simplest case of the single-band model. In particular, consider the single-band
Hubbard Hamiltonian on a square lattice
†
H =− ti,j ciσ cj σ + U ni↑ ni↓ − μ niσ , (22)
i,j,σ i i,σ
†
where ciσ creates an electron on site i with spin σ . The interaction term U denotes
the energy cost associated with having two electrons on the same site. In reciprocal
space, the Hamiltonian reads
† U † †
H = k ckσ ckσ + c c c−k+qσ ckσ , (23)
2N σ k σ −k +qσ
kσ k,k ,q
QAF
ky
kx kx kx
Fig. 8 Evolution of the Fermi surface topology for the commensurate AF state based on the
single-band model for layered cuprates. Due to the breaking of translational symmetry at the
antiferromagnetic momentum QAF M = (π, π ), the original energy dispersion, εk , in the
paramagnetic metallic state folds with the one shifted by the antiferromagnetic momentum
εk+QAFM . The original large Fermi surface (a) in the first Brillouin zone gets reconstructed as
an antiferromagnetic gap, W , opens on the “hot spots” εk = εk+QAFM (b). For intermediate W ,
the antiferromagnetic state is still metallic, and the residual Fermi surface consists of small hole
pockets, centered on (±π/2, ±π/2), and electron pockets, centered on (±π, 0), (0, ±π )
644 I. M. Eremin et al.
with
σ W
c
† † k kσ
HSDW = (ckσ ck+Qσ ) , (25)
σ
σ W k+Q ck+Qσ
k
U † †
where W = − N k [ck+Q↑ ck↑ − ck+Q↓ ck↓ ] is the AF order parameter.
Diagonalization of themean-field Hamiltonian leads to the following energy
±
spectrum: Ek = k+ ± (k− )2 + W 2 , k± = k 2k+Q . The magnetic gap equation
α,β
is usually solved self-consistently for a given set of values of the hopping integrals
t = 1, t , the Coulomb repulsion U , and the doping.
The electronic structure in the AF state folds and yields the new Fermi surface
topology, illustrated in Fig. 8. The problem immediately becomes a two-band one
as there are now two types of fermionic bands, α and β. These give rise to electron
and hole pockets. In this regard, it is then more practical to consider the Cooper
pairing in terms of the α and β fermions, obtained after diagonalization of the
mean-field AF Hamiltonian. In particular, for the magnetization pointing along the
z-direction, the quasiparticle operators are related to the bare electron operators by
the transformation:
Using the new basis allows to account naturally for the umklapp Cooper pairing,
ck,↑ c−k−QAFM ,↓ , absent in the paramagnetic state, and the renormalization of
the chemical potential in the AF state, μ. In addition, one has to bear in mind that
the AF state breaks spin-rotational invariance, which yields parity (momentum in
the reduced BZ and its inversion) as the only good quantum number of the Cooper
pairs. The Cooper pairing has to be considered between quasiparticles residing
† † † †
in the same band, i.e., αkσ α−kσ and βkσ β−kσ . In addition, one has to take
into account the possibility of anomalous pairings between fermions belonging to
† †
different pockets, i.e., αkσ β−kσ . The complete mean-field Hamiltonian includes
then the pair scattering processes between normal and anomalous gaps, as well as
scatterings between anomalous gaps. Such a pairing has been considered in the
context of the iron-based superconductors [96] and layered cuprates [98] as it
13 Magnetism and Superconductivity 645
couples linearly to the normal intraband gaps with a coupling constant proportional
to the SDW order parameter.
† †
In principle, anomalous pairs of the form αkσ β−kσ involve fermions far from
the Fermi level for T < TN , since the two bands are gapped by the antiferromagnetic
β
gap |Ekα − Ek | ≥ 2W . Nevertheless, the anomalous gaps become sizeable due to
the coupling to the normal intraband pairs and exist only in the AFM background,
since the coupling between normal and anomalous gaps is proportional to W . A
detailed analysis [98] of the interaction Hamiltonian reveals, however, that even
† † † †
parity intraband gaps, i.e., αk↑ α−k↓ −αk↓ α−k↑ , couple to even parity anomalous
interband gaps. In the iron-pnictide study of Ref. [96], the reported anomalous
gap was dubbed spin triplet and coupled to an even parity singlet intraband gap.
However, one has to bear in mind that in this case the triplet gap is actually
of even parity, which is allowed due to the band index. Nevertheless, the spin-
singlet and spin-triplet gaps do coexist in the AFM background both having the
same parity. As the spin-rotational and the time-reversal symmetry for a given
sublattice is broken, one could even find the so-called s + it even parity state, as
shown in Fig. 9. However, to avoid confusion, we believe that it may be better to
classify the superconducting gaps by parity rather than by spin quantum numbers, as
spin-rotational symmetry (and to some extent time-reversal symmetry) is explicitly
broken, while the parity is conserved.
So far, the interactions yielding superconductivity have not been specified. They
are often considered on a phenomenological level. At the same time, the most
interesting situation is when the Cooper pairing arises from the same interaction
which drives the AFM transition. In the single-band Hubbard model, the source
of Cooper pairing is the spin and charge fluctuations. In particular, higher-order
interactions in U generate superconductivity on top of the AFM order through
Fig. 9 The spin structure of the gap function in an AFM background for the iron-based supercon-
ductor and the arrows refer to the relative phase of the intra- and interband order parameter: (a)
pure spin-singlet (s) even parity s +− -wave state, (b) pure spin-triplet (t) even parity s ++ -state, and
(c) s + it state with π/2 phase difference between s- and t-components as adopted from Ref. [96].
Figure taken with permission from [86]. Copyright 2014 by the American Physical Society
646 I. M. Eremin et al.
the longitudinal and transverse pairing potentials achieve their maximum strengths.
The reason is that in the limit where electron pockets are small, the structure of
the intrapocket pairing potentials is purely attractive and this strongly supports a
d-wave solution. At critical electron doping for which W → 0, the Fermi arcs
just touch the magnetic zone boundary, and as a consequence, nesting by Q on the
paramagnetic side is rapidly weakened upon increased electron doping. There is a
jump in the magnitudes of the eigenvalues for the three leading gap symmetries in
the paramagnetic state. Their ordering, however, remains the same as in the SDW
phase, with the p solution, which in the paramagnetic phase takes the simpler form
[cos(kx ) − cos(ky )] sin(kx ), the least favorable. The jump in the eigenvalues is due
to the weak nesting properties of the Fermi surface on the paramagnetic side. In
fact, the paramagnetic Fermi surface, which is a hole pocket centered at (π, π ), is
roughly circular, thereby preventing nesting not only at Q but also at any q-vector.
As a result, spin-fluctuation-mediated superconductivity rapidly dies off.
It is interesting that the arguments on the stability of the dx 2 −y 2 -wave symmetry
on the AF background change if the Cooper pairing is mediated by an exchange
interaction which involves only nearest-neighbor sites, while the discussed approach
above deals with the on-site Coulomb repulsion and its renormalization in the
Cooper channel at higher orders. The similarity of the treatment of the coexistence
phase in Refs. [102] and [98] allows for a direct comparison of the interaction
Hamiltonians. In the simplified case of only hole pockets at the Fermi surface, the
interaction Hamiltonian reads generally
Hhole = Γ (k, k )βkσ
† †
β−kσ β−k σ βk σ , (28)
k,k σ
J (k − k ) 2
Γt−J (k, k ) = − [m (k, k ) + l 2 (k, k )]
2
−J (k + k )[n2 (k, k ) + p2 (k, k )], (29)
with J (q) = J [cos(qx ) + cos(qy )] and J > 0. In the Hubbard model we have
+−
ΓHub (k, k ) = Γk,k
z
± 2Γk,k , (30)
with the longitudinal and transverse effective interactions. The lower sign of Eq. (30)
belongs to the triplet channel, and this is the source of an effective intrapocket
repulsion on the hole-doped side. On the contrary, the effective interaction as stated
in Eq. (29) gives rise to a purely attractive triplet potential for k and k residing
on the same hole pocket, and therefore the p-wave solution would indeed appear
to be the dominating instability. Note also that the model of Ref. [102] cannot be
considered strictly as a strong-coupling limit of the single-band Hubbard model
648 I. M. Eremin et al.
Ferromagnetic Superconductors
limit field in the first three compounds [114]. Further ferromagnetism does not
suppress superconductivity with triplet pairing, and no traces of spatial modulation
of magnetic moment directions on a scale smaller than the coherence length have
been revealed [18]. It is therefore natural to assume that these ferromagnetic
superconductors are triplet superconductors similar to superfluid phases of 3 He.
One has to keep in mind, however, that unlike liquid helium, which is a completely
isotropic neutral Fermi liquid, superconductivity in ferromagnetic superconductors
develops in strongly anisotropic ferromagnetic metals. In particular, all these
materials have an orthorhombic structure with the magnetic moment oriented either
along the a-axis like it is in UGe2 or along the c-axis in URhGe and UCoGe. The
magnetic moments are mostly concentrated around uranium ions, and at T → 0,
they are equal to 1.4μB in UGe2 [115], 0.4μB in URhGe [116], and 0.07μB
in UCoGe [117]. Although these values are much smaller than the moment per
uranium atom as deduced from the uniform susceptibilities above TC , this is still
not sufficient to treat uranium compounds as completely itinerant ferromagnets.
Instead, they are dual localized and itinerant ferromagnets. The interaction between
conduction electrons by means of spin waves in a system of localized moments
is considered to be the most plausible pairing mechanism. Models of this type have
been previously applied to the superconducting antiferromagnet UPd2 Al3 [118] and
to reentrant superconduc- tivity in the ferromagnetic URhGe [119]. In application
to the orthorhombic ferromagnets, the general structure of the order parameter,
dictated by symmetry, was proposed by [120, 121]. Subsequently, the microscopic
formulation based on the pairing interaction due to exchange of magnetization
fluctuations in orthorhombic ferromagnets with strong magnetic anisotropy was also
recently formulated [122, 123]. In the following, we quickly outline the details of
this consideration assuming Tsc < TC .
In the ferromagnetic state, the simplest model system consists of two bands,
ε↓ (k) and ε↑ (k), for the spin-down and spin-up bands, respectively. The spin-triplet
superconducting state arising in a ferromagnetic metal consists of spin-up, spin-
down, and zero-spin Cooper pairs described by the vector order parameter
650 I. M. Eremin et al.
Δ(k, r) = Δ↑ (k, r)| ↑↑ + Δ0 (k, r)(| ↑↓ + | ↓↑) + Δ↓ (k, r)| ↓↓, (31)
where Δ↑ (k, r), Δ0 (k, r), and Δ↓ (k, r) are the spin-up, zero-spin, and spin-down
amplitudes of the superconducting order parameter, depending on the Cooper
pair center of gravity coordinate r and the momentum k of pairing electrons.
Equivalently, one can write
1
d(k, r) = −Δ↑ (k, r)(x̂ + i ŷ) + Δ↓ (k, r)(x̂ − i ŷ) + Δ0 (k, r)ẑ, (33)
2
and x̂, ŷ, and ẑ are the unit vectors along the corresponding coordinate axes.
Most of the ferromagnetic superconductors are ferromagnetic orthorhombic
crystals with a strong spin-orbit coupling fixing the spontaneous magnetization
along one of the symmetry axes chosen as the z-direction. Superconducting states
with different critical temperatures are described by the basis functions of the
different irreducible representations of the symmetry group of the normal state of the
crystal [124]. There are only two different representations, dubbed A and B of the
group GF M [120, 121]. The resulting vector order parameters are five-component
dA (k, r) and four-component dB (k, r). In particular, the symmetry considerations
[120] give the following form:
↑
ΔA (k, r) = k̂x ηx↑ (r) + i k̂y ηy↑ (r)
↓
ΔA (k, r) = k̂x ηx↓ (r) + i k̂y ηy↓ (r) (34)
and
↑
ΔB (k, r) = k̂z ζz↑ (r)
↓
ΔB (k, r) = k̂z ζz↓ (r) (35)
Δ0B (k, r) = k̂x ζx0 (r) + i k̂y ζy0 (r)
where k̂x , k̂y , and k̂z are the components of the unit momentum vector k̂. It is
important to note that the five-component order parameter of the A state and the
four-component order parameter of the B state include by symmetry the zero-spin
components. In other words, they are not equal-spin-pairing states consisting of
Cooper pairs with opposite spins, as one would expect naively for the ferromagnetic
state. This property originates from the spin-orbit coupling. However, although
13 Magnetism and Superconductivity 651
the pairing amplitudes for the zero-spin components can indeed arise due to the
spin-orbit terms in the ferromagnet gradient energy, they were shown on the basis
of microscopic considerations to be small [125]. Therefore, one can in the first
approximation ignore this amplitude Δ0 in the A and B states.
In this case, one deals with a two-band superconducting state similar to the
A2 state of superfluid 3 He [126]. Microscopically, the interaction between two
electrons driving the Cooper pairing is assumed to be due to the attraction of one
electron by the magnetic polarization cloud of the other. The pairing of electrons in
a ferromagnetic metal occurs in an anisotropic medium due to polarization of the
electron liquid and the localized moments.
This theory in application to the ferromagnetic superconductors was elaborated
in the context of ferromagnetic superconductors [123, 125]. It is important to
mention that the results of the microscopic considerations seem to agree with the
pure symmetry considerations, yet the experimental verification of the symmetry
of the superconducting order parameter is still absent. Part of the complication is
that in the ferromagnetic superconductor, there is an internal field Hint acting on
the electron charges even in the absence of an external field. The internal magnetic
field in all uranium ferromagnets is larger than the lower critical field Hc1 . Hence,
the Meissner state is absent and the superconductor is in an Abrikosov vortex state
with spatially inhomogeneous distributions of the order parameter and the internal
magnetic field, which complicates the analysis. Nevertheless, a comprehensive
state-of-the-art review on the subject can be found in [125].
Conclusions
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Part II
Magnetic Materials
Magnetism of the Elements
14
Plamen Stamenov
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
The Magnetism of Iron, Cobalt and Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
Band Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
Thin Films of Fe, Co and Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
Iron, Steels and Other Iron-Based Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
Phase Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
Manganese and Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
Manganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
Spin Density Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
Rare Earths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
Magnetism of the Rare Earths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
Magnetic Structures and Phase Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
Fermi-Level Spin Polarisation of the Magnetic Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
Spin Polarisation of the 3d Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
Spin Polarisation of the 4f Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 682
Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
Molecular Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
Other Examples of Magnetic Order in the p- and d-Shell Elements . . . . . . . . . . . . . . . . . . 689
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
Abstract
P. Stamenov ()
School of Physics and CRANN, Trinity College, University of Dublin, Dublin, Ireland
e-mail: [email protected]
bulk form – iron, cobalt, nickel, manganese, chromium, most of the rare earths
and oxygen. All except oxygen are metals. The importance of spin polarisation
at the Fermi level is illustrated by the three room-temperature ferromagnets:
iron, cobalt and nickel. Manganese and chromium are atypical antiferromagnets;
α-Mn is a multi-sublattice antiferromagnet, β-Mn is a spin liquid, and Cr exhibits
an incommensurate spin density wave. A summary of the magnetism of the
rare earth elements emphasises the effects of the crystal field, their moments
and exchange integrals on their magnetic structures and phase transitions.
Some magnetoelastic effects are discussed, and a detailed account of the spin
polarisation of the heavy rare earths concludes the section. Finally, more exotic
forms of magnetism such as the molecular antiferromagnetism of oxygen and
defect-induced magnetism, exhibited by p and d-shell elements, such as carbon
and ruthenium, are presented.
Introduction
This is a short tale of the very foundations of material magnetism – the properties of
the magnetic elements. It is also a rather confined story; for as far as possible, it is
restricted to the properties of the essentially pure elements in their bulk form, rather
than their compounds and alloys. Crystal structure is a critical factor for determining
the magnetism of a solid. A glance at the magnetic periodic table in Fig. 1 reveals
that most of the elements possess a magnetic moment when they exist as free atoms.
The moment is determined by Hund’s rules. Only those elements with filled s, p, d,
or f shells or an electronic configuration such as p2 or d 4 , where L and S cancel,
have no moment to call their own. But everything changes when they enter the
community of a solid. Bonding with their neighbours often effaces all traces of their
former identity and eliminates their electrons with unpaired spin, be it covalent or
metallic. The moments survive to order ferromagnetically below a Curie point TC
or antiferromagnetically below a Néel point TN in just 16 of the 88 stable elements.
Only four of these order above room temperature, the ferromagnets (Fe, Co, Ni and
Gd) and the antiferromagnet (Cr), as vividly illustrated on Fig. 1. The importance of
crystal structure is underlined by the behaviour of different allotropes of the same
element; α- or γ -Fe, α- or β-Mn, β- or γ -Ce, for example, each have quite different
magnetic properties.
A common, yet striking comparison can be made of the magnetic and super-
conducting periodic Table 2. Despite both superconductivity and ferromagnetic
order being critical phenomena occurring below some well-defined temperature,
superconductivity is twice as common amongst the pure element, as can be seen
from an inspection of Fig. 2, where at least 32 pure elements have non-vanishing
superconducting Tc , albeit at temperatures that are much lower than their magnetic
counterparts. No element exhibits both types of order. This, of course, reflects
the quantum mechanical origins of these two phenomena. While in the case of
elemental superconductivity, the underpinning requirements are to have a metal,
which the vast majority of elements are (having a partially filled valence band) and
14 Magnetism of the Elements 661
Fig. 2 The periodic table of the superconducting transition temperatures. (After: www.
webelements.com)
662 P. Stamenov
Band Structures
It is instructive to look into the detail of the DOS for the three primary 3d
ferromagnets and analyse the differences that exist between them. In the case of iron,
while the overall difference of the spin-up and spin-down DOS, integrated from EF
down, and therefore the net available magnetic moment is the largest, the DOS in the
vicinity of EF is actually the smallest. Courtesy of the large exchange splitting of the
peak of the d states ∼2.8 eV, a lot of the available DOS for spin-down is unoccupied,
while the peak of the spin-up states is pushed to about 1 eV below EF . This results in
a reasonably high positive DOS polarisation P > 50%. The situation is different for
Co, as of both the different crystal symmetry (hcp), rather than bcc, and the different
total electron count. The exchange splitting of the peak of the d states is substantially
smaller or about 2 eV. The purely DOS spin polarisation is negative, P ∼ −70%.
14 Magnetism of the Elements 663
Out of the three primary elemental ferromagnets, Ni suffers the most of the high
occupancy of d states, at 3d 8 . This minimises further the exchange splitting of the
peak of the d states to approximately 1 eV and minimises further the net disbalance
of the spin-up and spin-down occupied DOS, resulting in the smallest magnitudes of
the net polarisation and Curie temperature in the tetrad. More surprising is the fact
that the purely DOS polarisation is rather large and negative at P ∼ −80%, as the
Fermi level is ‘pinned’ at the large peak of the d-states spin-down PDOS. This large
negative polarisation has been the source of much controversy in the early efforts
for matching theoretical predictions of the band structure with experiment (Fig. 3).
Magnetic Properties
While thin films of the pure elements are rarely used for spin electronic applications,
perhaps with the exception of epitaxial Fe, grown on MgO, the 3d random alloys and
ordered phases are critical building blocks for modern devices. The reader is referred
to Chap. 16, “Metallic Magnetic Thin Films,” for details on these (Table 1).
Phase Diagram
Soft Steels
Electrical Steel Silicon is a common ternary addition to low-carbon steel, which
helps to suppress and delay the α → γ transition from ferrite to austenite, normally
occurring about 912◦ C. As can be seen in the phase diagram in Fig. 5, the nominal
phase border is at 3.8 at. %, for otherwise pure iron. About 6 at. % of Si are usually
added, to account for leftover carbon, which substantially extends the austenitic
stability region, potentially all the way down to 727◦ C (see Fig. 4). The discovery
of the process is attributed to Robert Hadfield, around 1900, who had realised that
the compositions around 6 at % Si are sufficiently ductile to hot-roll to thin sheets.
The optimal thickness depends largely of the frequency band of application and the
skin depth, typically at main frequencies of 50–60 Hz. The largest amounts (about 7
B$) are produced with thickness of about 300 μm. There are additional gains as Si
lowers both the anisotropy and the magnetostriction in mild steel, while increasing
its electrical resistivity and corrosion resistance.
Goss Texture While in motor and generator applications isotropic microstructure is
appropriate, as the direction of the conducted flux can change substantially during
a cycle of the rotary machine (typically close to the ends of the pole pieces), in
transformer applications, the direction of the conducted flux stays locally largely
restrained onto a particular axis. This is, of course, the case away from zero
magnetic induction B, when changes in magnetic induction result in Eddy currents
being induced perpendicular to core lamination. Providing a crystallographic
texture and associated magnetocrystalline anisotropy can, indeed, be beneficial to
14 Magnetism of the Elements 665
Fig. 4 The carbon-iron phase diagram, at carbon concentrations below the cementite border.
(After: www.himikatus.ru/art and www.asminternational.com, Binary Alloy Phase Diagrams,
1986, Ed. T. B. Massalski, ISBN: 978-0-87170-403-0)
the minimisation of the core losses. The additional restriction provided by the
anisotropy, especially active at small B values, helps to keep the Eddy current
density low and eases the process of domain growth along the easy axis (in-plane).
Permalloy Permalloy is an all-purpose soft magnetic material that has been called
‘the fourth ferromagnetic element’. It is a partially ordered f cc alloy of Fe and
Ni, with approximate composition Fe20 Ni80 . The saturation polarisation is a little
more than 1 Tesla, but the alloy owes its success to the fortuitous cancellation of
both magnetostriction and intrinsic anisotropy at the same composition – a lucky
coincidence in a binary alloy; both change sign at a composition close to 80% Ni.
The soft magnetic properties are essentially impervious to strain. The soft magnetic
properties are improved by annealing and by small alloy additions of Cu and Mo, to
make alloys known as Supermalloy and MuMetal which can have permeabilities as
high as 105 and are very effective for magnetic shields.
Permendur The name permendur is reserved for the soft magnetic alloys of iron
and cobalt with compositions close to 50/50. It can contain up to 1% carbon
and undergoes order-disorder transition at 730◦ C, as illustrated in Fig. 6. Modern
compositions often have additional alloying elements, such as vanadium and silicon,
used to increase the machinability by increasing the eutectoid temperature and
666 P. Stamenov
1538°C
1500 L
1410°C 1414°C
1394°C
1300 23.5
19.5
Temperature °C
500
0 10 20 30 40 50 60 70 80 90 100
Fe Atomic Percent Silicon Si
Hard Steels
Special Steels
Magnetic and Anti-magnetic Stainless Steel
Stainless steels are generally separated into three main classes, based on their
underlying crystalline structure – austenitic (f cc), ferritic (bcc) and martensitic
(bct). Out of these only the first one can be classified as essentially non-magnetic or
anti-magnetic. This is due to the austenitic structure being antiferromagnetic, with
an ordering temperature, which is strongly dependent on the amount and type of the
additive(s) used to stabilise the γ -phase, with Cr and Ni being the most commonly
used ones, in concentrations of up to 20%. The transitions generally occur at
14 Magnetism of the Elements 667
L 1538°C
1500 1495°C
(δFe)
∼33%,1476°C
1394°C
1300 (αCo,γFe)
Temperature °C
1121°C
1100
Ma
Tra g. ∼55%,985°C
ns.
∼75 912°C
900 ∼27 Ma
(αFe) Tra g.
ns.
∼50%,730°C
770°C
700
α1
500
0 10 20 30 40 50 60 70 80 90 100
Co Atomic Percent Iron Fe
cryogenic temperatures (5–50 K) and create significant problems for the application
of stainless steels in the construction of sensitive magnetometers and their use in
components designed for operation in high magnetic fields. The judicious choice of
composition and thermal treatment allows for the delay of both the Neel transition
and the transformation to the equilibrium martensitic or ferritic phase to be delayed,
with rather large amount of super-cooling, all the way down to He temperatures [3].
Manganese
Crystal Structure
The crystal structure of α-Mn may be represented as a closed-packed intermetallic
compound, containing strongly magnetic (MnI) and (MnII), the weaker (MnIII), and
the even weaker (MnIV). Low-temperature magnetic moments are, respectively, 2.8,
1.8 and 0.5 μB . Atomic moments and exchange interactions in manganese and its
alloys are very sensitive to the Mn-Mn separation (Fig. 4).
Magnetic Structure
The non-collinear magnetic structure is a result of the weakly magnetic (MnIV)
being arranged on the triangular faces of polyhedra and exhibiting a frustrated anti-
ferromagnetic coupling, somewhat similar to that of the triangular antiferromagnets.
The other magnetic moments are rotated slightly from their otherwise collinear
antiferromagnetic orientation as a consequence of their finite interaction with the
(MnIV) [4] (Fig. 7).
Chromium
Crystal Structure
Paramagnetic chromium has a relatively simple bcc crystal structure, with an a =
2.884 Å. This is, however, altered below its TN = 311 K, by effects such as exchange
14 Magnetism of the Elements 669
striction. Since the details of the atomic order are in this case dependent on the spin
order, it is useful to understand better the underlying reasons for the existence of the
so-called charge density wave (CDW) state.
Magnetic Structure
Chromium is the prototypical 3d itinerant antiferromagnet. The underlying structure
is that of an alternating (001) spin planes, with the ones containing the corner atoms
opossing the ones passing through the body centring ones. Should this spin structure
have been perfectly commensurate, it would have been described by [5] (Fig. 8):
This would imply that for the commensurate structure and in thermodynamic
equilibrium, three different domains would co-exist with the spins aligned along the
three main crystallographic directions. Reality is somewhat more complicated, with
an incommensurate linearly polarised spin density wave (I-SDW) structure, being
observed below the Néel point. This is a sinusoidal modulation of the magnetic
moment density of the type:
(r ) = μ
μ 0 sin Q ± · r (3)
± = 2π 1 1 2π
Q − [001] = (1 − δ) (4)
aCr ΛSDW aCr
Both the commensurate and incommensurate states have been the subjects of
very detailed experimental and theoretical investigations, imploying a variety of
techniques, including neutron scattering and ultrasound attenuation, in order to
characterise both the order parameters and their influence on the electronic structure.
A detailed account of the state of investigations on elemental chromium [6] and its
alloys [7] is given by Fawcett and collaborators.
The microscopic theory of the formation of the commensurate SDW has been
the subject of many debates, but the underlying principle seems to be related to
670 P. Stamenov
Fig. 8 The magnetic structure of α-Cr and a typical spin density wave. (After: [5])
the nesting properties of the Fermi surface, in this case [6]. The nesting implies
that the electron and hole Fermi surfaces are rather similar and can be essentially
In a situation, similar to the one
superimposed by translation by a nesting vector Q.
appearing in some rare earths, this leads to anomalous electron-magnon scattering,
with both static and dynamic consequences. The SDW wave vector Q therefore is,
in most cases, very close to Q.
Commensurate SDWs
Highly defective Cr, resulting, for example, from a cold-working process, can
display rather high Neel transition (up to 475 K) to a commensurate AFM struc-
ture. This is attributed to the build-up of strain-induced dislocations [6]. It is
worth noting that in the commensurate AFM state, the PDOS of the d states
in chromium is not completely unpolarised. The small differences in the local
environment on the α and β sites should result in a rather small, yet potentially
observable Fermi level polarisation as indicated on Fig. 9. It probably comes to
a little surprise that some finite polarisation (P ∼ 5%) can be recovered in
experiments involving nano- and micro-indentation-based contact formation, such
as PCAR.
Incommensurate SDWs
14 Magnetism of the Elements 671
Fig. 9 The d-states DOS of Cr in the commensurate spin density wave regime. (After: [6])
Rare Earths
The properties of the rare earth elements in their metallic form are determined
primarily by the relative localisation of the 4f electrons, whose states resemble
closely the ones of the free atoms and ions, and forming the majority contribution to
the magnetic moments. The 5d and 6s states, on the other hand, delocalise and serve
a dual purpose, as quasi-free carriers and as mediators of the exchange interactions.
This separation, although not absolute, is a good starting point for the discussion
of the properties of the 4f states. Their interactions with the surroundings can be
classified into two classes – single-ion interactions, which are independent on each
672 P. Stamenov
crystal site i and contribute energy sums to the Hamiltonian, which are independent
on the different ionic residues, and two-ion interactions, which involve sums over
pairs of ions, indexed by i and j .
Crystal Field
The most important single-ion contribution is the effect of the crystal field. This
is effectively the influence of the charge distribution around an ionic site with
a particular local point symmetry, resulting in the large magnetic anisotropies,
characteristic of the rare earths, even in their metallic form. In first-order terms,
the crystal field contribution to the potential energy can be written as:
eρ(R)
vcf (r) = dR (5)
|r − R|
where ρ(R) is the charge density distribution created by the surrounding ionic
residues (both electronic and nuclear parts). If the overlap of the 4f electronic cloud
can be considered small, the solution of the Laplace’s equation may be written in
terms of an expansion over spherical harmonics of the type:
vcf (r) = Am l
l r Ylm (r ) (6)
lm
with the coefficients of the expansion Aml , given by the appropriate integrals of the
type:
m 4π ρ(R)
Am = (−1) dR l+1 Yl−m (R ) (7)
l
2l + 1 R
The Racah operators O lm (J) are defined via the spherical harmonics, projected
over Cartesian coordinates, by replacing r by J and symmetrising. Convenient tables
14 Magnetism of the Elements 673
of these are readily available in the literature. The convenience in using the Racah
operators, however, is not complete, as they transform as tensor operators and
behave under rotations like spherical harmonics. It is, therefore, rather customary
in the field to introduce the Stephens operators Olm (J), so that the crystal field part
of the Hamiltonian can be written as [8]:
Hcf = Blm Olm (Ji ) (9)
i lm
The first few of the Stephens operators can be expressed in terms of X ≡ J (J +1)
and J± ≡ Jx ± iJy as:
1 2
O22 = J+ + J−2
2
1
O21 = (Jz Jx + Jx Jz )
2
O20 = 3Jz2 − X
Despite the apparent simplicity of the expression for the crystal field, in terms of
the Stephens operators, the coefficients Blm are still quite difficult to estimate with
an adequate accuracy, due to the non-spherical shapes of the charge distributions and
the existence of substantial charge redistribution and shielding effects. Two practical
approaches are very often deployed. One is to consider an adjustable magnitude
point-charge model for the charge distribution (compensating for the electronic
screening). The other is to treat BlM simply as experimental parameters, fixed based
on experimental data. For the rather popular hexagonal case, the crystal field can be
specified by fixing the values of four independent parameters:
⎡ ⎤
Hcf = i⎣ Bl0 Ol0 (Ji ) + B66 O66 (Ji )⎦ (10)
l=2,4,6
For effectively all rare earths, these parameters have been determined experi-
mentally, taking into consideration data available from a number of experimental
techniques, with the resulting multiplet splitting typically being in the range of 10-
ns to 100-ths of meV.
Magnetoelastic Effects
When the lattice is strained, both the crystal field and the two ion terms of the Hamil-
tonian are affected. This results in a substantial magnetoelastic coupling energy and,
courtesy of the modest elastic constants of the rare earth metals, to the possibility
of having large additional equilibrium strain and/or large magnetostriction. As the
strain scaling of the elastic energy is quadratic and the one of the magnetoelastic
energy is linear, balance situations may occur, indeed, for non-zero values of
equilibrium strain. Within the pure rare earths and their alloys is, indeed, where we
674 P. Stamenov
find the largest magnetostriction coefficients; see, for example, Table 2. An example
of great practical importance is the alloy system Terfenol-D (Tbx Dy1−x Fe2 ) , for
x ∼ 0.3 , which exhibits magnetostriction coefficient λs > 2 · 10−3 . Before leaving
strain behind, it should be mentioned that the magnetoelastic effects can, indeed, be
considered to be strain-dependent renormalisations of the crystal field parameters.
There is, however, also a dynamic side to the coupling, which results in the crossing
and anti-crossing of the dispersion relations of magnons and phonons, in particular
high-symmetry directions, and can result in the formation of combined excitations,
sometime referred to as elasto-magnons.
Out of the two-ion couplings, the most important one to consider is the indirect
exchange, by courtesy of which the ions are coupled via the conduction electrons.
The general form of this interaction can be written as [8]:
2
Hsf (i) = − drI (r − R)Si · s(r) = − drHi (r) · μ(r) (11)
N
with N being the number of ions, s(r) is the conduction electron spin density and
the magnitude of the exchange integral I is determined by the geometric overlap
between the charge distributions of the 4f and the conduction states. The same
expression also defines an inhomogeneous effective magnetic field Hi (r) acting on
the conduction electron moment density μ(r) = 2μB s(r). Employing the standard
approach of the generalised susceptibility theory, a spin located at Ri contributes to
the moment μiα like:
14 Magnetism of the Elements 675
1
μiα (r) = dr χαβ r − r Hiβ (r ) (12)
V
β
or in vector notation μi = χ̂ · Hi .
In order to try and exploit the periodicity of the crystal lattice, it is convenient
to define the forward and backward Fourier transforms of the generalised non-local
conduction electro-susceptibility as:
1
χ (q) = drχ (r)e−iq·r
V
V
χ (r) = drχ (q)eiq·r
(2π )3
which is valid within a scalar approximation and written this way for simplicity.
Moments and Exchange Integrals
The additional term in the Hamiltonian, corresponding to the f − f coupling
thorough the conduction electrons, is then simplified, defining I (q) to be the Fourier
transform of the exchange integral to:
1
Hff = − JS (ij )Si · Sj (13)
2
ij
taking the form of the familiar Heisenberg exchange, with JS (ij ) computed as:
1
JS (ij ) = JS (q)eiq·(Ri −Rj ) (14)
N q
V
JS (q) = |I (q)|2 χ (q) (15)
Nμ2B
1 1 m∗
H (ij ) ∼ Si · Sj 4
2kF Rij cos(2kF Rij ) − sin(2kF Rij ) (17)
4 (Rij ) h̄
676 P. Stamenov
Fig. 10 The indirect exchange interaction coupling strength, as deduced from neutron scattering
measurements of magnon dispersions in Pr. (After: [8] and [9])
where kF = q(EF ) is the Fermi wavevector for the conduction electrons, m∗ is the
conduction electron effective mass and Rij = Ri − Rj . The form of this interaction
is decaying oscillatory, with it covering typical distances of up to a couple of
nanometre.
The appearance of the so-called Kohn anomalies in J (q), due to the resonance
matrix elements for interaction of filled and empty states in the immediate vicinity of
the Fermi surface, separated by q gets Fourier transformed into Friedel oscillations
in J (R). The long periodicity of these is associated with the smallness of the
difference in energy and momenta of the above conduction states and is critical
for the interpretation of both the magnetic structures of the rare earths and their
magnetic and electronic excitations.
A rather famous example of the verification of this type of dependence is shown
on Fig. 10 and is based on the processing of neutron data for the low-temperature
magnon excitations in praseodymium [9].
Yet, more generally, for cases, where L is large, a large orbital component
of the moment is expected, which can lead to anisotropic contributions to the
effective Heisenberg exchange Hamiltonian. A more general form of the interaction
is therefore required, with different interaction constants coupling the different
effective dipole moments of the 4f electrons:
1
Hdd = − Jαβ (ij )Jiα Jjβ (18)
2
ij
14 Magnetism of the Elements 677
The basic modes of the magnetic structures, which can be found in hexagonal
systems and specifically in the heavy rare earths are illustrated on Fig. 11.
The effects of the spin-orbit interaction in the transition metals are relatively week. It
is well-known that the latter is dominated by the crystal-field splitting, and generally
the orbital angular momentum is well-quenched. The existence of small orbital
momentum contributions, while experimentally verifiable, produces little effect on
the conduction electron spin polarisation [13]. The theoretical predictions for even
the most prototypical elemental ferromagnets vary substantially, depending on what
is the appropriate velocity averaging probed by a particular experiment. This is well
illustrated by the work of Mazin [11], which compares in detail the diffusive limit
spin polarisation for the magnetic 3d elements with the density of states one. The
DOS for the case of iron is featuring a rather high positive polarisation of about 70%,
while the same for Ni is even higher in magnitude, but opposite in sign: −80%,
close to EF . The latter is due to the essentially twice smaller exchange splitting
of the bands close to Fermi level and the band filling resulting in the equilibrium
Fermi level laying within the peak of the minority electron DOS. The situation is
altered dramatically in the ballistic case, with Fe and Ni both supposed to exhibit
|P | of between 35% and 45% and especially in the fully diffusive case, where Ni is
predicted to exhibit rather negligible polarisation (Fig. 12).
Spin-Polarised Photoemission
Before dabbing in the historical measurements of spin polarisation in the 3d
elements utilising photoemission, it is worth to note that some evidence of the
general understanding of the spin-split DOS can be obtained by experiments
involving optical excitation of direct intra- and inter-band transitions, too. This is
illustrated by a direct broad wavelength measurements of the optical conductivity
of single crystal specimen of iron, as illustrated on Fig. 13. The good agreement
between the calculated and computed absorption structure in the few eV vicinity of
EF justifies the validity of the band structure calculations based on local spin-density
approximation density functional theory.
The polarisation of the deeper states (10–100 eV) can be evaluated by techniques
related to photoemission, where electron beam rather than a photon one is bom-
barding the sample, such as Auger spectroscopy with polarisation analysis [14].
Polarisation levels as high as 70% are recovered, as illustrated in Fig. 14.
Later Photoemission Experiments
More elaborate experiments follow in UPS with and without polarisation of
the incoming photons and with and without polarisation analysis of the emitted
electrons. The latter analysis is performed, in most cases, using post-acceleration
14 Magnetism of the Elements 681
Fig. 12 Density of states and diffusion averaged density of states (dashed lines) for Fe (left panel)
and Ni (right panel) (After: [11])
to several keV and antisymmetric scattering from thin Au foil in a Mott detector.
These later investigations bring about more moderate values for the near-Fermi
level spin polarisation P of the 3d metals. One such example is the analysis
of thin in situ deposited films of Fe, Co and Ni by [16]. The reported values
of +54%, +21% and +15%, respectively, are all positive and shown to depend
little on the exact incoming photon energy and scale with the external field, in
a fashion resembling closely the bulk magnetisation of the materials. This latter
effect depends on two factors, the sensitivity towards projection of the photo-
electronic polarisation and the relatively large (millimetric) size of the illuminated
spots, containing a large number of magnetic domains. The exact relation between
the observed photoelectron polarisation and the DOS polarisation P (EF ) is, as
usual, more difficult to establish. The dominant contribution to the observed energy
distribution curves arises from a DOS peak, located at 0.30–0.35 eV below EF ,
attributed to the d-like states. The energy dispersion of the matrix elements to the
escape electron states has been shown to be negligible in the UPS of the transition
elements, as are the electron-magnon scattering, electron-plasmon coupling and
spin-orbit coupling. The sign problem, however, remains: most band structure
calculations predict negative band polarisation close to the Fermi level for Co and
Ni and positive for Fe; however, positive polarisation is evidenced experimentally
in both photo-emission and transport experiments.
682 P. Stamenov
60 b c 3
d 40
a
e
30
2 1
40 f
20
2
15
20 0
5 1
0
1 2 3 4 5 0 1 2 3 E, eV
E, eV
Fig. 13 Experimental optical conductivity in Fe and its separation into intra- and inter-band
components (left panel) and calculated total and spin-resolved optical conductivity (right panel).
(After: [15])
Field Emission
Considerable amount of experimental effort has been focused on the determination
of the spin polarisation of field-emitted electrons of both polycrystalline tips of Fe,
Co and Ni and material coated onto W tips. While wild variations are present in the
detected polarisation, depending on surface preparation, crystallographic direction
probed and adsorbed impurities, the maximal values quoted for Fe and Co are both
positive, at +80% and +47%, respectively; Ni shows a small negative polarisation of
−3.5% along the <111> axis, when pure and +15%, with hydrogen absorbed, which
makes for a difficult interpretation of the results [17].
PCAR
Individual reports exist on the spin polarisation of the 4f elements by means of
PCAR. The spin polarisation in Gd and Dy has been evaluated at 52% and 50%,
respectively, for epitaxial thin films, grown on (1120) sapphire (Al2 O3 ). These
14 Magnetism of the Elements 683
are relatively high, especially when compared with the ones measured by other
superconductor-based techniques [18]. Thulium is another example of a heavy rare
earth, exhibiting relatively high P of 41%, even in a polycrystalline form [19].
Tedrow-Messervey
One of the most complete measurements of Fermi level polarisation in the heavy
rare earths has been performed using artificially structured Al-Al2 O3 -RE junctions
[20]. The same reveals tunnelling polarisations ranging from about 13% for Gd,
down to only 2.7% for Tm. Interestingly, within the restrictions of absolute accuracy
that the technique permits, an essentially linear scaling is established between the
net moment and the polarisation evaluated within about 1 meV of EF , as visualised
in Fig. 15. Unfortunately, this simple finding does not carry through the rest of
techniques for polarisation measurements, as will be discussed later.
SXPS, ARUPS and SARPES
The use of synchrotron radiation has allowed for faster and more precise work in
not only deep states spectroscopy but also UV photoemission spectroscopy, using
photons with both linear and circular polarisation. Apart from the determination
of surface states spin splittings as low as 10-ns of meV, these types of datasets also
684 P. Stamenov
allow for the extraction of the spin polarisation. An example is the case of Gd, where
a value of 64% has been determined [21].
Field Emission
Measurements of the spin polarisation of field-emitted electrons of rare-earth films
evaporated onto W tips [17] show large variability with preparation conditions,
with both positive and negative values ranging from −35% to +66%, often showing
considerable applied magnetic field dependence, as well. A focus on the positive
values, occurring more often and somewhat more stable towards small amounts of
surface contamination, reveals an even-odd pattern with the following values +53%,
+31%, +45%, +34%, + 66% and +13% for Gd, Tb, Dy, Ho, Er and Tm, respectively.
Polarisation of the Heavy Rare Earths
There have been rather few experimental investigations of the spin polarisation
of the heavy rare earths in the last couple of decades, despite the relative ease of
surface preparation for these, stemming directly from their better chemical stability.
While isolated efforts have been made to characterise individual elements in their
polycrystalline form, as the examples of Er and Tm in Refs. [12] and [19], are
useful for the illustration of discrepancies of the absolute values of P , evaluated
by different techniques and the illustration of the effects influence of spin-orbit
coupling in these, there is a growing need to reconcile the available data from
all accessible techniques and elements. Such an attempt is presented in Fig. 16. A
few peculiar observations can be made straight away. The available data segregates
into two groups of two techniques, which share large similarities in the trend of P
as a function of number of the element Z. The results of TM and photoemission
experiments reveal relatively low polarisation values, scaling almost linearly down
from about 15%, for Gd. Quite unlike the latter, the data from field emission
experiments and from PCAR exhibits much higher polarisation values, with a peak
of about 65% for Er and a clear even-odd disparity, where even values of Z bring
along an additional 10–20% of polarisation. While the two techniques involved
are probing with rather different energy resolution, they are both predominantly
14 Magnetism of the Elements 685
Fig. 16 The polarisation of the heavy rare earths. (TM data form Ref. [11], PE data from Ref. [20]
FE data from Ref. [17])
Oxygen
Molecular Magnetism
and magnetic properties, spanning the best part of last century, is found in [25].
The susceptibility of α − O2 is anisotropic, with an easy axis along the primary
twofold direction of the monoclinic structure. Discrepancies between the sublattice
and intersublattice exchange constants extracted from the parallel and perpendicular
susceptibilities, from the antiferromagnetic resonance frequencies and from heat
capacity measurements suggest that the appropriate model requires multiple non-
collinear magnetic sublattices to account for all observations. The susceptibility of
β − O2 is essentially anisotropic with strong temperature dependence, due primarily
to the lattice expansion and a corresponding modulation of the exchange constants.
The paramagnetic susceptibility of γ −O2 does not follow the Curie-Weiss law, with
a substantially weaker temperature dependence than expected, due to a combination
of the existence of short-range correlations and the partial obstruction of free
rotation for the molecular units [25].
The relatively high susceptibility of liquid and solid oxygen is often an item
of practical experimental concern in high sensitivity magnetisation measurements
at cryogenic temperatures, as air can be easily admitted through various seals
in the sample space and condense in the vicinity of the tested sample [26]. In
order to measure the susceptibility of oxygen specimen with a sufficient accuracy,
early experiments have been typically conducted by absorption onto Vycor or
Graphite or on crystals prepared by directional solidification [27]. While thin partial
monolayer coverages exhibit transitions which are rather blurred, it takes only
four to five monolayers to establish the ordering at close to bulk parameters, with
sharp and well-defined critical temperatures, close to the ones shown in Fig. 17.
The magnetism here is strictly of molecular origin with the ground state 3 Σg−
exhibiting a spin of S = 1 and an orbital angular momentum of L = 0. The
next two available molecular states of spin S = 0 are sitting 0.98 eV (1 Δg ) and
1.63 eV (1 Σg+ ) above the ground state. This substantial spacing ensures negligible
population at temperatures where oxygen is solid [28]. The solid oxygen system
can be represented as antiferromagnetically interacting molecular spins, with rather
substantial anisotropy of K ≈ 16 J and therefore a gapped harmonic spin-wave
excitation spectrum Eg /kB = 80.5 K, as clarified by a set of muon spin rotation
(μSR) experiments [28].
More recent works focus on the completion of the magnetic and structural phase
diagram in the higher pressure-temperature region, with new phases, such as δ
and
, requiring tighter control of experimental conditions in order to clarify how
antiferromagnetic coupling between nearest-neighbour O2 molecules results in the
formation of larger O4 units in a singlet state and a second-order phase transition to
an orthorhombic structure [29, 30]. The nature of the high-pressure
phase (seen
in Fig. 18) is still currently under debate. The problem for the relative stability of
the couple of possible antiferromagnetic arrangements in four-molecule (tetramer
units, which are essentially flat and have opposing oxygen molecular moments
either sharing diagonal or a side in the unit rhombus) units versus the non-magnetic
solution is approached by a combination of high-accuracy DFT electronic structure
calculations and experimental observations of the evolution of lattice parameters
with pressure [31].
688 P. Stamenov
Fig. 17 The low-frequency susceptibility of solid oxygen. This has been measured at a frequency
of 155 Hz, with an excitation field of 0.19 mT, for a bulk specimen of 250.1 mg, below the boiling
point at ambient pressure Tb = 90.2 K. (After: [27])
Fig. 18 The high-pressure phase diagram of oxygen. The γ phase is paramagnetic. (After: [30])
14 Magnetism of the Elements 689
Fig. 19 AFM/MFM images, together with XMCD spectromicroscopy images of the same proton-
irradiated area of a thin carbon film. (After: [37])
layers [39]. If independently confirmed, this would represent the first demonstration
of a single element 4d ferromagnet, with a transition point above room temperature,
appreciable saturation magnetisation of Ms 0.15 MA/m and useful anomalous Hall
resistance. There is even a theoretical possibility for the realisation of a substantial
perpendicular anisotropy, as high as a MJ/m3 , if an out-of-plane texturing is to
be achieved. A resurgence of the interest in similar systems, narrowly missing on
satisfying Stoner’s criterion, such as Pd and Pt, is to be expected.
Heavy f-Shell Elements
These are the four stable paramagnetic actinides: Th, Pa, U and Np. The f -electrons
are more delocalised than for the corresponding 4f elements, forming hybridised
energy bands and none of the four order magnetically, although there are some
magnetic alloys and compounds. As a result of the strong spin-orbit coupling, the
L − S scheme that gives Hund’s rule moments for the rare earths breaks down for
the actinides, where the J − J coupling scheme is more appropriate, as the electrons
become more localised with increasing atomic number.
14 Magnetism of the Elements 691
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Contents
Magnetic Metallic Glasses and Nanocrystalline Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695
Alnicos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 698
Intermetallic Compounds of d-d and d-p Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705
Magnetic Shape Memory Alloys and Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705
Magnetic Heusler Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717
Intermetallic Compounds of 3d-4f Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 727
Sm-Co Permanent Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
Nd-Fe-B Permanent Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
Magnetocaloric Intermetallics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766
Heavy-Fermion Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
Abstract
J. P. Liu
University of Texas at Arlington, Arlington, TX, USA
e-mail: [email protected]
M. Willard
Materials Science and Engineering, Case Western Reserve University, Cleveland, OH, USA
e-mail: [email protected]
W. Tang
Materials Science and Engineering, Ames Laboratory, Ames, IA, USA
e-mail: [email protected]
© This is a U.S. Government work and not under copyright protection in the U.S.; 693
foreign copyright protection may apply 2021
J. M. D. Coey, S. S. P. Parkin (eds.), Handbook of Magnetism and Magnetic
Materials, https://doi.org/10.1007/978-3-030-63210-6_16
694 J. P. Liu et al.
E. Brück
Delft University of Technology, Delft, The Netherlands
e-mail: [email protected]
F. de Boer
University of Amsterdam, Amsterdam, The Netherlands
E. Liu · F. Hu · Y. Liu · J. Sun · B. Shen
Institute of Physics, Chinese Academy of Sciences, Beijing, China
e-mail: [email protected]; [email protected]; [email protected]; [email protected]
J. Liu
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences,
Ningbo, China
e-mail: [email protected]
C. Felser · G. Fecher · L. Wollmann
Max-Planck-Institute für Chemische Physik fester Stoffe, Dresden, Germany
e-mail: [email protected]; [email protected]
O. Isnard
Institute Néel and Université Grenoble Alpes, Grenoble, France
e-mail: [email protected]
E. Burzo
Babes-Bolyai University, Romania, Cluj-Napoca, Romania
e-mail: [email protected]
S. Liu
University of Dayton, Dayton, OH, USA
J. F. Herbst
Research & Development, General Motors R&D Center, Warren, MI, USA
A. de Visser
Van der Waals-Zeeman Institute, University of Amsterdam, Amsterdam, The Netherlands
e-mail: [email protected]
15 Metallic Magnetic Materials 695
Fig. 1 Elemental makeup of typical nanocomposite soft magnetic alloys with four major compo-
nents: magnetic transition metals (MTM), early transition metals (ETM), metalloid/post-transition
metals (PTM), and late transition metals (LTM)
Fig. 2 Magnetocrystalline anisotropy (K1 ) energy density for BCC Fe single crystal (dark blue)
as a function of angle from the [001] direction when viewed from the [100] projection and the
effective magnetocrystalline anisotropy (light green) for nanostructured BCC Fe (where N grains
are exchange coupled in a volumetric exchange length (Lex 3 ))
the exchange correlation length. The value of N in a cubic volume with sides
Lex can be estimated by the relation N = (Lex /D)3 . Using these equations and
the definition of Lex , the effective anisotropy can be determined in terms of the
crystalline material parameters, K1 , A, and D: K = K14 · D 6 /A3 . The exchange
softening described by this model breaks down as the grains become decoupled,
especially when the Curie temperature of the amorphous intergranular phase is
exceeded. This effective anisotropy is proportional to the coercivity and inversely
proportional to the permeability of nanocrystalline alloys.
Due to the small value of the averaged anisotropy, amorphous and bulk amor-
phous alloys have relatively small coercivity (again proportional to K1 ) [8–11]. In
these materials, the magnetoelastic anisotropy dominates the coercivity. An unfortu-
nate correlation between the square of magnetization and the magnetostrictive coef-
ficient is found for amorphous alloys. This effect is absent in nanocrystalline alloys
due to the two-phase microstructure which can be adapted to provide near-zero
values of magnetostrictive coefficient together with moderate magnetization [12].
There are a number of advantages that amorphous and nanocrystalline soft
magnetic alloys have over conventional large-grained materials, as summarized
in Fig. 3 and Table 1. Among the advantages, an important one is their better
performance at switching frequencies above 1 kHz. This is due in part to (a) the
smaller interaction of domain walls with the nanocrystalline grains and (b) their
higher resistivity. The hysteresis loss is present at all frequencies and proportional
to frequency. Controlling the microstructure and composition of the alloy can lead to
reduction of hysteretic losses. As the switching frequency is increased, eddy currents
in the alloy enhance the core losses. Reducing lamination thickness and increasing
the resistivity of the alloy help to limit the eddy currents. At high frequencies
(especially above 10 kHz), dynamic eddy current losses dominate. These eddy
currents are localized at the domain walls and can be minimized by refinement of
the domain structure in the alloys.
Alnicos
Fig. 3 The magnetic permeability at 1 kHz plotted against the saturation induction (μ0 Ms ) for
soft magnetic materials [8–11]
(darker matrix), and Cu-rich phases (white spots located between the corners of
α 1 -phase). The transverse microstructure of Alnico 8 is similar to that of Alnico
9, but the longitudinal α 1 -phase is elongated in two orthogonal <100> by the
applied field [27]. The magnets can be grouped into two main categories: isotropic
and anisotropic, distinguished by the different alloy crystallization processes and
thermomagnetic treatments.
700
Table 1 Magnetic properties of commonly used soft magnetic materials [13–16]. Metglas is amorphous, Senntix is bulk amorphous, and Finemet is
nanocrystalline. The saturation magnetization for alloys marked with “†” exceeds 1 T. Core loss (Pcm ) is reported for 60 Hz sinusoidal switching at 1T
maximum induction amplitude. Js is the magnetic polarization at saturation; μmax is the maximum permeability; Tx1 is the primary crystallization temperature
(10−8
Material Js (T) μmax (103 ) Hc (A/m) m) TC (K) Pcm (W/kg) λs (ppm) Tx1 (K)
Fe49 Co49 V2 2.4 5–50 16–398 27 1203 1.10 60
Soft Fe 2.16 10–50 4–80 10 1044 20 −2
Fe 3.2%Si 2.0 0.5–5 6 48 1018 0.84 7
Fe67 Co18 B14 Si1 1.8 50 3.5 123 658 0.66 35 703
Metglas 2605CO
Fe81 B14 Si3 C2 1.56 600 0.1 130 668 0.08 27 783
Metglas 2605SA1
Ni50 Fe50 1.4–1.6 70 4–20 40–50 753 0.33 18
Permalloy
Fe77 P7 B13 Nb2 Cr 1.31 2.5 556 0.65 W/m3 795
Senntix
Fe73.5 Si13.5 Nb3 B9 Cu 1.23–1.35 80 0.6–2.5 110 843 0.01 0–2 780
Finemet
Fe40 Ni38 Mo4 B18 0.88 800 0.4 160 626 † 12 683
Metglas 2826MB
Co70 Fe5 Ni2 B3 Si15 0.77 600 0.8 136 638 † 0 793
Metglas 2705M
Ni78 Fe17 Mo5 0.65–0.82 100–800 0.25–0.64 60 673 † 2–3
Supermalloy
J. P. Liu et al.
Table 2 Nominal composition and magnetic properties of cast Alnico 8 and 9 magnets [28, 29]
No. Characteristics Type Composition (wt.%, balanced Fe) Magnetic properties
Co Ni Al Cu Others Br(T) Hc (kA/m) (BH)max (kJ/m3 )
1 A 5–7 24.3 14.0 8.2 2.3 1.0 Nb 1.35 58.9 60.0
15 Metallic Magnetic Materials
Fig. 4 Microstructure images of a commercial Alnico 9 magnet (a) longitudinal, (b) transverse
[27]. (With kind permission from Elsevier)
Much work has been done on the composition, targeted at enhancing magnetic
properties, especially coercivity. The early studies on the relationship of columnar
crystallization conditions to compositions obtained a Br of 0.89–1.0 T, Hc of 141.7–
167.2 kA/m, and (BH)max of 87.6–93.1 kJ/m3 in the grain-oriented alloy containing
about 39 wt.% Co and 7–8 wt.% Ti [30]. By varying the Co and Ti content and
optimizing the microstructure, the magnetic properties of Alnico 9 were improved
as shown by No. 4–5 [29] in Table 2. Alnico 9 magnets are obtained by grain
orientation of Alnico 8 alloys with higher Co content [28]. By increasing the Co
content from 34 to 40 wt.%, as shown by No. 6–9 [28] in Table 2, Br decreases,
while Hc increases. A record (BH)max for Alnico of 104.3 kJ/m3 was achieved in
the magnet with 36 wt.% Co.
Several studies have confirmed that the addition of Ti effectively improves the
coercivity by increasing the local shape anisotropy constant [31], altering the lattice
mismatch between α 1 - and α 2 -phases [32], or narrowing the miscibility gap between
α 1 - and α 2 -phases [33]. Simultaneously increasing Co from 24 to 39 wt.% and Ti
from 0 to 7.5 wt.% resulted in an increase of Hc from 56.6 to 166.4 kA/m [31].
The addition of Nb showed a similar effect to that seen in Ti [34]. The addition
of 1.5 wt% Nb increased Hc by ∼ 24 kA/m. Moreover, Nb was found to help the
growth of columnar grains and suppress the precipitation of undesirable γ phase
[35]. Co-addition of Ti and Nb can significantly improve the coercivity, as shown
by No. 10–13 in Table 2, with a record Hc of 209.3 kA/m. Although Ti can improve
the coercivity, it makes the columnar crystallization of Alnico 9 difficult due to
fine-grained size. Therefore, a small amount of sulfur, selenium, or phosphorus
can be added to increase grain size and improve columnar crystal growth [36]. Cu
addition is necessary to separate the well-formed mosaic Fe-Co structure by forming
a Cu-rich phase [37], as shown in Fig. 4b. The Cu-rich phase forms as rods of 2
15 Metallic Magnetic Materials 703
nm diameter between α 1 -phase regions [27]. Cu was also thought to increase the
diffusion rate of atoms in the α 2 -phase [33].
Alnico magnets are manufactured using one of two processes: casting by
conventional foundry methods and powder metallurgical processing. The grain
orientation of cast Alnico 8 is random, whereas Alnico 9 with a perfect columnar
grain orientation is obtained by directional solidification. All the Alnico magnets
can be made from a powdered mixture of chemical elements or pre-alloyed powder
between 1250 ◦ C and 1350 ◦ C, but the grain orientation of magnets is random
[38, 39]. The magnetic alignment of cast and sintered magnets is achieved by
thermomagnetic treatment.
Gas atomization (GA) is an efficient technique to make Alnico powder [39]. The
powder is oval in shape and has an average size of 119 m. [40]. The powder can
be consolidated by techniques including hot pressing (HP), hot isostatic pressing
(HIP), and compression molding with subsequent sintering (CMS) [39, 41]. Table 3
shows the magnetic properties and grain size of HP, HIP, and CMS samples made
from the GA powder [41]. These magnets showed comparable magnetic properties
to cast magnets with the same composition. Injection-molded magnets are prepared
by mixing as-milled Alnico 8 powder with a binder [38]. The technique may allow
sintered magnets to be made with complex shapes.
A typical heat treatment process is shown in Fig. 5, where the alloys are first
solutionized (homogenized) at 1250 ◦ C for at least 30 min and then quenched to
obtain a single α-phase. Subsequently, the alloys are heat treated in a magnetic field
of 1.0–1.5 T, between 810 ◦ C and 840 ◦ C for 10–20 min to initiate the spinodal
decomposition. As a result, the α-phase separates into α 1 - and α 2 -phases, leading
to an initial coercivity. The applied magnetic field makes the Fe-Co particles to
preferentially grow in the field direction. A tempering treatment is performed at
lower temperatures for 15–30 h in two or more steps to promote chemical diffusion
between the α 1 - and α 2 -phases. These processes further increase the magnetic
anisotropy of the α 1 -phase, leading to enhanced coercivity.
The effects of thermomagnetic treatment at different conditions on microstruc-
ture and magnetic properties have been extensively investigated [20, 24, 26, 34,
37, 42, 43]. Iwama’s studies on thermomagnetic processing of Alnico magnets
established a linear relationship between a square of the wavenumber of the
modulated structure and the annealing temperature [44]. The relationship was
consistent with Cahn’s theoretical predictions on spinodal decomposition [18].
More recent studies confirm that achieving the highest Hc is closely related to
704 J. P. Liu et al.
3.0
Fe – V
ATOMIC MOMENT IN BOHR MAGNETONS
Fe – Cr
2.5 Fe – Ni
Fe – Co
Ni – Co
2.0 Ni – Cu
Ni – Zn
Ni – V
1.5
Ni – Cr
Ni – Mn
1.0 Co – Cr
Co – Mn
PURE
0.5 METALS
0
Cr Mn Fe Co Ni Cu
6 7 8 9 10 11
ELECTRON CONCENTRATION, C
Fig. 6 Average atomic moments of binary alloys of the iron-group elements. (Reprinted figure
with permission from [47] by the American Physical Society)
optimizing the microstructures [26]. Chu’s studies explained that there exist two
splittings of Fe-Co particles during magnetic annealing which leads to a decrease of
mean diameter of Fe-Co particles and thus increases coercivity [42]. High magnetic
fields (up to 10 T) strongly influence the modulated (or mosaic) microstructure [43]
but did not improve Hc .
15 Metallic Magnetic Materials 705
Magnetic shape memory (MSM) alloys and compounds are ferromagnets that
exhibit large strains under an applied magnetic field due to martensitic phase
transformation [173–175]. Currently, the materials with the best MSM properties
are the near-stoichiometric Ni2 MnGa compounds (a Heusler alloy) with five- and
seven-layer stacked martensite structures that show magnetic-field-induced strains
(MFIS) of 6.0% and 9.5% in a field less than 800 kA/m, respectively. This exceeds
the normal magnetostriction based on magnetoelasticity by orders of magnitude.
The origin of the MFIS in MSM alloys is due to magnetically induced twin boundary
motion in the martensitic phase. The MSM operation temperature is between
150 and 330 K depending on composition. These characteristics render the MSM
alloys promising functional materials for the development of magneto-mechanically
controlled actuators or dampers. The composition, crystal structure and struc-
tural/magnetic transition temperatures, and field-induced strain in single-crystalline
Ni-Mn-Ga alloys are given in Table 5. The characteristics and performance of Ni-
Mn-Ga alloys in other forms of polycrystals, composites, and thin films are collected
in Table 6.
In the second part of this section, the multifunctional MSM systems such as Ni-
Mn-(In, Sn, Sb) and Ni-Co-Mn-Ti Heusler alloys and hexagonal MM’X compounds
are addressed. Magnetic-field-induced reversible martensitic transformation has
been achieved in newly developed alloys, where a metamagnetic transition occurs
from weak magnetic martensite (austenite) to ferromagnetic austenite (martensite)
by applying a magnetic field. These alloys have the following advantages: (i) shape
recovery can be obtained in polycrystals, (ii) high blocking stress can be obtained,
and (iii) multifunctionality with large magnetocaloric effect and magnetoresistance
706
Table 4 Structure and magnetic properties of d-d and d-p types of intermetallic compounds (F stands for ferromagnetic, FI for ferrimagnetic, AF for
antiferromagnetic, SDW for spin density wave, and H for helimagnetic order. We include P for paramagnets if peculiar observations, e.g., metamagnetism,
are reported. The values given for the magnetic moment are per atom if not stated differently. Compositions can be either stated as weight % or atom a/o. RT
stands for room temperature, MCE for magnetocaloric effect, TC for Curie temperature, TN for Néel temperature sol. soln for solid solution and stoichiom fo
stoichiometry). Compounds are listed in order of 3d element
System Compound Type of order TC /TN (K) μ(μB ) Comment Ref.
Sc-Fe ScFe2 F 542 1.37 C14 Laves phase [48]
F >300 2.1 C36 Laves phase [49]
Sc-In Sc3 In F 16 0.06 [50]
Sc-Co ScCo2 P Metamagnet [51]
Ti-Be TiBe2 AF 10 1.64 C15 Laves phase [52]
Ti-Fe TiFe2 AF 0–65 C14; 67a/o Fe-64.5a/o Fe [53]
F 424–323 2.1–1.1 C14; 71.4a/o Fe-69.5a/o Fe [54]
Ti-Co TiCo3 F <80 Excess Co [55]
TiCo2 F 44 0.12 C36 [56]
AF 43 C15 [56]
Ti-Ni (Ni,Ti) F 627–0 0.6–0 15% Ti results in vanishing moment [57]
V-Fe σ -phase F 210–100 <0.2 D8b weak itiner. F 40–54a/o [V] [58]
α (V, Fe) F 0.6–1.3 B2 superstructure [59]
V-Co (V, α-Co) F Steep decrease of TC [57]
<RT @ 25%[V]
V-Ni (V, Ni) F Steep decrease of TC [57]
<RT @ 6%[V]
σ -phase F 52 D8b 64.2a/o [V] [60]
Cr-Be CrBe12 F 50 0.2 [61]
Cr-Mn (α-Cr, Mn) AF 300–800 [62]
Cr-Fe σ -phase F 9–47 0.04–0.13 D8b weak itiner. F 49–43a/o [Cr] [58]
(α-Cr, Fe) F 1045–0 2.2–0 Complete solubility if quenched. Initial increase of TC <RT @ 70% [Cr] and [57]
J. P. Liu et al.
Table 4 (Continued)
System Compound Type of order TC /TN (K) μ(μB ) Comment Ref.
Mn-Zn MnZn F ∼500 K 0.7 Doping with Ga enhances F moment [84]
Mn-Ru (Mn,Ru) AF <300 Strong concentration dependence; also spin glass [85]
Mn-Rh Mn3 Rh AF 855 [83]
Mn-Pd Mn(Pd,Pt) AF 870 [83]
Mn2 Pd3 AF 640 Superstructure of double CuAu type slightly changes TN [86]
Mn-Ir Mn3 Ir AF 960 [83]
MnIr AF 1145 [83]
Mn-Pt MnPt3 F 400 3.6/Mn 0.4/Pt TC strongly composition dependent [87]
MnPt AF 975 4.3/Mn [87]
Mn3 Pt AF 475 3.3/Mn [87]
Mn-B MnB2 F 157 0.25 [88]
Mn3 B4 AF 392 2.92/2c; 0.44/4g T < 262 K spiral structure [89]
MnB F 578–572 1.92–1.84 [90]
Mn-Al MnAl F 656 1.65 L10 type [91]
Mn-Ga Mn3 Ga2 F 658–748 0.5–0.9 60–67% Mn L10 tetragonal low-temperature phase [92]
(high-coercivity phase)
Mn8 Ga5 F 210 1 62% Mn 973 K annealed and quenched cubic γ brass [93]
Mn2 Ga FI 470 70–72% Mn DO19 hexagonal high temp phase [94]
Mn3 Ga AF/FI 600/800 Magnetostructural phase transitions at 600 and 800 K [95]
Mn-In Mn3 In FI 80 Spin-glass state? [96]
Mn-C Mn23 C6 AF 105 [97]
Mn-Si MnSi H 29.5 0.4 Helimagnet; skyrmions [98]
Mn-Ge Mn11 Ge8 AF/F 140/274 Low T AF spin flop at 140 K to F [99]
Mn5 Ge3 F 300 [100]
Mn5 Ge2 AF/F 315/470110/204 Two superstructures with two TC and first-order spin reorientation [101]
J. P. Liu et al.
Table 4 (Continued)
System Compound Type of order TC /TN (K) μ(μB ) Comment Ref.
Fe-Rh FeRh F-AF RT AF 3.3/FeF3.1/Fe; 1.0/Rh Ordering temperature quite sensitive to slight deviations [116]
from stoichiometry; large MCE
FePd F 760 L10 superstructure; hard magnetic [117]
Fe-Hf Fe2 Hf F 427 1.52/Fe C15 [118]
F 588 C14 [118]
Fe2 (Hf,Ta) F RT C14, exchange inversion [119]
Fe-Os α-Fe,Os F Strong reduction of TC [57]
Fe-Ir α-Fe,Ir F Strong reduction of TC [57]
Fe-Pt FePt3 AF 170 3.3/Fe [120]
FePt F 750 2.8/Fe;−0.25/Pt Hard/soft magnet order/disorder, nanocomposites [121]
Fe3 Pt F 280/430 2.7/Fe;0.5/Pt Disordered/ordered; Invar [122]
Fe-B FeB F 590 1.1 [90]
Fe2 B F 1013 1.91 [123]
Fe-Al α-Fe,Al F Decrease of TC with Al; <RT @ 16%[Al] [57]
Fe3 Al F 823 2.2/FeI1.5/FeII [124, 125]
Fe-Ga α-Fe,Ga F 19a/o Ga magnetostrictive material [126]
Fe3 Ga4 AF/F 360/62 Metamagnet [127]
AF 390 Four inequivalent Fe sites [128]
Fe3 Ga F >870 FCC; F L12 phase transforms to NM DO19 @ high T [129]
F 600 2.5/FeI1.7/FeII BCC; Fe3 Al type [125, 129]
Fe-C Fe3 C F 483 [83]
Fe-Si FeSi F 15 Crossover in magnetic properties, susceptibility max. [130]
above RT
(Fe,Co)Si H Helimagnet and skyrmions [131]
Fe3 Si F 800 K 2.4/FeI1.2/FeII [124]
J. P. Liu et al.
Fe-Ge FeGe2 AF 190 2.4/Fe Two-sublattice ferrimagnet due to vacancies on one sublattice [132]
FeGe H 279 1.0 Cubic B20; skyrmions [133]
AF 340 1.7, 0.5, <0.4 Monoclinic; three different magnetic moments; simple AF above 120 K; [134]
incommensurate at low T
AF 411 1.7 Hexagonal B35 [135]
Fe1.67 Ge F 485 1.6 Ni2 In type; two Fe sublattices S=1 and S= ½, respectively [132]
Fe3 Ge F 740/640 2.2/2.0/Fe Cubic/hexagonal [136]
Fe-Sn FeSn2 AF 378 1.7/Fe Tt = 93 K [137]
FeSn AF 370 1.5/Fe [138]
15 Metallic Magnetic Materials
Table 4 (Continued)
System Compound Type of order TC /TN (K) μ(μB ) Comment Ref.
Co-Y CoY3 F <2 ∼0 [148]
Co3 Y4 F <2 0.03/Co 43 a/o [Co] [148]
Co2 Y P Metamagnet [148, 149]
Co3 Y F 306 0.55/Co [148]
Co7 Y2 F 639 1.06/Co [148]
F 987 1.50/Co [148]
F 1186 1.62/Co [148]
Co-Zr Co2 Zr F 55 0.2/Co Co2.8 Zr [150]
F 160 0.4/Co Co3.0 Zr [150]
Co4 Zr F 760 [57]
Co23 Zr6 F 766 1.4/Co [151]
Co11 Zr2 F 769 1.24/Co Co5.1 Zr [152]
Co-Nb Co3 Nb ? ? 0.17/Co Probably impurity phase [153]
Co-Ru Co80 Ru20 F ∼800 HCP sol. soln [154]
Co94 Ru6 F 1167 1.47 FCC sol. soln [154]
Co-Rh Co70 Rh30 F ∼990 HCP sol. soln [154]
Co93 Rh7 F 1277 1.61 FCC sol. soln [154]
Co60 Pd4 0 F ∼1080 HCP sol. soln [154]
Co73 Pd27 F 1205 1.49 FCC sol. soln [154]
Co-La Co19 La5 F 616 0.1/Co [148]
Co5 La F 840 [155]
Co13 La F 1297 1.58/Co [148]
Co-Hf Co3 Hf F 40 0.12/Co [153]
Co23 Hf6 F 499 0.66/Co [153]
J. P. Liu et al.
Co7 Hf F 600 1.14/Co [153]
Co-Re Co50 Re50 F Sol. soln; no magnetic data found [156]
Co-Os Co80 Os20 F ∼630 HCP sol. soln [154]
Co99 Os1 F 1258 1.66 FCC sol. soln [154]
Co-Ir Co70 Ir30 F ∼680 HCP sol. soln [154]
Co90 Ir10 F 1108 1.43 FCC sol. soln [154]
Co-Pt CoPt3 F 460 1.29/Co; 0.45/Pt Stoichiom.; disordered [157]
∼430 22 a/o [Co]; disordered [158]
F 320 1.64/Co; 0.26/Pt Stoichiom.; ordered [157]
15 Metallic Magnetic Materials
Table 6 Martensitic transformation temperature, T0 ; Curie temperature, TC ; the martensitic structure type and the field-induced strain for Ni-Mn-Ga
polycrystals, composites, and thin films
Composition T0 (K) TC (K) Martensitic structure type Field-induced strain Remarks Ref.
Ni50.9 Mn27.1 Ga22 328 371 5M 0.1% Magneto-thermal training [190, 191]
epoxy resin
Ni50.9 Mn27.1 Ga22 1% – [192]
polycrystalline fibers
Ni50.6 Mn28 Ga21.4 – – – 0.115% Introducing pores with similar sizes [193]
polycrystalline foam to grain size
8.7% Introducing pores smaller than the [194]
grain size
Ni51 Mn29 Ga21 328 – 5M 0.16% Free strain [195]
polycrystalline
1% Polyurethane fills the cracks; after [196]
thermomagnetic training
Ni50 Mn29 Ga21 polycrystalline 328 – 5M 1% – [197]
Ni50.5 Mn24 Ga25.5 226 – – 1.5% Temperature varies under [198]
polycrystalline 1.5 T bias field
Ni51.4 Mn28.3 Ga20.3 311 – 5M 0.8% [199]
film
J. P. Liu et al.
15 Metallic Magnetic Materials 717
can be realized . Data on these non-Ni-Mn-Ga single crystals and polycrystals are
listed in Tables 7 and 8, respectively.
Table 7 Martensitic transformation temperature, T0 ; Curie temperature, TC ; the martensitic structure type and the field-induced strain for non-Ni-Mn-Ga
single-crystal compounds. 14M, 14-layer stacked martensite
Martensitic Field-induced
Composition T0 (K) TC (K) structure type strain (%) Remarks Ref.
Mn50 Ni25 Ga25 588 270 NM 4.0 Thermal induced Ref[200]
2.0 Magnetostrain
Co45 Ni25 Ga20 351 – NM 1.0 Oriented polycrystalline [201]
Ni51 Fe18 Ga27 Co3 338 300 14M 0.7 At room temperature [202]
Ni45 Co5 Mn36.6 In13.4 292 382 14M 2.9 3% pre-strain at room temperature [203]
Ni45 Co5 Mn36.5 In13.5 260 400 – 3.13 Compressive stress 125 MPa, [100] single crystal [204]
Ni49 Fe18 Ga27 Co6 – – NM 8.5 Pre-strain (8 MPa), single variant at room temperature [205]
Ni49.5 Fe14.5 Mn4 Ga26 Co6 320 420 – 11.3 Pre-strain (8 MPa), single crystal at room temperature, [206]
variant rearrangement
Fe43 Mn28 Ga29 213 – NM 0.6 Volume change +1.35% [207]
Fe70 Pd30 293 FCT 0.6 Single crystal, 256 K, axial field [208, 209]
2.3 kOe/978-3-030-63208-3/[100], applying field in
(100) plane, reversible, variant rearrangement
J. P. Liu et al.
Fe68.8 Pd31.2 293 FCT 3.1 Single variant, 77 K, [100], variant rearrangement [210]
Fe3 Pt 85 FCT 2.3 Single variant, 4.2 K, [100], variant rearrangement [210][211]
Fe3 Pt 85 FCT Recoverable, 0.6 Single crystal, [001], 4.2 K, capacitance method in a pulsed [212]
magnetic field
1.7
Fe3 Pt 85 FCT Recoverable, 0.45 Single crystal, [001], 20 K [213]
Recoverable, 0.95
Mn0.965 CoGe 292 – Orthorhombic 11.6 (c-axis Derived from XRD analysis; volume change +4% [213]
expansion)
15 Metallic Magnetic Materials
Mn0.84 Fe0.16 NiGe 241 – Orthorhombic 12.3 (c-axis Derived from XRD analysis; volume change +2.7% [214]
expansion)
Mn0.9 Ni0.1 CoGe 290 – Orthorhombic 11.3 (c-axis Derived from XRD analysis; volume change +3.9% [215]
expansion)
Mn0.64 Fe0.36 NiGe0.5 Si0.5 348 – Orthorhombic 12.6 (c-axis Derived from XRD analysis; volume change +3.6% [216]
expansion)
719
720
Table 8 Martensitic transformation temperature, T0 ; Curie temperature, TC ; the martensitic structure type and the field-induced strain for non-Ni-Mn-Ga
polycrystalline compounds. 10M, ten-layer stacked martensite; 6M, six-layer stacked martensite
Field-induced strain
Composition T0 (K) TC (K) Martensitic structure type (%) Remarks Ref.
Ni53 Mn25 Al22 234 310 NM 0.1 [217]
Ni50 Fe25 Ga25 142 430 NM 0.3 Ribbon [218]
Ni50 Mn34 In16 305 210 10M 0.12 [219]
Co50 Ni20 Ga20 270 >400 NM 0.15 Ribbon [220]
Ni45 Co5 Mn37 In13 320 390 NM 0.25 [221]
Ni50 Mn33 Fe4 In13 140 320 10M 0.28 [222]
Ni43 Co7 Mn39 Sn11 305 400 6M + 10M 1.0 1.3% pre-strain at 310 K [223]
Ni49 Fe1 Mn36 Sn14 170 322 NM 0.2 Thermal induced [224]
Ni50 Mn35 Sn15 230 – – 0.2 Thermal induced [225]
Ni46 Cu4 Mn38 Sn12 280 – – 0.12 [226]
Fe50 Mn22.5 Ga27.5 132 – NM 3.6 Thermal induced, volume [227]
change +0.85%
Ni35 Co15 Mn35 Ti15 255 391 5M 0.25 Volume change −1.95% [228]
J. P. Liu et al.
15 Metallic Magnetic Materials 721
Fig. 7 (a) Zinc-blende crystal structure: red spheres, Ga; green spheres, As. (b) Half-Heusler
structure: red spheres, Mg (Ni); blue spheres, Li (Zr); green spheres, As (Sn). (c) Schematic density
of states of ZrNiSn: green, bonding and antibonding sp3 -states; red, non-bonding d10 -states. (d)
Schematic density of states of half-metallic NiMnSb (see Refs. [236, 237])
to an octahedral field due to the filling of the voids at the 4d position of the C1b
structure.
Many compounds (≈1000) are known in this family [230]. Due to the complex
interplay of atomic interactions, a variety of magnetic phenomena have been
observed, of which ferromagnetism, ferrimagnetism, or antiferromagnetism are the
most intensively investigated. In case of X2 YZ Heusler compounds, semiconductors
are found with 8, 18, or 24 valence electrons per formula unit such as Fe2 Val [238].
If the number of valence electrons differs from 24, these materials are usually ferro-
or ferrimagnetic, where the magnetic moment per formula unit is directly related
to the number of valence electrons minus 24 resulting in a Slater–Pauling type
behavior [239, 240]. Compounds containing Co, Mn, or Fe atoms on the X and/or
Y sites usually follow the Slater–Pauling rule. Prominent examples are Co2 MnSi
and Co2 FeSi that exhibit a strong localized moment at Mn or Fe and an itinerant
moment at Co. The local moments sum to 5 or 6 μB , respectively. Another out of
many possible examples is ferromagnetic Co2 TiSn where the magnetic moments
mainly reside on the Co sites [241]. The compound has a magnetic moment
of 2 μB , and a Curie temperature of ≈ 350 K is observed. Co2 MnSi performs
best of all Heusler compounds in magnetic tunneling devices. Fe-doped Co2 MnSi
electrodes exhibited giant tunnel magnetoresistance (TMR) ratios of 2610% at
4.2 K and 429% at 290 K [242]. Co2 MnSi was subject of a detailed investigation
accessing its surface spin polarization which has been shown to be certainly half-
metallic within the accuracy of spin-polarized photoelectron spectroscopy [243].
For ferromagnetic, half-metallic Heusler compounds, a general relation between
valence electron count NV and Curie temperature was established according to
which TC scales approximately linearly by 175 K per electron deviating from
NV = 24 [244]. Co2 FeSi is ferromagnetic with the Fermi energy being located at
the upper edge of the minority band gap. Therefore, it is at the borderline between
a regular and a half-metallic ferromagnet. It exhibits the highest Curie temperature
of all known Heusler compounds with TC ≈ 1120 K [245].
In Heusler compounds, the X sites are located in a hetero-cube (tetrahedral
symmetry) that is formed by the Y and the Z atoms (Fig. 8). Within a unit
cell, eight such sites exist. The electronic states of the X atoms develop to a
delocalized magnetic sublattice in comparison to the localized moment of Mn at
the Y site. The presence of two strong magnetic sublattices on the X and Y sites may
lead to complex magnetic structures such as ferrimagnetic order. For example, in
hypothetically cubic Mn3 Ga, the moments on the X and Y sites are expected to be
coupled in an antiparallel manner [246]. Similar to the ferromagnetic systems, in
ferrimagnetic half-metallic Heusler compounds, the Curie temperature scales with
the sum of the local magnetic moments on the two antiparallelly aligned sublattices
[247].
The Wyckoff position 4b is most often occupied by the most electropositive
element (i.e., earlier transition metal). The 8c position of space group 225 can be
split into the positions 4c and 4d of space group 216 keeping the fcc lattice. In many
Mn2 -based Heusler compounds, an arrangement is observed where half of the Mn
atoms occupies site 4b and the other half is found on 4d of space group 216. This
15 Metallic Magnetic Materials 723
a b 6
4
E-εF [eV]
2
0
-2
-4
Energy
-6
-8
-10
-12
c d
Magnetic moment per atom m [µ8]
C
Co2FeGa
o
o
Fe
Tc
2
FeCo Calc.
M
Co2TM
Si
nS
2.0 FeNi 1000
i
FeCo
C
NiCu
o
FeV 800
M
2
1.5 Co2FeSi
nS
CoCr
n
o
NiCr
C
2
NiMnSb Co2MnSi
rG
C
600
o
a
M
2
1.0
C
nA
CoMnSb Co2MnAl
o
VG
2
l
a
Co2CrGa 400
C
Ni
o
0.5
C
2
Co2VAI
rA
l
GGA 200
Co2TiAl
0.0 Cr Co2TiAl Co2VSn
0
6 7 8 9 10 11 25 26 27 28 29 30
Valence electrons per atom Nv. Valence electrons per f.u. Nv.
Fig. 8 (a) L21 Heusler structure, (b) band structure of Co2 MnSi, (c) Slater–Pauling rule, and (d)
scaling of the Curie temperature in Co2 YZ Heusler compounds (see references [236, 237])
situation leads to the inverse Heusler structure with the lower symmetry of space
group 216 (Fig. 9). This space group does not contain an inversion center, and it has
been argued that the Dzyaloshinskii–Moriya interaction may play a crucial role on
the magnetic properties. Most prominent examples of the ferrimagnetic materials in
the inverse structure are Mn-rich Heusler compounds [247–249]. As already stated
by Kübler in 1983, Mn plays the unique role in Heusler compounds, due to the
localization of its site moment, that is traced back to a strong exchange split [250].
An example for an inverse Heusler compound is (MnCo)MnAl [251]. Mn occupying
the 4b site shows a localized moment of ≈ 3 μB . The moment of the atoms in the
Mn-Co plane (Mn(4d) and Co(4c)) counterbalances the strong local moment by
moments of mMn(4d) = −2 and mCo(4c) =1 μB , resulting in a total moment of 2 μB
according to the Slater–Pauling rule: Mtot = NV − 24 = 7(Mn4d) + 9(Co4c) +
7(Mn4b) + 3(Ga4a) − 24.
Contrary to expectations, D03 -type ordered cubic Mn3 Ga could not be obtained
as stable bulk material from chemical synthesis. Hexagonal antiferromagnetic
Mn3 Ga also turned out to be metastable. Surprisingly though, a stable and tech-
nologically useful tetragonal, ferrimagnetic structure exists (prototype: TiAl3 , tI8,
I4/mmm, 139). Tetragonal magnetic Heusler compounds are of special interest,
thanks to their potential for spin transfer torque magnetic random access (STT-
MRAM) devices [24, 252], and they have been considered as candidate materials
724 J. P. Liu et al.
Fig. 9 Crystal structure of (a) the magnetic Heusler compound Mn2 VAl, (b) the inverse Heusler
compound Mn2 CoGa
band structure. In general, such singularities may additionally lead to a very high,
peaked density of states at the Fermi energy. One particular van Hove singularity is
associated with a saddle point in the dispersion curves in the vicinity of the Fermi
energy. It appears sometimes very pronounced in the direction of the fcc Brillouin
zone. It often causes less pronounced maxima in the density of states compared to
other global maxima. The occurrence of the saddle point-type van Hove singularity
in Heusler compounds is often associated with the band Jahn–Teller effect. Similar
to the removal of a high density of states at the Fermi energy, the van Hove
singularity is removed or shifted away from the Fermi after a structural distortion.
The distortion will open a gap or more often a pseudo-gap in the band structure
to lower the total energy of the system by lowering the band energy. A pseudo-
gap describes the state in which the band structure may not be completely gapped
after the distortion. Examples of known tetragonally distorted Heusler compounds
are the magnetic shape memory compounds: Ni2 MnGa or Mn2 NiGa [200, 255]. At
increased temperature or in a distinct magnetic field, these materials are cubic. It is
found that the origin of the tetragonal distortion at low temperature is a localization
of a van Hove singularity near to the Fermi energy. Following this observation,
a series of new compounds such as Mn3−x Fex Ga (0 ≤ x ≤ 2), Mn2−x Co1+x Ga
(0 ≤ x ≤ 0.5) was synthesized where such a van Hove singularity is responsible
for the tetragonal distortion. In rhodium-containing Heusler compounds such as
Rh2 FeSn, a tetragonal distortion also occurs because of a van Hove singularity
in the vicinity of the Fermi energy. This tetragonal distortion was attributed to an
electronic instability of the band Jahn–Teller type by Suits [256].
The tetragonal distortion is further influenced by a strong spin–orbit interaction.
This is the case for 4d or 5d transition metals on the tetrahedral (8c) sites. Known
compounds are, for example, Rh2 FeSn, Rh2 CoSn, and Rh2 FeSb [256]. The splitting
of the d states into d3/2 and d5/2 will have an additional impact on the states at
the Fermi energy that are responsible for the band Jahn–Teller effect. Furthermore,
the spin–orbit interaction results in a pronounced magnetocrystalline anisotropy in
tetragonal Heusler compounds.
The formation of new alloys using two known Heusler compounds offers a
possibility to create new alloys and tune their properties such as the structural
parameters, as well as magnetic characteristics or electric transport quantities. An
example for mixing of similar compounds is the series of alloys between the
cubic systems Mn2 CoGa and tetragonal Mn3 Ga [246, 251, 254]. Tetragonal, hard
magnetic Mn3 Ga was doped in thin films with Co which caused magnetic moment
to drop and the coercive field to increase [251]. The systems with a Mn content
of x ≤ 0.5 remain in the tetragonal lattice but become cubic for x > 0.5 [249].
The magnetic moments of both cubic and tetragonal compounds vary linearly with
respect to the valence electron count. This is the famous Slater–Pauling rule for
the cubic compounds (x > 0.5) and a pseudo-Slater–Pauling-type behavior for the
tetragonal alloys as shown in Fig. 10 and Ref. [249].
In case of cubic compounds, this means that the magnetic moment per formula
unit is exactly the number of valence electrons minus 24. The Slater–Pauling-type
behavior is often a sign of bulk half-metallicity (100% spin polarization) in that
726 J. P. Liu et al.
Fig. 10 (a) Structure of a tetragonal inverse Heusler compound and corresponding behavior of
the calculated spontaneous magnetization due to the tetragonal distortion of the (b) Mn2 Y3d Ga,
(c) Mn2 Y4d Ga, and (d) Mn2 Y5d Ga compounds
varying the number of valence electrons varies the filling of the metallic spin-
polarized band such that the moment is increased or decreased directly proportional
to the number of valence electrons. This is true as long as the Fermi energy
remains within the energy gap of the semiconducting spin-polarized band. These
experimental observations are in agreement with the finding that a tetragonal
distortion occurs when a high density of states appears in the vicinity of the
Fermi energy. Cubic Mn3 Ga and tetragonal Mn3 Ga doped with Co are only two
possibilities. The knowledge about the Slater–Pauling rule helps to identify other
compositions such as the 1:1 combination of Fe2 MnAl (26 valence electrons) and
Mn2 VAl (22 valence electrons). Deviations of the 24-electron rule are possible in
case of tetragonal, inverse Heusler compounds [249]. Work on Ru-doped Mn2 Ga
shows that crossing the compensation point, where the anomalous Hall effect
chances sign, is possible [257].
Fully compensated half-metallic ferrimagnets are very interesting materials
[246]. An overview, predicting a large number of half-metallic fully compensated
ferrimagnetic Heusler compounds, is given in Ref. [258]. In the system Mn-Pt-
Ga, a new tetragonal Heusler compound with a compensated ferrimagnetic state
was designed using density functional theory [259], explicitly treating Mn-Pt
substitution. In the vicinity of the compensation point xcomp , a giant exchange
bias of more than 3 T and a large coercivity were established. The large exchange
15 Metallic Magnetic Materials 727
anisotropy originates from the exchange interaction between the compensated host
and ferrimagnetic clusters that arise from intrinsic anti-site disorder [259].
In magnetic Heusler compounds, the alignment of adjacent spins often is
assumed to be collinear, which has been proved correct in many systems, especially
for the soft magnetic Co2 YZ alloys. With the observation of spin canting and
reorientation in Mn2 RhSn and the persistent interest in topological properties,
noncollinear order found its way back into the focus of Heusler compound research.
Spin reorientation from collinear to canted spins was observed for Fe2 MnSi [260,
261], and a conical ground state has even been suggested for thin films of Mn3 Ga.
The study of some other compounds is enlightening [260, 261]. A phase transition
in the magnetization in Mn2 RhSn could be resolved with the help of density
functional theory [262]. The phase transition could be modeled through a spin
reorientation transition from a noncollinear to a collinear ferrimagnetic structure.
Mn2 RhSn is only one compound with a small energy difference between the out-
off-plane and in-plane magnetization [249]. The relatively small magnetocrystalline
anisotropy may be counteracted by the Dzyaloshinskii–Moriya exchange in this
non-centrosymmetric structure [262]. Mn2 RhSn exhibits a topological Hall effect
and – similar to related Heusler compounds – shows evidence for skyrmions.
However, we are sure that Mn2 RhSn is not the only Heusler compound revealing
noncollinear magnetic order, and new physics will emerge in this subgroup of
Heusler compounds.
The class of intermetallic compounds formed between the rare-earth elements (4f
elements) and the 3d transition metals (Fe, Co, and Ni) contains a huge number of
binary and ternary systems. Here we survey selected systems which are of particular
interests for hard magnetic and magnetocaloric applications.
The R2 M7 (R = rare earth, M = Fe, Co, Ni) may exist in either hexagonal
Ce2 Ni7 -type (P63 /mmc) or rhombohedral Gd2 Co7 -type (R3m) structures. Both
allotropic forms often occur together [263]. Th2 Fe7 is the only reported R2 Fe7 phase
to date. It has a ferromagnetic structure below 570 K and a saturated magnetization
of 9.59 μB /formula unit [264]. For M = Co or Ni, the R2 M7 compounds form for
all the rare-earth elements. The magnetic properties of the R2 M7 compounds are
summarized in Tables 9 and 10 for M = Co, Ni, respectively.
A newly studied stable system R5 M17 was identified in the Nd-Fe binary
diagram [284] with ferromagnetic order and a TC of 503 K, later identified as
Nd5 Fe17 [285] crystallizing in the P63 /mcm space group. Its magnetization is 46.5
and 37.5 μB /formula unit at 4 and 300 K, respectively [286] (see Table 11). This
corresponds to a large magnetic moment per Fe atom of 2.1 μB /f.u but with a
basal plane spin orientation. Nd5 Fe17 and Sm5 Fe17 are the only reported R5 Fe17
phases to date. The Sm isotype is more difficult to synthesize and was first reported
from the investigation of the Sm-Fe-Ti system where partial Ti for Fe substitution
is possible [287] and more recently in a similar manner in the Sm-Fe-V ternary
728
Table 11 Magnetic properties and room temperature lattice parameters of R5 Fe17 compounds
Easy Ms at
magnetization 300 K
a(10−3 nm) c(10−3 nm) Space group direction TC (K) Ms at 4 K (μB /f.u.) Hc (MA m−1 ) (μB /f.u.) Ref.
Nd5 Fe17 2021.4 1232.9 P63 /mcm Basal plane 503 46.5 – 37.5 [285, 286]
Sm5 Fe17 2052.0 1229.0 P63 /mcm c 550 – 1.9 25 [287, 288, 293]
J. P. Liu et al.
15 Metallic Magnetic Materials 731
orbital moment on one Co site is attributed to its peculiar and asymmetric atomic
local environment.
In the RCo5 compounds, the Co sublattice anisotropy is dominant at high
temperature along the whole R series. For R = Pr, Nd, Tb, Dy, and Ho, a
spin reorientation occurs due to competition with the R anisotropy. The easy
magnetization direction is along the a-axis for R = Nd, Tb, and Dy, whereas for
Pr and Ho it is tilted away from the c-axis by 23◦ and 84◦ , respectively [303, 304].
Unlike for the RM5 compounds with M = Fe and Co, the RNi5 ones have
nonmagnetic M atoms, and the R elements are the only one carrying a magnetic
moment. For R = La, Y, Ce, Lu, and Th, the RNi5 phases are Pauli paramagnets,
whereas the PrNi5 exhibits Van Vleck paramagnetism. PrNi5 does not order
magnetically due to crystal electric field effects which lead to a nonmagnetic singlet
ground state lying below the first magnetic level [305]. Due to their exchange-
enhanced Pauli paramagnetism, YNi5 and CeNi5 have been considered as nearly
ferromagnetic [306, 307]. For the other R elements, magnetic order occurs at low
temperature, the largest ordering temperature being 32 K for GdNi5 [308]. Most of
the RNi5 compounds exhibit ferromagnetic order. It is worth noting that Ni atoms do
not carry a significant ordered magnetic moment in the RNi5 structure type, although
a small induced polarization of order 0.1 μB /Ni has been reported by several authors.
However, the Ni atoms are found to contribute to the paramagnetic state in particular
for the light R elements since the effective magnetic moments deduced from the
paramagnetic regime are much larger than for the free Pr3+ or Nd3+ ions [305, 309].
The main structural and magnetic properties of the other RNi5 -type compounds are
summarized in Table 14.
The experimentally determined second-order crystal electric field parameter of
the RNi5 compounds is compared in Table 15 to that of the RCo5 isotypes. It is
clearly seen that the negative sign is preserved when passing from one series to the
other; however, the values are much larger for the RNi5 compounds. A comparison
of the crystal electric field and magnetic behavior of the RNi5 and RCo5 compounds
has also been done on the basis of the Mössbauer spectroscopy at the R nucleus
(161 Dy, 166 Er, 169 Tm) [310]. For the RNi5 series of compounds, the set of the
crystal electric field parameters (up to the sixth order) has been determined from
investigation of single-crystal magnetization data. The corresponding values are
listed in Table 16 for R = Pr, Nd, Tb, Dy, Ho, Er, and Tm [311, 312]. For SmCo5 , a
A0 2 <r2 >/kB value of about −200 K has been determined from a polarized neutron
study on a single crystal [313]. The result is agreement with other investigations
[314–316]. Values of 0 K and 50 K were derived in SmCo5 for the higher-order
terms A0 4 <r4 >/kB and A0 6 <r6 >/kB , respectively [313].
The magnetocaloric properties of the RNi5 compounds have been systematically
studied (R = Pr, Nd, Gd, Tb, Dy, Ho, Er). Theoretical calculations are compared to
experimental data recorded on polycrystalline samples in the following reference
[317]. Around the ordering temperature, the magnetic entropy values of about
−
Smag = 7, 6, 7, 5 J/mol, K are obtained for R = Er, Ho, Dy, or Tb, respectively.
The adiabatic temperature change
Tad is 4, 6, 6 8, 9, 12 K for R = Nd, Gd,
Tb, Ho, Dy, and Er, respectively. An anomalous magnetocaloric effect is reported
Table 14 Lattice parameters and magnetic properties of RNi5 compounds
Easy
magnetization
a(10−3 nm) c(10−3 nm) Space Group axis TC (K) Ms (μB /f.u.) θp (K) Meff (μB /f.u.) Various Ref.
YNi5 489.1 396.1 P6/mmm – Pauli para. 0 −804 1.75 [306]
LaNi5 501.4 397.6 P6/mmm – Pauli para. 0 [307]
CeNi5 P6/mmm – Pauli para. 0 −275 1.34 [307]
PrNi5 495.7 397.6 P6/mmm – Van Vleck para. 0 9.2 [305]
495.2 397.6 P6/mmm 7 2.14 [309]
15 Metallic Magnetic Materials
NdNi5
SmNi5 492.4 397.4 P6/mmm c 27.5 0.7 [333]
EuNi5 491.1 397.5 P6/mmm – No order 0 [334]
GdNi5 490.6 396.8 P6/mmm c 32 6.90 31. 7.9 VZZ = 8.5 [335,
1021 nV/m2 336]
TbNi5 489.4 396.6 P6/mmm a 23 7.60 17.0 11.5 −
SM max = [337]
56 J/(mole
K)
H =
5T
Tad max =
7.3 K
DyNi5 487.2 396.8 P6/mmm b 11.6 8.5 8.2 [338]
HoNi5 487.2 396.6 P6/mmm 5 9 4.5 10.7 [311]
ErNi5 485.8 396.5 P6/mmm c 8 8.7 4.2 9.5 [339]
TmNi5 485.3 396.0 P6/mmm c 4.5 6.76 1.75 [340]
YbNi5 484.7 395.7 P6/mmm a 0.55 3.9 [341]
LuNi5 481.6 398.2 P6/mmm – Pauli para. – [342]
ThNi5 497.0 401.0 P6/mmm – Pauli para. 0 [332, 343,
344]
735
736
Table 15 Comparison of some second-order crystal electric field parameters reported for RCo5 and RNi5 compounds
R Pr Nd Sm Gd Tb Dy Er Tm
RNi5 A0 2 <r2 >kB −270 −521 [312] −520 [333] – −501 [312] −499 [345] −271 [312] −376 [312]
(K) [312]
RCo5 A0 2 <r2 >kB – −455 [345] −213 [313, 314, −206 [310] −124 [315] −167 [315] – –
(K) 346]
Note that the A0 2 parameter has been found to decrease upon increasing the Co stoichiometry [310]
J. P. Liu et al.
15 Metallic Magnetic Materials 737
Table 16 Crystal electric field parameters and exchange interaction coefficients reported for some
RNi5 and RCo5 single-crystal compounds at 4.2 K
nR-M (T/μB ) B0 2 (K) B0 4 (10−2 K) B0 6 (10−4 K) B6 6 (10−4 K)
NdCo5 [301, 347] 3.71 0.25 −5.0 −124
PrCo5 [348] 1.21 2.4 10
HoCo5 [349] 0.69 0.14 0.04 –
PrNi5 [305] 2.1 5.84 4.53 8.86 314
NdNi5 [309] 3.35 1.45 −3.50 135
TbNi5 [311] 3.84 −0.039 −0.40 −4.0
DyNi5 [312] 2.30 0.22 0.10 2.7
HoNi5 [311] 1.15 0.19 −0.02 −3
ErNi5 [311] −0.69 0.0 0.53 3.5
h [339] −3.80 −1.26 1.83 −7.6
for PrNi5 [317]. Magnetocaloric effect has also been investigated in a HoCo5
single crystal in the temperature region around the spin reorientation. A significant
anisotropic behavior has been reported when applying the magnetic field along
different directions [318].
The RCo5 compounds have been widely investigated by neutron diffraction
experiments, and results are given in Table 17 for the compounds with R = Y, La,
Ce, Nd, Sm, Tb, Ho, and Th. ThCo5 has been found to present a sharp itinerant
electron metamagnetic behavior in its the magnetization curve, a feature highly
sensitive to the Co stoichiometry [319]. At 4.2 K, whereas in ThCo5 the critical
field occurs at 2.2 T or ThCo5.1 , the Co magnetic moments are already in a high
magnetization state. The Co magnetic moment increases from about 1.0 μB to
1.5 μB /atom at the transition [320]. The effect of pressure on the metamagnetic
transition has also been reported to be large [321], the transition being shifted to
higher critical field at a rate of 2.8 T/kbar.
The R2 M17 (M = Fe, Co, Ni) compounds have the richest M content of the
binary phase diagram and crystallize in superstructures deriving from the RM5
(CaCu5 ) type by an ordered substitution of two Co atoms (forming a dumbbell pair)
for R atoms following the sequence 3 RM5 – R + 2M => R2 M17 . Depending on
the relative size of the R and M atoms, these phases may exist in either hexagonal
Th2 Ni17 type (P63 /mmc) [343] for M = Fe and Ni or rhombohedral Th2 Zn17
type (R3m) structure [351] for M = Fe, Co. Some compounds can be obtained
in either allotropic form depending on the synthesis conditions or composition.
Whereas the Th2 Zn17 type is a well-ordered structure, the Th2 Ni17 type can present
some disorder and is better described as the R2−δ M17+2δ [352–355] as a result
of the replacement of part of the R atoms by a dumbbell M pair. Magnetic data
concerning the R2 M17 compounds are listed in Tables 18 and 19 for M = Fe and
Co, respectively. Partial replacement of these three transition metal elements is
possible in particular by Mn. The properties of such pseudo-binary compounds are
not described below due to space limitation; for more details, the reader is referred,
for example, to [356].
738
Table 17 Magnetic structure determined from neutron diffraction for RCo5 compounds
Th[319] Th[319] Th[320] Th[320]
RCo5 Y[350] Y[302] La[295] Ce[328] Nd[301] Sm[313] Sm[313] Tb[328] Tb[328] Tb[328] Ho[349] Ho[349] ThCo5 ThCo5 ThCo5 ThCo5.10
T (K) 4.2 300 300 4.2 4.2 300 4.2 300 453 4.2 300 110 4.2
@
4.4 T
Easy c c c Perp to c c a a c Perp c c c c c
direc- c to c
tion
MR −0.4 – <0.3 2.82 3.8 0.04 8.35 6.30 4.10 10.0 4.8 – – – –
(μB )
MCo 1.68 1.77 1.60 1.3 1.88 1.86 1.86 1.55 1.35 1.45 1.65 1.7 1.21 1.19 1.4 1.63
2c
(μB )
MCo 1.67 1.72 1.76 1.3 1.91 1.75 1.75 1.70 1.55 1.45 1.65 1.7 0.96 1.06 1.4 1.63
3g
(μB )
J. P. Liu et al.
Table 18 Lattice parameters and magnetic properties of R2 Fe17 compounds (EMD stands for easy magnetization direction)
a −ΔSmax
(10−3 c(10−3 V(10−3 Type/space TC Ms dTc /dP dT /dP K1 (4 K) K2s (4 K) (J/kg
nm) nm) nm) group (K) EMD (μB /f.u.)4 K (K/kbar) (K/kbar) (MJ/m3 ) (MJ/m3 ) K) Ref.
Th2 Fe17 857.1 1247.4 798.2 Th2 Zn17 /R3m 315 Ferro 30.5 −4 [386,
387]
Ce2 Fe17 848.9 1241.3 774.8 Th2 Zn17 /R3m 225 Plane 29.7 −2.5 −40 [358,
(Tc ) fan to 359,
15 Metallic Magnetic Materials
heli- 361,
cal 362,
388]
Pr2 Fe17 858.1 1246.3 794.8 Th2 Zn17 /R3m 293 a 36.4 −3 −3.7 0.55 [372,
387]
Nd2 Fe17 857.9 1246.1 794.3 Th2 Zn17 /R3m 326 38.0 −3.6 KNd 1 = −55 KNd 2 = 3 [370,
23 (@2 T) 389]
Sm2 Fe17 855.4 1244.3 788.4 Th2 Zn17 /R3m 385 a 35.4 −3 <0.1 1.72 [372,
(@1.5 T) 390]
Gd2 Fe17 853.9 1243.3 785.5 Th2 Zn17 /R3m 461 a-b 21.5 −2 0.5 0.89 [390,
(Tc ) plane (@1.5 T) 391]
Tb2 Fe17 846.2 831.5 515.6 Th2 Ni17 /P63 /mmc 425 b 20.0 0.3 −5 1.32 [390,
(Tc ) (@1.5 T) 392,
393]
Dy2 Fe17 846.2 830.0 514.6 Th2 Ni17 387 a 16.2 −4.8 −K1 −2K2 −3K3 1.59 [390,
P63 /mmc (Tc ) = −1.5 (@1.5 T) 394,
(80 K) 395]
Ho2 Fe17 845.3 828.9 513.1 Th2 Ni17 335 b 19.5 −5.6 1.75 [371,
P63 /mmc (Tc ) −K1 −2K2 −3K3 394]
= −2 (80 K)
739
(continued)
740
Table 18 (continued)
a −ΔSmax
(10−3 c(10−3 V(10−3 Type/space TC Ms dTc /dP dT /dP K1 (4 K) K2 (4 K) (J/kg
nm) nm) nm) group (K) EMD (μB /f.u.)4 K (K/kbar) (K/kbar) (MJ/m3 ) (MJ/m3 ) K) Ref.
Er2 Fe17 843.8 828.2 510.7 Th2 Ni17 300 a 17.9 −4.3 −K1 −2K2 −3K3 1.68 [390,
P63 /mmc (Tc ) = −1.5 (80 K) (@1.5 T) 393,
394]
Tm2 Fe17 842.0 827.2 507.9 Th2 Ni17 274 c 21.2 6.6 −2.2 [368,
P63 /mmc (Tc ) T<74 K 396,
(TSR ) a 397]
T> TSR
Yb2 Fe17 841.4 824.9 507.2 Th2 Ni17 278 b [398]
P63 /mmc (Tc )
Lu2 Fe17 840.6 827.5 506.4 Th2 Ni17 270 b fan 34.2 −1.9 −48 −2.3 4.1 [365,
P63 /mmc (Tc ) LT to (@5 T) 394,
helical 1.5 399]
(@2 T)
Y2 Fe17 842.2 830.6 515.1 Th2 Ni17 327 Ferro 34.6 −4.7 −2.3 −0.11 2.4 [355,
R3m also or fan (@2 T) 364,
found as 4 to 5 369,
Th2 Zn17 (@5 T) 399]
P63 /mmc
J. P. Liu et al.
Table 19 Lattice parameters and magnetic properties of R2 Co17 compounds
K1 K2 K1 K2
(MJ/m3 ) (MJ/m3 ) (MJ/m3 ) (MJ/m3 )
15 Metallic Magnetic Materials
a (10−12 m) c (10−12 m) Space Group TC (K) Ms (μB /f.u.) BA (T) 300 K 300 K 77 K 77 K Ref.
Th2 Co17 843.8 1225.4 R3m 1035 24.14 [264]
Ce2 Co17 836.8/837.1 1220.4/813.6 R3m/P63 /mmc 1083 26.1 −0.6 [351,
1.15 T at 378,
300 K 400]
Pr2 Co17 843.8/ 1225.3 R3m 1171 31.0 −0.6 [351,
1.38 T at 378,
300 K 400]
Nd2 Co17 842.2 1224.6 R3m/P63 /mmc 1150 30.5 −1.1 [351,
1.39 T 378,
400]
Sm2 Co17 838.5/826.0 1221.4/851.5 R3m/P63 /mmc 1190 20.1 3.3 0.35 [351,
1.2 T at 378,
300 K 400]
Gd2 Co17 837.7/8.351 1219.8/8.125 R3m/P63 /mmc 1209 14.4 −0.5 −0.47 0.05 [351,
0.73 T 378,
300 K 400]
Tb2 Co17 835.7/834.8 1218.6/812.5 R3m/P63 /mmc 1180 (Tc) 10.7 −3.3 [351,
0.68 T 378,
300 K 400]
741
(Continued)
742
Table 19 (Continued)
K1 K2 K1 K2
(MJ/m3 ) (MJ/m3 ) (MJ/m3 ) (MJ/m3 )
a (10−12 m) c (10−12 m) Space Group TC (K) Ms (μB /f.u.) BA (T) 300 K 300 K 77 K 77 K Ref.
Dy2 Co17 834.6/832.8 1281.0/812.5 R3m/P63 /mmc 1152 (Tc) 8.3 −2.6 −2.8 0.2 [351,
0.70 T at 378,
300 K 400]
Ho2 Co17 833.2/832.0 1220.1/811.3 R3m/P63 /mmc 1173 (Tc) 7.7 −1.0 −2.0 0.15 [351,
0.83 T at 378,
300 K 401]
Er2 Co17 –/831.0 –/811.3 P63 /mmc 1187 (Tc) 10.1 18 T 0.41 1.7 0.4 [351,
0.90T at (295 K) 378,
300 K 402]
Tm2 Co17 –/828.5 –/809.5 P63 /mmc 1182 (Tc) 11.3 0.5 2.7 0.4 [378,
1.13 T at 401]
300 K
Yb2 Co17 –/830.9 –/809.6 P63 /mmc 1180 (Tc) 20.46 9.9 T 0.38 0 [398,
(4.2 K) (295 K) 402,
26.8 403]
(295 K)
Lu2 Co17 –/824.7 –/809.3 P63 /mmc 1175 (Tc) 26.9 −0.20 0.02 −0.58 0.09 [384,
1.87 T 401]
300 K
Y2 Co17 835.5/834.1 1218.3/812.5 R3m/P63 /mmc 1167 27.8 −0.3 <0.01 −0.58 0.05 [400]
1.25 T
300 K
J. P. Liu et al.
15 Metallic Magnetic Materials 743
The R2 Fe17 compounds have attracted much interest due to their large mag-
netization mostly resulting from the large Fe content. However, their relatively
low ordering temperature ranging from 225 (Ce) to 461 K (Gd) hampers their
use as magnets at room temperature. The low Curie temperatures and unfavorable
magnetic anisotropy can be resolved by introducing N or C in interstitial sites
surrounding the rare-earth atoms. Generally, the R2 Fe17 compounds are ferromag-
netic for light rare-earth and ferromagnetic for heavy rare earth. Exceptions are
Ce2 Fe17 and Lu2 Fe17 which have been reported to be at the limit of ferro- and
antiferromagnetic ordering. In a limited temperature range, noncollinear magnetic
structures were observed in Ce2 Fe17 , Lu2 Fe17 , or even Tm2 Fe17 compounds where
negative exchange interactions are due to short Fe-Fe distances [357]. At low
temperature, these compounds can present helimagnetic structures, the Fe magnetic
moment lying in the basal (a,b) plane. The orientation of the magnetization of the
ferromagnetic planes rotates from one (001) plane to the following one forming
a helix whose period varies with temperature [357–359]. An antiferromagnetic
behavior occurs for Lu2 Fe17 between the magnetic ordering temperature 270 K and
the second critical temperature Θ T of 140 K below which it becomes ferromagnetic
[357]. This second critical temperature decreases rapidly upon application of
pressure dΘ T /dp = −48 K/kbar, whereas the ordering temperature is much less
sensitive to the pressure [360] dTN /dp = −1.9 K/kbar. Recent studies on Ce2 Fe17
[361, 362] established that below 118 K additional superstructure reflexions appear
in the antiferromagnetic state leading to a doubling of the chemical unit cell along
the c direction in hexagonal notation with the same space group R3m. dΘ T /dp
= −40 K/kbar.
Y2 Fe17 is a collinear ferromagnetic with magnetic moments lying in-plane up
to the TC ; however, application of high pressure induces a change of its magnetic
structure to helical incommensurate phases [363]. A similar effect of pressure has
been reported for Ce2 Fe17 and Lu2 Fe17 [359, 364, 365]. A helimagnetic ground
state has been induced in Y2 Fe17 and Lu2 Fe17 intermetallics by hydrostatic pressure
above 1.05 and 0.3 GPa, respectively [364].
The TC of R2 Fe17 ferromagnetic compounds decreases upon increasing applied
pressure, and values of dTc /dP = −3.6 and −4.7 K/kbar have been reported
for Nd2 Fe17 and Y2 Fe17 , respectively. The iron sublattice magnetization is about
34 μB /formula unit for both R = Y and Lu compounds, corresponding to a
mean Fe moment of 2 μB in the ordered state. In the paramagnetic state, an
effective magnetic moment of 3.87 μB /Fe atom has been reported indicating the
itinerant electron character of the magnetism in Y2 Fe17 [366]. All the R2 Fe17
compounds present planar anisotropy, except Tm2 Fe17 . A spin reorientation occurs
at 74 K upon heating, temperature above which the magnetic moments tilt toward
the (a,b) plane [357, 367, 368]. Magnetocrystalline anisotropy has been deter-
mined on single-crystal Y2 Fe17 [369] and Nd2 Fe17 [370] leading to values of
KFe 1 = 0.255 MJ/m3 and KFe 2 = −3.11 MJ/m3 for the Fe sublattice anisotropy
against KNd 1 = −57 MJ/m3 and KNd 2 = 26 MJ/m3 . The magnetocrystalline
anisotropy of Ho2 Fe17 has been determined at 4.2 K: K1 = −5.6 MJ/m3 and K2 =
1.7 MJ/m3 [371]. For Sm2 Fe17 , a value of K1 = −3 MJ/m3 has been estimated from
high field measurements on powder sample [372]. FOMP (first-order magnetization
744 J. P. Liu et al.
processes) have been reported to occur at low temperature for several R2 Fe17
compounds [373]. Neutron diffraction experiments and Mössbauer spectroscopy
analysis agree to show that the largest Fe magnetic moment is observed on the
dumbbell Fe sites (6c and 4e in the R3m and P63 /mmc, respectively), the other
Fe moment being close to 2 μB in the R2 Fe17 compounds [374, 375]. The
magnetocaloric properties of several R2 Fe17 compounds have been determined; the
values are also listed in Table 18.
In the R2 Co17 series, the compounds show ordering at high temperature ranging
from 1035 K for Ce to 1209 K for Gd, the Co magnetic moments being coupled
ferromagnetically for R = Lu, Y, Ce, or Th. According to room temperature neutron
diffraction experiments on Y2 Co17 , the Co magnetic moment is about 1.88 μB /Co
for the different crystal sites and even 2.1 μB on the 6c position [376]. Y2 Co17
presents a planar anisotropy featured by K1 = −0.34 MJ/m3 at room temperature
and a saturation magnetization of 1.25 T. Thanks to its high magnetization of 1.2 T
and large magnetic anisotropy K1 = 3.3 MJ/m3 at room temperature, Sm2 Co17
exhibits exceptional magnetic properties for high-temperature, high-performance
permanent magnet applications [377–379] leading to a maximum energy product
of 287 kJ m−3 [377, 379]. Many efforts have been made to play with substitutions
and/or additions of elements such as Zr, Cu, and Fe, in order to improve the
synthesis process and get optimized microstructure leading to high-performance
magnets [380].
Compounds containing R = Tm, Er, and Yb are the only other ones to exhibit
positive values of the first-order anisotropy constant at 4.2 K K1 = 0.189, 0.5 MJ/m3 ,
and 0.34 MJ/m3 , respectively [381]. The anisotropy parameters determined at either
300 K or 77 K are listed in Table 19 together with the ordering temperature
and other magnetic properties of the R2 Co17 compounds [273]. At 77 K, the
anisotropy parameter of the Co sublattice estimated from the compounds with R
= Y and Lu is K1 = −0.58 MJ/m3 , and values of K2 = 0.05 MJ/m3 and K2 =
0.09 MJ/m3 are reported for Y and Lu, respectively [382, 383]. In a recent study on
a Lu2 Co17 single crystal, a spontaneous magnetic moment of 27.6 μB /formula unit
corresponding to about 1.62 μB /f.u. per Co atom has been reported at 5 K [384], and
the easy plane magnetocrystalline anisotropy is confirmed as the ground state since
K1 = −0.57 MJ/m3 and K2 = −0.058 MJ/m3 . As a consequence of this second-
order phase transition, the compound becomes easy axis at elevated temperature
between 730 K and the Curie temperature [384]. A polarized neutron diffraction
study performed at 5 K on single crystal of Er2 Co17 leads to the following magnetic
moments values: mEr (2b) = 8.3 μB , mEr (2d) = 9.0 μB , mCo (4f ) = 2.1 μB , mCo
(6g) = 1.6 μB , mCo (12j) = 1.9 μB , and mCo (12k) = 1.2 μB [385].
R2 M14 B compounds are found for M = Fe, Co and X = B or C in a tetragonal
structure whose prototype is Nd2 Fe14 B crystallizing in the P42 /mnm space group.
The crystal structure has two inequivalent sites for R elements, six for the iron
and one for the boron atoms [404–406]. These phases are line compounds with
a defined stoichiometry. The lattice parameters and the main magnetic properties
corresponding to the R2 Fe14 B, R2 Co14 B, and R2 Fe14 C compounds are listed in
Tables 20, 21, and 22, respectively.
Table 20 Magnetic properties and room temperature lattice parameters of R2 Fe14 B-type compounds
EMD Ms K1 (MJ/
a(10−3 c(10−3 TC at TSR Ms (μB /f.u.) μ0 Ms (T) K1 K2 4.2 K (μB /f.u.) μ0 Ms (T) m3 )
nm) nm) (K) 4K (K) 4.2 K 4.2 K BA (T)4.2 K 4.2 K(MJ/m3 (MJ/m3 ) 300 K 300 K 300 K Ref.
15 Metallic Magnetic Materials
Th2 880.5 1218.7 487 c 29.8 1.4 1.0 24.7 1.25 1.3 [422]
Fe14 B
La2 882 1234.0 542 c 30.8 1.50 1.3 0.7 28.4 1.39 1.1 [423]
Fe14 B
Ce2 876 1211.0 427 c 30.0 1.52 3.0 1.8 23.9 1.17 1.8 [423]
Fe14 B
Pr2 880 1223.0 565 c 37.6 1.76 29 55 −87 31.9 1.55 5.0 [424]
Fe14 B
Nd2 Fe14 B 880 1220.0 592 Canted 135 37.5 1.86 35 −16.6 39.3 32.5 1.61 4.9 [412,
30◦ /c 425]
Sm2 Fe14 B 880 1215.0 621 a 33.3 1.57 40 −26.0 30.2 1.51 −12.0 [424,
426,
427]
Gd2 Fe14 B 879 1209.0 664 c 17.9 0.9 2.1 0.7 17.5 0.83 1.0 [428]
Tb2 Fe14 B 877 1205.0 620 c 13.2 0.65 40 6.9 14.0 0.92 3.4 [423]
Dy2 Fe14 B 876 1201.0 589 c 11.3 0.58 23 3.8 14.0 0.72 4.2 [423,
424]
Ho2 Fe14 B 876 1199.0 569 Canted 57 11.2 0.57 18 −1.1 4.4 15.9 0.80 2.0 [417,
24◦ /c 423]
745
(continued)
746
Table 20 (continued)
EMD Ms K1 (MJ/
a(10−3 c(10−3 TC at TSR Ms (μB /f.u.) μ0 Ms (T) K1 K2 4.2 K (μB /f.u.) μ0 Ms (T) m3 )
nm) nm) (K) 4K (K) 4.2 K 4.2 K BA (T)4.2 K 4.2 K(MJ/m3 (MJ/m3 ) 300 K 300 K 300 K Ref.
Er2 Fe14 B 873 1195.0 554 a 328 13.1 0.66 16 −1.4 17.7 0.90 1.3 [417,
423]
Tm2 Fe14 B 873 1193.0 545 a 314 18.2 0.93 17 −3.6 22.6 1.15 – [423,
429]
Yb2 Fe14 B 871 1185.0 527 a 120 ∼23 ∼1.2 ∼23 – [429–
431]
Lu2 Fe14 B 876 1200.0 534 c 28.5 1.47 2.4 1.2 22.5 1.13 1.5 [423,
432]
Y2 Fe14 B 876 1200.0 566 c 29.5 1.55 1.5 0.8 26.05 1.44 1.1 [428]
TSR Temperature of spin reorientation transition
J. P. Liu et al.
Table 21 Magnetic properties and room temperature lattice parameters of R2 Co14 B-type compounds
Ms
a(10−3 c(10−3 TC TSR μ0 Ms (T) K1 (MJ/m3 ) (μB /fu) K1 (MJ/ K2
nm) nm) (K) (K) 300 K 300 K EMD 4.2 K μ0 Ms (T)4.2 K BA (T)4.2 K m3 )4.2 K (MJ/m3 ) Ref.
La2 Co14 B 867 1201 955 1.00 −1.4 (001) 20.4 1.1 3.4 −1.4 [427]
plane
15 Metallic Magnetic Materials
Pr2 Co14 B 863 1187 995 664 1.09 6.0 c to (001) 24.8 1.3 75 [433]
plane
Nd2 Co14 B 864 1186 1007 37 1.06 2.2 Canted 25.7 1.3 30 −1.4 19 [427,
543 15◦ to c 434,
(4.2 K) 435]
then c
(300 K) to
perp. to c
Sm2 Co14 B 861 1179 1029 (001) 18.1 1.0 [436]
plane
Gd2 Co14 B 861 1176 1050 −1.3 (001) 5.4 0.3 14 −1.4 [427,
plane 436]
Tb2 Co14 B 860 1173 1035 795 c to (001) 0.1 [436]
plane
Dy2 Co14 B 876 1201 [433]
Y2 Co14 B 860 1171 1015 1.00 −1.4 (001) 19.2 1.0 3.0 −1.3 [410,
plane 436]
747
748
Table 22 Magnetic properties and room temperature lattice parameters of R2 Fe14 C-type compounds
a(10−3 c(10−3 Ms μ0 Ha μ 0 Ms μ0 Ha
nm) nm) TC (K) EMD TSR (K) (μB /f.u.)4 K (T)4.2 K (T)300 K (T)300 K Ref.
La2 Fe14 C 882 1214
Ce2 Fe14 C 874 1184 345 c 23.9 [437]
Pr2 Fe14 C 882 1204 513 c 33.7 1.27 14.8 [438]
Nd2 Fe14 C 880.9 1205.0 530 Cone to 140 31.4 1.41 10.1 [438]
c-axis
Sm2 Fe14 C 879.8 1194.5 580 (a,b) plane 30.2 1.41 8.5 [432]
Gd2 Fe14 C 879.1 1189.3 630 c 18.1 2 0.73 3.38 [432]
Tb2 Fe14 C 877.0 1186.5 585 c 12.0 40 0.58 19.4 [439]
Dy2 Fe14 C 875.4 1182.6 555 c 10.5 0.62 15.4 [432]
Ho2 Fe14 C 873.9 1179.7 525 Cone to 35 10.9 0.0.73 8.2 [432, 440]
c-axis
Er2 Fe14 C 873.0 1177.5 510 Plane to 325 12.5 0.95 [441, 442]
c-axis
Tm2 Fe14 C 872.1 1174.9 500 [100], then 308 18.4 [443]
[001] for
T>TSR
Lu2 Fe14 C 871.3 1172.2 495 c 27.2 2.5 1.16 3.25 [432, 444]
Y2 Fe14 C 876 1186 520 c [445]
J. P. Liu et al.
15 Metallic Magnetic Materials 749
The R2 Fe14 B compounds have density ranging from 7.4 to 8.86 g/cm3 for
R = La and Th, respectively. They have attracted much interest due to their large
magnetization mostly resulting from their large Fe moments and the discovery that
due to the large magnetocrystalline anisotropy, one can obtain large coercive field in
alloys containing the Nd2 Fe14 B-type phase. At room temperature, a large saturation
magnetization of 1.61 T is reached for Nd2 Fe14 B, which is an interesting property
since the energy product of a magnet scale with Ms 2 [407]. The anisotropy constant
K1 of Nd2 Fe14 B is about 4.9 MJ/m3 at room temperature [408–410], whereas the
best magnets present excellent performances such as energy products larger than
400 kJ/m3 . Their ordering temperature, ranging from 427 K (Ce) to 664 K (Gd), is
high enough to permit their use as permanent magnets at room temperature [408,
409]; however, these Curie temperatures are relatively low compared with those
of other ferromagnetic materials used in permanent magnets (e.g., the R-Co-type
magnets). Generally, the R2 Fe14 B compounds are ferromagnetic for light rare-earth
elements and ferrimagnetic for heavy rare-earth elements. The compounds with R =
La, Ce, Lu, Y, and Th are ferromagnetic, their magnetic properties being determined
by the Fe sublattice only. They exhibit magnetocrystalline anisotropy of about 2 T
[410–412] at room temperature and MS of typically 30 μB /f.u. (1.5T) at 4.2 K and
28 μB /f.u. (1.4T) at 300 K (Table 20). This corresponds to a large value of the mean
Fe moment of about 2 μB at room temperature and even 2.14 μB at 4.2 K. The
Mössbauer effect spectroscopy [413], neutron diffraction experiments [374, 414–
419], and theoretical calculations [420, 421] agree to reveal that the magnitude of
the Fe magnetic moment varies significantly for the inequivalent atomic positions,
the largest value (up to 2.8 or even about 3.0 μB ) being reported for the 8j2 position
[374, 417, 420]. At 4.2 K, the Fe sublattice K1 anisotropy parameter ranges from 0.8
to 1.2 MJ/m3 for the Fe sublattice depending on the R element (Table 20). Sm2 Fe14 B
is the only compound exhibiting a planar character, its easy magnetization direction
remaining within the (a,b) plane up to TC [448]. For the other R elements, the Fe
sublattice anisotropy dominates at high temperature favoring uniaxial anisotropy.
More complex behavior is observed at lower temperature due to the increasing
influence of the R sublattice anisotropy that is reinforced at cryogenic temperatures.
The magnetic phase diagram of the R2 Fe14 B compounds is schematically repre-
sented in Fig. 11 [446]. Typical thermal variation of the K1 anisotropy parameter
is shown in Fig. 12 for R = Nd, Pr, and Dy. At low temperature, several R2 Fe14 B
compounds undergo a spin reorientation phenomenon occurring at 135 K, 57 K,
328 K, 314 K, and 120 K for R = Nd, Ho, Er, Tm, and Yb, respectively [408, 409].
For R = Er, Tm, and Yb, the spin reorientation results from the competition between
the R and Fe sublattice magnetocrystalline anisotropy, the R one being dominant
at low temperature inducing an easy plane magnetization at 4.2 K as witnessed
by the anisotropy parameters reported in Table 20. For R = Nd and Ho, the spin
reorientation is of different origin; the magnetic moments are tilted away from the
c-axis below TSR [416, 417]. This phenomenon is a consequence of the different
temperature variation of the various magnetocrystalline anisotropy terms associated
750 J. P. Liu et al.
Fig. 11 Schematic representation of the magnetic phase diagram of the R2 Fe14 B [446, 447]
to the R sublattice [449, 450]. In Nd2 Fe14 B, this results in a non-strictly collinear
magnetic structure and different tilt angles within the (1–10) plane of the Fe and
Nd sublattices. Due to their nonequivalent atomic positions and the consequently
different crystal electric field parameters, the Nd sites can have different tilt angles
too [417] as shown in Fig. 13. The existence of this spin reorientation for R = Nd is
a drawback for low temperature applications as permanent magnet. Consequently,
Pr2 Fe14 B is often preferred due to its large uniaxial anisotropy even at 4.2 K. It is
worth to point out that neutron diffraction revealed that due to the spin reorientation,
a lowering of symmetry is observed [417, 418]. As a consequence, the R 4f and 4g
sites are further subdivided magnetically into f1 , f2 , g1 , and g2 sites as derived from
inelastic neutron scattering measurements [451].
The R6 M13 A phases (A= Cu, Ag, Au, Si, Ge, Ga, Al, Sn, Sb, Tl, Pb, Bi)
have been discovered in the frame of the search of phase stability; they can be
observed as secondary phase in some starting materials for R2 Fe14 B-type permanent
magnets when some A additives are used [453, 454]. Often referred to as δ phase,
the R6 M13 A compounds attracted much interest since such secondary phases have a
critical influence on the magnetic performances of the magnets (i.e., the coercitivity)
[455, 456]. These R6 M13 A-type compounds crystallize in the La6 Co13 Ga-type
structure [453, 454, 457] an ordered version of the Nd6 Fe11 Ga3 and are observed
15 Metallic Magnetic Materials 751
40
Pr2Fe14B
20
K1 (MJ/m3) Dy2Fe14B
Nd2Fe14B
-20
-40
0 200 400 600
Temperature (K)
Fig. 12 Temperature dependence of the anisotropy constant of the R2 Fe14 B with R=Pr, Nd, and
Dy [452]
for light R elements such as La, Pr, Nd, and Sm. Such tetragonal structure retains
the I4/mcm space group and is shown in Fig. 14. The R elements are located on
two positions 16l and 8f, whereas the iron atoms are found on four inequivalent
sites 4d, 16k, 16l1 , and 16l2 . Finally, the A atom sits on the 4a position. Such
structure can be seen as a multilayer structure where slabs of iron alternate with
slabs of rare-earth atoms. The lattice parameters are listed in Table 23 together with
some magnetic properties of the R6 Fe13–x Ax -type compounds. Depending on the A
nature, this crystal structure can accommodate a certain homogeneity range leading
to R6 Fe13–x Ax formula. For example, with A = Ga, it has been shown that Ga is
filling up successively the 4a Si and the 16l Fe4 sites of the prototype Nd6 Fe13 Si
752 J. P. Liu et al.
Fig. 14 Schematic representation of the crystal structure and collinear antiferromagnetic struc-
tures in Pr6 Fe13 Sn (left part) and Nd6 Fe13 Sn (right part) with the moments, respectively,
perpendicular to or along the c-axis. The inequivalent atomic positions are indicated with different
symbols for R, Fe, and X = Sn [464]
structure with increasing x [458]. Even larger solubility limit has been reported for A
= Al since Nd6 Fe9.5 Al4.5 compound has been reported [459, 460]. On the contrary
for A = Cu, a line compound with x = 1 [461] is found. It is worth to point out that
low amount of heavier rare-earth elements like Gd or Dy can be partially substituted
to the light one in the R6 Fe13–x Ax (A=Ga, Al) [461].
The R6 M13 A compounds exhibit antiferromagnetic properties, properties that
have sometimes been hidden by the presence of traces of ferromagnetic-type
impurities like R2 Fe17 [454]. For A = Au, Ag, Cu, Si, and Ga, the ordering
temperature is around 415 K [461]. The ordering temperature decreases upon
increasing the A content: in R6 Fe13–x Gax compounds, TN = 433 and 365 K for
x = 1 and 2, respectively. Similar trend has been reported for other systems since
15 Metallic Magnetic Materials 753
for R = Pr TN = 390, 335, and 320 K for x = 1, 2, and 3, respectively ([458] and
reference therein).
Several neutron diffraction experiments have reported the magnetic structure
of some R6 M13 A-type compounds. Pr6 Fe13 Ag and Pr6 Fe13 Au exhibit collinear
antiferromagnetic structure [462], the magnetic moments being confined within the
(a,b) plane but change sign collectively when passing to the next (R-Fe) block
along the c direction, that is, crossing the A layer. The magnetic moments of the
four iron and two Nd crystallographic sites are ferromagnetically coupled within
one block along the c-axis, and the resulting magnetic moments of this block
are antiferromagnetically coupled with that of the adjacent block along the c-axis
through the A atom layer. Antiferromagnetism is preserved over the anticentering
magnetic lattice translation so that two successive blocks have opposite signs.
The average Fe magnetic moment is about 2.2 μB in agreement with Mössbauer
spectroscopy results [463]. Similar magnetic structures have been reported for
Pr6 Fe13 Sn [464] (see Fig. 14), whereas the Nd isotype compound presents similar
alternating magnetic blocks but with an alignment of the magnetic moments along c.
The prototype Nd6 Fe13 Si compound presents an original behavior with a spin
reorientation occurring at about 100 K. Above and below 100 K, the magnetic
moments are found to be parallel to the c-axis and within the (a,b) plane of
the tetragonal unit cell, respectively. This reorientation occurs via a first-order
spontaneous zero field spin reorientation and is accompanied with an anisotropic
unit cell expansion at the spin reorientation [463]. A detailed 57 Fe Mössbauer
spectroscopy analysis of Nd6 Fe13 Si compound is also described in the same article.
754 J. P. Liu et al.
The lattice parameters and main magnetic properties of the R6Fe13-xAx compounds
are summarized in Table 24. For Nd6 Fe13–x Gax (x = 0 to 2) compounds, an easy-
axis antiferromagnetic structure is found below the Néel temperature and down
to a spin reorientation temperature below which an easy cone antiferromagnetic
structure is observed with a tilt angle of 9.2◦ versus c-axis at 1.5 K [458]. This
antiferromagnetic coupling between the magnetic blocks on both sides of the A
layer can be broken by the application of an external magnetic field, thus leading
to a metamagnetic transition occurring via a first-order magnetic phase transition
[465–467]. The magnetization obtained in such a forced ferromagnetic state has
been reported to be over 41 μB /f.u. for R6 Fe13 A compounds [461]. A large
hysteresis in the field dependence of the magnetization is present in all compounds
including La6 Fe11 Al3 , indicating the role of the Fe-sublattice anisotropy [461]. The
influence of Co for Fe substitution on magnetic properties and thermal expansion
of Nd6 Fe13 Si intermetallic compounds has been reported [468, 469]. The Néel
temperature has been found to increase due to reinforcement of the 3d–3d exchange
interactions, whereas the spin reorientation phenomenon occurs also at higher
temperature upon Co substitution for Fe [468].
Studying the transport properties of some R6 Fe11 Al3 compounds, about 4%
negative magnetoresistance has been reported in Nd6 Fe11 Al3 at 5 K in a field
of 6 T, but there is no magnetoresistance in La6 Fe11 Al3 [474]. An additional
magnetoresistance effect has been reported to occur at the metamagnetic transition
for R6 Fe13–x Al1+x with both R = Nd and La. Indeed, at the critical field, a 3–5%
resistivity drop has been found [475].
Hydrogen insertion can be performed in the crystal structure of the R6 M13 A
compounds. The maximum hydrogen content ranges from 13 to 20 depending on
the sample and authors [461, 471, 476–478]. Hydrogen has been reported to be
accommodated in four to six inequivalent interstitial sites of either tetrahedral or
octahedral type in Pr6 Fe13 AuD13 and Nd6 Fe13 GaD12 [477, 478], and it induces a
large and highly anisotropic deformation, being an order of magnitude greater along
c than along a [471]. The lattice parameters and main magnetic properties of the
R6 M13 AHx compounds are summarized in Table 25.
Contrary to the antiferromagnetic ground state of the R6 M13 A compounds, the
corresponding hydrides are all ferromagnetic for light R elements and have an
easy magnetization direction along the c-axis due to the Fe-sublattice anisotropy.
The effect of H insertion on the magnetization curves of Nd6 Fe13 A compounds
has been studied for the compounds with R = Au and Sn [471]. The magnetic
order of the hydrides has been estimated to about 450 K, just slightly above
that of the parent compounds [461]. Reference [476] gives a comparison of the
Mössbauer spectra for the R6 M13 A compounds and the corresponding hydrides for
A = Sb, Bi, and Cu and R = Pr and Nd. Studying Nd6 Fe13 Au and Nd6 Fe13 AuH13 ,
increases in hyperfine field and isomer shift are observed upon hydrogenation [473].
The ferromagnetic ground state of the hydrides has been also shown by neutron
diffraction investigation, and large magnetic moments have been reported for Fe
atoms in Pr6 Fe13 AuD13 compounds (Table 25). Complementary investigation of
the 119 Sn Mössbauer spectroscopy has been performed on both R6 M13 Sn and
Table 24 Magnetic moment in (μB ) as derived from neutron diffraction experiments at 1.5 K for some R6 Fe13–x Ax compounds
15 Metallic Magnetic Materials
Nd6 Fe13 Sn
Nd6 Fe13 Au Pr6 Fe13 Si Pr6 Fe12 Ga2 Nd6 Fe12 Ga2 1.5 K Pr6 Fe13 Sn Nd6 Fe13 Si Nd6 Fe13 Si Pr6 Fe13 Au Pr6 Fe13 AuD13
1.5 K 1.5 K 1.5 K 1.5 K [464]tilted 1.5 K 2K 150 K 1.5 K 2K
Site [470]planar [470]planar [479]planar [479]axial 10◦ /c [464]planar [463]planar [463]axial [462]basal [478]basal
R1 8f 3.4 2.8 2.6 2.97 3.06 2.91 3.1 2.4 2.6 2.7
R2 16l 2.5 2.7 2.4 2.67 2.45 2.73 2.5 1.7 2.6 1.7
Fe1 4d 2.6 1.8 2.1 2.4 2.0 2.3 2.8 3.0 0.8 2.2
Fe2 16k 2.6 2.0 2.1 2.4 2.67 2.57 2.6 2.9 2.6 1.7
Fe3 16l1 2.6 2.1 1.9 2.4 2.45 2.42 2.4 2.7 2.4 3.4
Fe4 16l2 2.6 2.1 1.9 2.4 2.53 2.54 1.8 2.0 2.2 1.6
755
756 J. P. Liu et al.
Table 25 Lattice parameters and magnetic properties of R6 M13–x Ax Hy (M=Fe, Co) compounds
Ms Ms
(μB /f.u.) (μB /f.u.)
R6 Fe13–x Ax Hy a (10−3 nm) c (10−3 nm) TC (K) 4K 293 K Ref.
La6 Fe11 Al3 H16 829.1 2604. 444 22.7 [461]
La6 Fe13 SnH14.5 819.9 2537.6 [480]
Pr6 Fe13 AgH17 827.0 2557.8 19.4 [471]
Pr6 Fe13 AuH17 820.4 2547.4 23.1 [471]
Pr6 Fe13 AuD13 817.4 2540.8 [477]
Pr6 Fe13 SiH14.7 812.3 2541.0 22.6 [471]
Pr6 Fe13 GeH13.9 812.8 2542.1 21.4 [471]
Pr6 Fe13 SnD12.4 818.9 2542.5 20.5 [471]
Pr6 Fe13 PbH13.1 819.9 2542.5 22.1 [471]
Pr6 Fe13 SbH13.1 816.3 2539.3 491 30.8 [476]
Pr6 Fe13 BiH13.8 818.5 2542.2 485 31.7 [476]
Nd6 Fe13 CuH20 817.7 2525.6 469 30.9 [476]
Nd6 Fe13 AgH18.0 819.8 2535 487 36.8 18.8 [471]
Nd6 Fe13 AuH16.6 808.4 2227 41.5 24.9 [461]
Nd6 Fe13 SiH14.7 810.3 2525.4 23.5 [461, 471]
Nd6 Fe13 SnH13.3 816.3 2524.5 22.8 [471]
Nd6 Fe13 GeH14.5 809.8 2526.6 22.8 [471]
Nd6 Fe13 GaH15 815.2 2521.0 458 40.1 [477]
Nd6 Fe13 PbH13.1 816.4 2526.7 22.6 [471]
Nd6 Fe13 SbH13.1 812.3 2522.0 31.9 [476]
Nd6 Fe13 BiH13.7 814.2 2526.6 33.1 [476]
corresponding hydrides R = La, Pr, Nd, and M = Fe, Co [480]. This has confirmed
the exclusive location of the Sn atom on one unique crystal position.
Such δ phase crystal structure can also be obtained with Co instead of Fe. In
La6 Co13 A (A = In, Tl, Sn, Pb, Sb, Bi), the mean cobalt magnetic moment has been
estimated to about 1 μB /Co atom [457], the ordering temperature being about 490 K
for La6 Co13 In. Lattice parameters and some magnetic properties of R6 Co13–x Ax
compounds are given in Table 26.
15 Metallic Magnetic Materials 757
The story of Sm-Co magnets can be traced back to the 1940s, when the study of
rare-earth metals was greatly accelerated because of advances in chemical sepa-
ration techniques developed in association with the Manhattan Project. Magnetic
properties of GdCo5 were first reported by Nesbit [481] in 1959 and Hubbard [482]
in 1960. However, the significance of their work was overlooked, perhaps due to the
high cost of Gd and low magnetization of GdCo5 .
In 1966, Hoffer and Strnat [483] reported the extremely large magnetocrystalline
anisotropy of YCo5 . They further predicted that YCo5 and most other RCo5
compounds were candidates for new high-performance magnet materials. The
significance of this discovery was immediately recognized, and extensive studies
followed to determine the magnetic properties of RCo5 (R = Y, Sm, Ce, La, Nd, and
mischmetal) [484]. The first YCo5 specimens made by Strnat’s group in 1966 had
(BH)max only around 8 kJ/m3 , and in 1967, the same group reported 41 kJ/m3 for
SmCo5 [485]. Further improvements in (BH)max for SmCo5 resulted in 147 kJ/m3
in 1968 by Velge and Buschow [322] and 159 kJ/m3 by Das [486], Benz, and Martin
[487]. Today, the best (BH)max of SmCo5 is around 199 kJ/m3 . Partial substitution
of Pr for Sm gave slightly enhanced magnetization and energy product.
R2 Co17 compounds possess higher magnetization and Curie temperatures than
RCo5 . However, it proved to be very difficult to develop useful coercivity in
Sm2 Co17 [488–490]. It took nearly 10 years for Sm2 (Co,Fe)17 -based magnets to
reach 240 kJ/m3 by using Cu and Zr substitution for Co, coupled with a long
and complex processing [491–493]. The best (BH)max of Sm2 (Co,Fe,Cu,Zr)17 -type
magnets is 271 kJ/m3 at room temperature.
Figure 15 shows the binary Sm-Co phase diagram [494–496]. There exist quite
a few intermetallic compounds in the Sm-Co system, where SmCo5 and Sm2 Co17
possess important technical significance. As shown in Fig. 16 [497], SmCo5 has
a hexagonal crystal structure (1:5H, space group: P6/mmm; prototype: CaCu5 ),
while Sm2 Co17 has a rhombohedral crystal structure (2:17R, space group: R 3 m;
prototype: Th2 Zn17 ) at room temperature and a hexagonal crystal structure (2:17H,
space group: P63 /mmc; prototype: Th2 Ni17 ) at high temperatures (1300–1340 ◦ C).
Though applications of Nd-Fe-B magnets have greatly expanded since the mid-
1980s, Sm-Co magnets are still important because of their excellent thermal stability
and better corrosion resistance. Sm-Co magnets can be used at temperatures up to
∼300 ◦ C owing to their high Curie temperatures.
The Sm-Co magnets are based on SmCo5 and Sm2 Co17 phases. The composition
of the SmCo5 magnet is slightly Sm-rich, as compared with its chemical stoichiom-
etry. Its microstructure is basically a featureless single phase. On the other hand, the
composition and microstructure of Sm2 Co17 -based magnets are more complicated.
Figure 17 shows the TEM microstructure of a Sm(Co0.715 Fe0.20 Cu0.06 Zr0.025 )7.1
magnet after sintering at 1200 ◦ C for 1 h, followed by a solid solution heat
treatment at 1180 ◦ C for 5 h, isothermal aging at 800 ◦ C for 40 h, and slow
cooling from 800 ◦ C to 400 ◦ C at 1 ◦ C per minute. Its intrinsic coercive force is
1200 kA/m.
758 J. P. Liu et al.
1200 1200°C
bCo7Sm2
1074°C 1074°C
1100
Temperature °C
1000 (g Sm)
(aCo) 922°C
a Co7Sm2
a Co17Sm2
800 (bSm)
Co5-xSm
Co2Sm
734°C
Co3Sm
695°C
605°C 595°C
600 575°C
~64 ~83
422°C
400
Co4Sm9
CoSm3
(εCo) (aSm)
200
0
0 10 20 30 40 50 60 70 80 90 100
Co Atomic Percent Samarium Sm
Fig. 16 Crystal structures of SmCo5 (H) (a), Sm2 Co17 (R) (b), and Sm2 Co17 (H) (c)
boundary phase is the origin of the high coercivity, while the high coercivity in
SmCo5 magnets is generally attributed to nucleation.
Sintered Sm-Co magnets are very hard and brittle; therefore, machining them
into the final shape and size is troublesome, especially for tiny magnetic parts.
This led to the development of bonded Sm-Co magnets [497], which are made
by consolidating a magnet powder with a polymer matrix. Thermosetting binders,
such as epoxy resin, are employed for use in compression-molded magnets, while
thermoplastic binders, like nylon, for injection-molded magnets, and elastomers
, such as rubber, are used for extruded magnets [498]. Table 27 lists magnetic
properties of some Sm-Co magnets.
A fundamental change takes place for the coercivity mechanism when the
grain size reduces from micrometer to nanometer range. Intrinsic coercivity
of 1240 kA/m was easily obtained after annealing a high-energy ball-milled
stoichiometric Sm2 Co17 specimen at 750 ◦ C for only 1 min [499]. Surfactant-
assisted high-energy ball milling has been used to produce anisotropic SmCo5
nanoflakes, and the subsequent magnetic alignment and compaction would yield
bulk, anisotropic, nanocrystalline SmCo5 magnets [500–503]. Alternatively, bulk,
anisotropic, nanograin SmCo5 magnets with coercivity of 795–3980 kA/m and
(BH)max of 88–135 kJ/m3 were synthesized by hot compacting the high-energy
ball-milled SmCo5 powder at 700 ◦ C, followed by hot deformation at 800–900 ◦ C
with a height reduction of 70–90% [501, 504].
760 J. P. Liu et al.
Table 27 Magnetic properties of some commercial Sm-Co magnets (TM stands for Co,Fe,Cu,Zr)
(BH)max
Magnets μ0 Mr (T) i Hc
(kA/m) B Hc(kA/m) (kJ/m3 ) Ref.
SmCo5 , (Sm,Pr)Co5 0.8–1.0 >1900 600–780 130–190 a,b
Sm2 TM17 0.9–1.2 >1900 710–840 180–255 a,b
Temp. compensated 0.5–0.75 >1900 400–600 64–120 a
SmCo5
Temp. compensated 0.8–0.95 >1900 480–720 80–175 a
Sm2 TM17
Bonded SmCo5 0.4–0.5 600–1600 240–520 32–65 [497],b
Bonded Sm2 TM17 0.6–0.8 400–1600 310–530 64–130 [497],b
a http://www.electronenergy.com/products/samarium-cobalt.htm
b http://www.western-magnet.com/product.php
[509]). From the scientific perspective, the identification of Nd2 Fe14 B spawned a
great deal of exploration for structural isomorphs, determination of their intrinsic
properties, and investigation of the mechanisms responsible for those properties. On
the technological side, magnets based on Nd2 Fe14 B continue to dominate the high-
performance magnet market. Larger energy products (BH)max in conjunction with
the cost advantage over Sm-Co have enabled progressive growth in the spectrum of
applications for Nd-Fe-B. Approximately 80,000 metric tons of Nd-Fe-B magnets
was produced in 2015 with forecasts of 120,000 tons in 2020.
Of the elemental, eight binary, and three ternary members of the Nd-Fe-B
phase diagram (Fig. 18), only Nd2 Fe14 B features sufficient magnetization and
magnetocrystalline anisotropy to qualify as a permanent magnet candidate. Its unit
cell, displayed in Fig. 19, is tetragonal (P42 /mnm space group, No. 136), contains
four formula units (68 ions), and comprises six crystallographically distinct iron
sites, two different rare-earth positions, and one boron site. There is an eight-layer
repeat structure perpendicular to the c-axis. All Nd and B ions and the four Fe(4c)
ions reside in the basal (z = 0) and z = ½ mirror planes. Between these planes, the
other Fe ions form three puckered nets. The Fe(16k1 ), Fe(16k2 ), Fe(8j1 ), and Fe(4e)
sites comprise two slightly distorted hexagonal meshes rotated by ∼30◦ with respect
to one another; they enclose a network of Fe(8j2 ) sites located above or below the
centers of hexagons in the neighboring layers.
Many similarities exist between Nd2 Fe14 B and other crystal structures. The
hexagonal Fe layers resemble the nets in the σ -phase occurring in the Fe-Cr and
Fe-Mo systems. Among features common to Nd2 Fe14 B and the hexagonal CaCu5
structure of SmCo5 is the centering of the rare-earth atoms within hexagonal prisms.
Further parallels can be identified since many rare-earth transition metal (RE-
TM) structures are derivatives of CaCu5 . For example, the rhombohedral Th2 Zn17
structure in which Sm2 Co17 and Nd2 Fe17 crystallize can be obtained from CaCu5
by appropriate ion substitutions.
A link to TM–metalloid systems is evident from the boron coordination in
Nd2 Fe14 B. As Fig. 20 shows, each boron occupies the center of a trigonal prism
formed by the three nearest Fe atoms above and the three below either the basal or
z = ½ planes. Connecting the Fe layers above and below the planes containing Nd
and B, the prisms clearly contribute to the stability of the structure. Such prisms
are fundamental to the structure of many TM–metalloid materials, crystalline (e.g.,
FeB, Fe3 C, Fe3 P) as well as amorphous.
Table 28 lists intrinsic properties of a few magnetic materials for comparison
purposes. The saturation magnetization Ms sets the theoretical upper limit (BH)theor
max
= (μ0 Ms )2 /4μ0 for the energy product, and the anisotropy field HA represents the
largest intrinsic coercivity Hci that can be achieved in a practical magnet. Commer-
cial magnets based on Nd2 Fe14 B, Pr2 Fe14 B, SmCo5 , Sm2 Co17 , Sm2 Fe17 N3 , and
ferrites are available. Although ferrites are characterized by (BH)max of at most
∼50 kJ/m3 , they are the least expensive hard magnets per unit energy product
and very broadly used. Pr2 Fe14 B and Nd2 Fe14 B exhibit similar properties, and
for that reason less abundant Pr is frequently not separated from rare-earth ores
and retained as a constituent of magnets primarily containing Nd2 Fe14 B. For low-
762 J. P. Liu et al.
temperature applications, Pr2 Fe14 B-based magnets are of significance, however, due
to the fact that the spin reorientation in Nd2 Fe14 B below 135 K does not occur
in Pr2 Fe14 B. Elemental Fe is included in Table 28 since its large Ms implies an
max = 920 kJ/m . Unfortunately, that cannot be realized since HA
enormous (BH)theor 3
is much too small; it must be substantially greater than Ms . While Dy2 Fe14 B and
Tb2 Fe14 B are not of interest as permanent magnets by themselves owing to the
scarcity of Dy and even more so Tb, their large anisotropy fields make Dy and Tb
very useful as low-level substituents to increase the coercivity of Nd2 Fe14 B-based
magnets and to improve its temperature dependence.
Fabrication of a practical permanent magnet from a compound having suitable
intrinsic properties, principally those of Table 28, requires a specific processing
method with an associated starting composition. The energy product and coercivity
are crucially dependent on the resultant microstructure, which involves the geometry
and orientation of the crystallites of the compound and the character and distribution
of secondary phases that can control domain wall formation and motion and,
hence, the magnetization and demagnetization behavior. Several methods are in
commercial use for the preparation of Nd-Fe-B magnets.
15 Metallic Magnetic Materials 763
diagram, Fig. 18), Nd oxides and pores. As the micrograph of Fig. 21 indicates, the
average Nd2 Fe14 B grain size is ∼10 μm; Nd2 Fe14 B occupies ∼85% of the volume.
The Nd-rich phase occurring at grain boundary junctions and in thin intergranular
layers is vital, serving as a liquid phase sintering aid.
Another important processing method is the rapid solidification technique of melt
spinning, in which molten starting alloy is ejected through a crucible orifice onto
the rim of a substrate disc rotating with surface velocity vS . The cooling rate is
proportional to vS and can reach 106 K/s. Ribbon fragments typically 30–50 μm
thick, 1–3 mm wide, and 1 mm-1 cm long are produced. The microstructure and
15 Metallic Magnetic Materials 765
magnetic properties are sensitive to the quench rate, with Hci and (BH)max each
featuring a maximum as a function of vS . The micrograph of Fig. 22 (a) shows
that optimally quenched ribbons consist of spheroidal Nd2 Fe14 B grains with an
average diameter of ∼30 nm, some two orders of magnitude smaller than that
of sintered magnets (cf. Fig. 21). Nd2 Fe14 B comprises ∼95% of the volume.
The brittle melt-spun flakes can be consolidated into bulk magnets by (i) cold
compaction with a binder; (ii) hot pressing, which yields full densification with
little change in the microstructure and only marginal alignment of the randomly
oriented grains in the as-cast ribbons; and (iii) die upsetting, a second hot press in a
larger diameter die that can lead to as much as ∼75% magnetic alignment and much
larger (BH)max . Remarkably, die upsetting transforms the spheroidal grains of the
hot-pressed precursor to platelets stacked transverse to the press direction with the
c-axes normal to the grain faces (Fig. 22b).
In the hydrogen disproportionation desorption recombination (HDDR) process,
starting Nd-Fe-B material is heated under flowing H2 gas and disproportionates
into Fe, Fe2 B, and Nd hydride. Continued heat treatment in vacuum desorbs the
hydrogen and, rather spectacularly, recombines the disproportionated products into
fine-grained, coercive Nd2 Fe14 B. HDDR is one means for preparing Nd-Fe-B
powder for the manufacture of anisotropic bonded magnets, and the method is also
promising for the recycling of sintered Nd-Fe-B material.
Nd-Fe-B magnets having energy products as large as ∼400 kJ/m3 (50 MGOe)
are available commercially, and research efforts to further enhance (BH)max toward
max [Nd2 Fe14 B] = 510 kJ/m (64 MGOe) continue. One
the ultimate limit (BH)theor 3
Fig. 22 (a) Bright field transmission electron micrograph (TEM) of optimally quenched Nd-Fe-B
ribbon. The inset is a selected area diffraction pattern demonstrating random distribution of the
Nd2 Fe14 B grains. The arrow indicates the thin (∼2 nm) Nd-rich, B-deficient amorphous phase
of approximate composition Nd0.7 Fe0.3 (near the eutectic in the binary Nd-Fe phase diagram)
occupying the intergranular regions (Mishra [515]). (b) TEM of a die-upset Nd-Fe-B magnet
(courtesy R. K. Mishra). (With kind permission from Elsevier)
to greater remanence. Minimizing the amount of the former would enable progress
max [Fe] = 920 kJ/m (120 MGOe).
toward the ultimate practical limit (BH)theor 3
Magnetocaloric Intermetallics
Gd5 (Si1−x Gex )4 , La(Fe,Si)13 , MnFe(P1−x Asx ), NiMn-based Heusler alloys, hexagonal MM’X compounds, and Mn(As1−x Sbx ), where
V/V denotes the
volume change of lattice across magnetostructural transformation,
S entropy change, and
Tad adiabatic temperature change (directly or indirectly obtained
by direct measurements or calculations)
Sample
V/V MCEa BCEa ECEa
S
Tad
S
Tad
S
Tad
0–
0–2T 5T 0–2T 0–5T
FeRh 0.9% 12 J/kgK I [522] 12 J/kgK I [522] −6 K I [520] – −12.5 J/kgK 8–10 K 13 J/kgKI [520] −5.17 K
316 K 316 K Direct 316 K C [522] C [520] 5.29 kbar I [520]
Fe49 Rh51 Fe49 Rh51 Fe49 Rh51 2.0kbar 2.5 kbar 316 K 5.29 kbar
316 K Direct Fe49 Rh51 Direct
Fe49 Rh51 316 K 316 K
Fe49 Rh51 Fe49 Rh51
Gd5 (Si1−x Gex )4 0.4∼ −14 J/kgK C [523] −18J/kgK C [523] 7.3 K C [523] 15.0 K C [523] −13 J/kgK −1.3 K – –
1.0% 276 K 276 K Indirect 276 K Indirect 276 K C [525] C [525]
Gd5 Si2 Ge2 Gd5 Si2 Ge2 Gd5 Si2 Ge2 Gd5 Si2 Ge2 2.9 kbar 276 K −2 kbar
Gd5 Si2 Ge2 Direct
276 K
Gd5 Si2 Ge2
La(Fe, Si)13 - −1.2∼ −14.4 J/kgK −19.4 J/kgK 8.1 K C [534] 12.1 K C [534] – – – –
based −1.6% C [528] 208 K C [528] 208 K Indirect 184 K Indirect 184 K
compounds LaFe11.4 Si1.6 LaFe11.4 Si1.6 LaFe11.7 Si1.3 LaFe11.7 Si1.3
−12 J/kgK C [530] −20 J/kgK C [530] – – 8.6 J/kgK I 2.3K I [537] – –
274 K 274 K [537] 2.1 kbar 2.1 kbar
LaFe11.2 Co0.7 Si1.1 LaFe11.2 Co0.7 Si1.1 250 K Direct 250 K
LaFe11.33 LaFe11.33
Co0.47 Si1.2 Co0.47 Si1.2
−16 J/kgK C [532] −20 J/kgK C [532]
155 K 155 K
LaFe11.5 Mn0.2 Si1.3 LaFe11.5 Mn0.2 Si1.3
J. P. Liu et al.
– −17 J/kgK C [533] 7.1 K C [534] 15.4 K C [534] – – – –
288 K Indirect Indirect
La(Fe11.5 Si1.5 )H1.3 184 K 184 K
LaFe11.7 Si1.3 H1.1 LaFe11.7 Si1.3 H1.1
– −12 J/kgK C [535] – – – – – –
250 K
La
(Fe11.6 Si1.4 )C0.6
MnFeP 0.06% −14 J/kgK C [539] −18 J/kgK C [539] – – – – – –
(As,Si,Ge) 304 K 304 K
15 Metallic Magnetic Materials
Table 29 (Continued)
Sample
V/V MCEa BCEa ECEa
S
Tad
S
Tad
S
Tad
0–2T 0–5T 0–2T 0–5T
Hexagonal −2.8∼ −11.6 J/kgK −30 J/kgK C [549] – – 52 J/kgK 18 K I [551] – –
MM’X −3.9% C [549] 322 K I [551] 3 kbar
compounds 322 K Mn0.96 Cr0.04 CoGe 3 kbar Indirect
Mn0.96 Cr0.04 CoGe 300 K 300 K
MnCoGe0.99 MnCoGe0.99
In0.01 In0.01
−7 J/kgK C [214] −19 J/kgK C [214] – – – – – –
266K 266K
MnNi0.77 Fe0.23 Ge MnNi0.77 Fe0.23 Ge
MnAs1−x Sbx −1.1∼ −32 J/kgK C [553] −32 J/kgK C [553] 5 K C [553] 13 K C [553] – – – –
−2.1% 318 K 318 K 318K 318 K
MnAs MnAs Indirect Indirect
MnAs MnAs
−26 J/kgK C [553] −26 J/kgK C [553]
309 K 309 K
MnAs0.95 Sb0.05 MnAs0.95 Sb0.05
−8.7 J/kgK −19 J/kgK C [555] – – – – – –
C [555] 315 K
315 K MnAs/- MnAs/GaAs(001)
GaAs(001)
−3.4 J/kgK −7 J/kgK C [555] – – – – – –
C [555] 315 K
315 K MnAs/- MnAs/GaAs(111)
GaAs(111)
a The superscripts I and C denote the inverse and conventional character of the caloric effect, respectively
J. P. Liu et al.
15 Metallic Magnetic Materials 771
Heavy-Fermion Compounds
γ * is the enhanced γ -value (me is the free electron mass). Thus, heavy-fermion
compounds allow investigation of the electron mass renormalization paradigm
processes. Around 1990, it was realized that in some heavy-fermion compounds,
Landau’s Fermi liquid breaks down, since a linear electronic term in the specific
heat is not attained, even at the lowest temperatures. Consequently, new ideas and
new theoretical models had to be developed to explain the non-Fermi liquid (NFL)
behavior [558, 559]. Nowadays, heavy-fermion compounds are considered to be
ideal laboratory tools for the investigation of quantum phase transitions, where non-
Fermi liquid behavior occurs right at the quantum critical point.
The archetypical heavy-fermion compounds are mostly intermetallic compounds
that contain the 4f -element cerium [560] or the 5f -element uranium [561]. Near
room temperature, the f -moments behave as local (weakly interacting) magnetic
moments. Upon cooling, below a characteristic temperature that is typically 10 K,
termed the coherence temperature, the heavy-fermion behavior sets in. The key
ingredient in the formation of the heavy-fermion state is the hybridization of the
f -states with the s, p, or d orbitals of the ligand non-f -electron atoms in the
compound. The hybridization delocalizes the f -electrons resulting in a narrow
electron band at the Fermi level. This in turn leads to the high electron density of
states that is probed by the electronic specific heat. The phenomenology is captured
by the relations
Here, c is the molar specific heat, kF is the Fermi wavenumber, and N(EF ) is the
enhanced density of states per atom per spin direction at the Fermi level, EF (Vm is
the molar volume, kB is the Boltzmann constant, -h is the Planck constant divided by
2π, and NA is Avogadro’s number).
On the microscopic level, the understanding of the strongly correlated electron
state has evolved historically via the concepts of valence fluctuations, virtual bound
4f states, Kondo-lattice formation, and the competition between the Kondo effect
and the Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction [562], to the fields
of magnetic quantum phase transitions (QPT), quantum critical points (QCP), and
non-Fermi liquid behavior [563].
Most heavy-fermion compounds exhibit the Kondo effect. In its most simple
form, the Kondo Hamiltonian describes the exchange interaction between a single
magnetic impurity with spin S and a conduction electron with spin s: HK = − 2J
s · S. For an exchange coupling parameter J < 0, the impurity spin is completely
screened at low temperature, and a Kondo singlet is formed. The binding energy
for this single-ion Kondo effect is kB TK ∝ e−1/J N (EF ) /N (EF ), where TK is the
Kondo temperature. Heavy-fermion materials represent a periodic lattice formed
of magnetic impurity atoms (e.g., Ce atoms), called a dense Kondo-lattice. Upon
cooling below room temperature, the single-ion Kondo effect is replaced, near the
coherence temperature, by complex electron correlations which may result in a
nonmagnetic correlated electron ground state. A second important energy scale in
15 Metallic Magnetic Materials 773
Fig. 23 Simplified schematic phase diagram for heavy-fermion compounds based on the competi-
tion between the Kondo effect and RKKY interaction [562]. The solid lines represent the variation
of TK and TRKKY as a function of the exchange parameter J. HF, heavy-fermion (gray); FL, Fermi
liquid (yellow). Magnetic ordering (blue) vanishes at the critical value of the exchange parameter
Jc . Heavy-fermion behavior is observed in the vicinity of Jc
Fig. 24 Generic phase diagram in the vicinity of a continuous magnetic quantum phase transition
(after Ref. [563]). (With kind permission from SciPris). Magnetic order is depressed as a function
of the control parameter δ and vanishes at the quantum critical point (QCP). Close to the magnetic
phase boundary (dark gray region), the critical behavior is classical. In the region between the
dashed lines, the system behaves quantum critically
Table 31 Basic properties of heavy-fermion superconductors. The crystal structure, year of discovery, γ *-value, type of ground state, superconducting
transition temperature, Tc , and the Néel temperature, TN , are tabulated. SC, superconductor at ambient pressure; SC(p), superconductor under pressure; AF,
antiferromagnet; FM, ferromagnet. For SC(p) compounds, the maximum Tc and corresponding pressure are listed. The γ *-value is expressed in J/molf-atom ·K2
Compound Structure Year γ * (J/mol·K2 ) Type Tc (K) TN (K) Remarks Ref.
CeCu2 Si2 Tetragonal 1979 1.0 SC 0.5 – First heavy-fermion superconductor; close to AF order [592, 593]
with TN = 0.8 K
UBe13 Cubic 1984 1.1 SC 0.85 – Two SC transitions when doped with Th [594, 595]
UPt3 Hexagonal 1984 0.45 SC 0.55 – Two SC transitions Tc + = 0.49 K and Tc − = 0.43 K; [596–598]
weak AF order at TN = 5 K
URu2 Si2 Tetragonal 1986 0.18 SC 0.8 – Hidden order at 17.5 K [599]
CeCoIn5 Tetragonal 2001 0.29 SC 2.3 – [600]
CeIrIn5 Tetragonal 2001 0.72 SC 0.4 – [601]
PrOs4 Sb12 Cubic 2002 0.35 SC 1.85 – Two SC transitions at 1.75 K and 1.85 K [602, 603]
Ce2 CoIn8 Tetragonal 2002 0.50 SC 0.4 – [604]
β-YbAlB4 Orthorhombic 2008 0.15 SC 0.08 – NFL compound [605]
Ce2 PdIn8 Tetragonal 2009 1.00 SC 0.65 – [606]
UNi2 Al3 Hexagonal 1991 0.12 AF, SC 1.0 4.2 Small moment AF [607]
UPd2 Al3 Hexagonal 1991 0.15 AF, SC 2.0 14.2 Large moment AF [608]
CePt3 Si Tetragonal 2004 0.39 AF, SC 0.75 2.2 Non-centrosymmetric [609]
structure
J. P. Liu et al.
Ce3 PtIn11 Tetragonal 2015 1.2 AF, SC 0.32 2 [610]
CeCu2 Ge2 Tetragonal 1992 0.2 AF, SC(p) 0.6510 GPa 4.1 [611, 612]
CePd2 Si2 Tetragonal 1996 0.06 AF, SC(p) 0.42.8 GPa 10 [613][614]
CeRh2 Si2 Tetragonal 1996 0.08 AF, SC(p) 0.350.8 GPa 36 [615]
CeIn3 Cubic 1997 0.14 AF, SC(p) 0.182.5 GPa 10.1 [616]
CeRhIn5 Tetragonal 2000 0.42 AF, SC(p) 2.11.9 GPa 3.8 [617]
CeRhSi3 Tetragonal 2005 0.12 AF, SC(p) 1.12.0 GPa 1.6 Non-centrosymmetric [618]
structure
CeIrSi3 Tetragonal 2006 0.11 AF, SC(p) 1.6 2.5 GPa 5 Non-centrosymmetric [619]
15 Metallic Magnetic Materials
structure
UGe2 Orthorhombic 1991 0.03 FM, SC(p) 0.81.2 GPa – Coexistence FM and SC; TCurie = 53 K [620]
URhGe Orthorhombic 2001 0.16 FM, SC 0.25 – Coexistence FM and SC; TCurie = 9.5 K [621]
UIr Monoclinic 2004 0.05 FM, SC(p) 0.12.7 GPa – Coexistence FM and SC; TCurie = 46 K [622]
UCoGe Orthorhombic 2007 0.06 FM, SC 0.6 – Coexistence FM and SC; TCurie = 3.0 K [623]
777
778 J. P. Liu et al.
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99 (2007)
Olivier Isnard received his PhD from Univ. Joseph Fourier and
Institut Laue Langevin Grenoble France in 1993. Now Profes-
sor of Physics at Néel Institute, University Grenoble Alpes, he
worked at the University of Missouri in USA, University of
Amsterdam NL. Doctor Honoris Causa of both Babes Bolyai and
Technical Universities in Cluj Romania, he works on magnetism
of rare-earth transition metal intermetallics.
15 Metallic Magnetic Materials 807
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 810
GaAs (001) Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
Structure and Magnetism of Magnetic 3d Transition Metals . . . . . . . . . . . . . . . . . . . . . . . . . . 812
Cr/GaAs (001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 812
Mn/GaAs (001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 814
Fe/Cu (001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 816
Co/GaAs (001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 819
Ni/GaAs (001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
Structure and Magnetism of Magnetic 3d Transition Metal Alloys . . . . . . . . . . . . . . . . . . . . . 826
Py/GaAs (001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
Cox Mn1−x /GaAs (001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829
Fex Cu1−x /GaAs (001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
Fex Pd1−x /Cu (100) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
Abstract
D. Wu
National Laboratory of Solid State Microstructures and Department of Physics, Nanjing
University, Nanjing, People’s Republic of China
e-mail: [email protected]
X.-F. Jin ()
Department of Physics and State Key Laboratory of Surface Physics, Fudan University, Shanghai,
People’s Republic of China
e-mail: [email protected]
(bcc) phase of Ni, which does not exist in nature, can be epitaxially grown on
GaAs (001). It is found that the interface structure and film growth temperature
play a crucial role in determining the film structure and magnetism. With these
metastable structure phase and precisely controlled composition of 3d transition
magnetic metal and their alloy films, we explore several interesting physics such
as the origin of the extremely small magnetocrystalline anisotropy in permalloy
and the correlation between the structure and magnetism in Co1−x Mnx alloys.
Introduction
Significant progress has been made in the epitaxial growth of magnetic metallic
films (MMFs) by molecular beam epitaxy (MBE) over the past four decades.
Nowadays it is routinely growing single-crystalline MMFs on different substrates
with submonolayer control. This allows us to understand the fascinating funda-
mental properties of the MMFs, which leads to important applications in current
information technologies. A remarkable example is the discovery of the giant
magnetoresistance (GMR) effect in metallic magnetic multilayers (e.g., Fe/Cr or
Co/Cu superlattices) [1, 2] and the employment of the GMR in the read head of
hard disks. Since then, a variety of spin transport phenomena were discovered and
applied to spintronic devices.
There are four ferromagnetic (FM) elementary metals, Fe, Co, Ni, and Gd. Fe,
Co, and Ni and their alloys have been dominant materials in magnetism in both
fundamental studies and applications, partially because their Curie temperature
(Tc) is much higher than room temperature. Cr and Mn are the only two anti-
ferromagnetic (AFM) metallic elements. According to the Slater-Pauling model
[3, 4], the magnetic state is related to the occupation of d band around the Fermi
level. These five magnetic elementary metals are all 3d transition metals with
atomic numbers continuously changing from 24 to 28. The binary metal alloys
with precisely controlled composition provide a model system to tune the Fermi
level and manipulate the corresponding magnetic properties. Therefore, they and
their alloys are the ideal platforms for a fundamental understanding of magnetism
in the thin film state. Moreover, the magnetic properties of the films such as the
magnetic anisotropy and the magnetic order are substantially different from these of
bulk. A comprehensive and systematic investigation of the 3d MMFs is important.
The recent technological applications of spintronics are mostly based on the 3d
MMFs, and spintronics is also an important driving force for their investigation. For
example, the spin-orbit torque phenomenon which can switch the magnetic moment
by a dc current occurs in AlOx /Co/Pt with Co layers a few monolayers thick [5].
The 3d transition metals and alloys have a variety of crystallographic and
magnetic phases in bulk, some of which only exist at high pressure or high
temperature. In addition to these thermodynamically stable phases, metastable
structures could be epitaxially grown on single-crystalline substrates. In this chapter
we focus on the epitaxial growth and magnetic properties of the magnetic 3d
transition metal and their alloy films.
16 Metallic Magnetic Thin Films 811
Among several film growth methods such as MBE, magnetron sputtering, and
pulsed laser deposition (PLD), MBE is the most powerful technique to grow the
highest-quality MMFs. GaAs (001) substrates are widely used for the epitaxial
growth of 3d transition metals and their alloys. The cubic lattice constant is
0.565 nm. The top view of the unreconstructed GaAs (001) together with the corre-
sponding Miller indices is schematically shown in Fig. 1a. If a cubic-structure film is
grown on GaAs (001) surface, there are two kinds of epitaxial growth geometry: (i)
the face-centered cubic (fcc) structure with (001)[110]film //(001)[100]GaAs , in which
the epitaxial film rotates 45◦ around the surface normal, and (ii) the body-centered
cubic (bcc) structure with (001)[100]film //(001)[100]GaAs , as schematically shown
in Fig. 1b, c, respectively. The lattice constants are 0.399 nm for the fcc structure
and 0.283 nm for the bcc structure without distortion. Lattice misfits are relatively
small for 3d transition metals and alloys, meaning that GaAs is the ideal substrate
for these metals. For example, the lattice misfits are 0.1% for bcc Co/GaAs film
and − 8.6% for fcc Mn/GaAs film.
Te-doped GaAs (001) single crystal wafers can be prepared by two different
procedures after cleaning in acetone, water, and alcohol in an ultrasonic bath in
Fig. 1 Schematic top view of the unreconstructed GaAs (001), together with rotated fcc
structure film with (001)[110]film //(001)[100]GaAs and unrotated bcc structure film with
(001)[100]film //(001)[100]GaAs [6]. LICENSE #: 4812820853366
812 D. Wu and X.-F. Jin
sequence. One is a standard method for most substrates. The GaAs substrate is
◦
bombarded by 800 eV argon ions and then annealed at 500 C for several cycles
in the ultrahigh vacuum (UHV). The other is a chemical etching method, using
H2 SO4 :H2 O2 :H2 O = 5:1:1 to etch the substrate. Then it is loaded into the UHV
◦
system and flashed to 580 C. The observation of a clear (4 × 1) low-energy electron
diffraction (LEED) or reflection high-energy electron diffraction (RHEED) pattern
indicates a clean surface. Auger spectra show the surface is free of carbon and
oxygen contamination. We find that the latter procedure gives a better substrate for
epitaxial growth.
Cr/GaAs (001)
Chromium has a bcc structure in bulk with a lattice constant of 0.2885 nm. The
lattice mismatch between GaAs (001) substrate and bcc structure Cr is less than
1.9%. The Cr film growth on GaAs (001) is expected to be bcc with the epitaxial
relationship: (001)[100]Cr //(001)[100]GaAs and (001)[100]Cr //(001)[100]GaAs , as
shown in Fig. 1c.
The structure of Cr films grown on the GaAs (001) substrate is dependent on the
growth temperature [7]. Figure 2a presents the typical RHEED pattern for a clean
GaAs (001) surface, with an electron beam along the GaAs [110] direction. In the
initial stage of the film growth at room temperature, the RHEED pattern shows some
polycrystalline circles, seen in Fig. 2b. After the thickness is beyond ∼1.2 nm, a new
diffraction pattern emerges and persists as long as Cr is being deposited. The typical
pattern at this stage is shown in Fig. 2c.
The previous study found that the orientation of the Cr/GaAs (001) film
is (112)[110]Cr //(001)[110]GaAs and (112)[111]Cr //(001)[110]GaAs , instead of the
geometry shown in Fig. 1c [8]. To determine the epitaxial orientation, we schemati-
cally draw these two growth geometries in Fig. 3a, b together with the corresponding
Miller indices. There are two types of structures labeled as (I) and (II) for (112)
plane growth geometry according to the structure symmetry. The RHEED patterns
of type I and type II structures are calculated and shown in Fig. 2f, i, respectively.
Comparing with the experimental results (Fig. 2c), we can immediately determine
that only type I structure is formed. This result is further confirmed by X-ray
diffraction (XRD) [7]. This growth geometry has not been found in other 3d
transition metals and their alloys. It is still not understood why the (112) plane
growth occurs since the lattice mismatch is as high as 25% along [110] direction
or why only type I structure can be grown from the symmetry point of view.
For growth temperatures between 130 and 160◦ C, the RHEED pattern is different
from the room temperature growth case after the initial deposition of ∼1.4 nm, as
shown in Fig. 2e. The growth geometry of Fig. 3a is calculated and shown in Fig. 2h,
in good agreement with the experimental pattern of Fig. 3e. Therefore, the growth
16 Metallic Magnetic Thin Films 813
Fig. 2 RHEED patterns of Cr grown on the GaAs (001) substrate at different growth temperatures
and thickness, taken with the incident electron beam along the substrate [110] direction: (a) clean
GaAs (001); (b) 1.0 nm, 25◦ C; (c) 5.0 nm, 25◦ C; (d) 1.6 nm, 100◦ C; (e) 4.0 nm, 160◦ C; (i–i)
calculated diffraction patterns explained in the text [7]
Fig. 3 Epitaxial relationships between Cr and GaAs: (a) (001)[100]Cr //(001)[100]GaAs and
(001)[100]Cr //(001)[100]GaAs ; (b) shadow I, (112)[110]Cr //(001)[110]GaAs and (112)[111]Cr //
(001)[110]GaAs ; shadow II, (112)[110]Cr //(001)[110]GaAs and (112)[111]Cr //(001)[110]GaAs [7].
LICENSE #: 4812840298511
Mn/GaAs (001)
Several stable structure phases are available for bulk Mn [9]. The α-phase, which
is a complex cubic structure with 58 atoms per unit cell, is stable below 1000 K.
It is antiferromagnetic (AFM) below 95 K. The β-phase, which is also a complex
cubic structure with 20 atoms per unit cell, is stable between 1000 and 1364 K and
can be retained at room temperature by quenching. The β-phase is nonmagnetic.
The γ -phase, which has the fcc structure, is stable between 1364 and 1410 K. The
δ-phase, which is bcc structure, is stable between 1410 and 1450 K. Both γ - and
δ-phases exist well beyond any magnetic ordering temperature. The metal-stable
phases of Mn were successfully grown on Pd (001) and Ag (001) surfaces with
distorted fcc structure [10, 11]. A nearly fcc structure with 3-monolayer (ML) Mn
layers can be obtained in the (Mn/Ag)n superlattice on Ag (001) [12]. Epitaxial
16 Metallic Magnetic Thin Films 815
Fig. 4 RHEED patterns for (a) the clean GaAs (001) surface and (b), (c) fcc Mn thin films of 8 nm
grown on the GaAs (001) substrate with different electron incident directions, respectively [13].
LICENSE #: 4812840822141
816 D. Wu and X.-F. Jin
Fe/Cu (001)
Iron exhibits a rich variety of magnetic phases. Fe is bcc and FM in bulk. The fcc
phase is stable above 910◦ C. It is predicted to be nonmagnetic, AFM, FM, or order
as a spin density wave (SDW), depending on the lattice constant [16–22]. The fcc-Fe
16 Metallic Magnetic Thin Films 817
Fig. 6 XRD spectra for Mn on GaAs (001), prepared at different growth temperature and film
thickness: (a) 300 K, 20 nm Mn; (b) 400 K, 10 nm Mn; and (c) 500 K, 20 nm Mn. (d) HRTEM
image for 10 nm Mn on GaAs (001) grown at 400 K [14]. LICENSE #: 4812841356913
Fig. 7 (a) and (b) Two types of RHEED oscillations for Fe/Cu (001) grown at 300 K [31].
LICENSE #: RNP/20/APR/024963
Fig. 9 Temperature-
dependent magnetization as a
function of temperature for 6,
7, and 8 ML Fe on Cu (100),
respectively; curves (a–e) are
some representative
hysteresis loops at different
temperatures; (f) coercivity
versus temperature for 8 ML
Fe/Cu (001) [31]. LICENSE
#: RNP/20/APR/024963
of Fig. 10 shows the incommensurate SDW along z direction. The fitting of the
experimental data to an SDW yields q = 2π/2.7d, where d is the interlayer distance
of fcc Fe, as shown by the solid line in Fig. 8. The good fitting strongly suggests that
the magnetic structure is SDW. The magnetic configurations of 6, 7, 8, and 9-ML
Fe on Cu (001) can be constructed one by one as schematically shown in Fig. 10.
Co/GaAs (001)
The hexagonal close-packed (hcp) and fcc structures are, respectively, the stable and
metastable phases of Co. Although the bcc structure is not available in bulk, it was
realized by epitaxial growth on GaAs (110) substrates. A negative cubic magnetic
anisotropy K1 and a strong in-plane uniaxial anisotropy Ku were proposed [33]. The
negative K1 denotes the easy axes along bcc Co <110> directions. However, it was
pointed out that bcc Co phase is not a true metastable phase but a force-induced
phase [34]. The bcc Co phase grown on GaAs (001) substrate was first reported by
820 D. Wu and X.-F. Jin
Blundell et al. [35] They found a positive K1 for 4-nm Co/GaAs (001), contrary to
a previous report. Another group reported that Co films grown on GaAs (001) were
not bcc but two-domain hcp, resulting in positive K1 [36]. Theoretical calculation
predicted that the surface layer contributes to a large positive K1 [37].
The structure of Co grown on GaAs (001) depends on film thickness and growth
temperature. Figure 11a shows a typical RHEED pattern for a clean GaAs (001)
surface, with an electron beam along the [110] direction. A new RHEED pattern
appears at ∼0.2 nm for Co films grown at 150◦ C. This new pattern is clearly seen
after ∼0.8 nm, shown in Fig. 11d [38]. The pattern remains the same by rotating the
electron beam 90◦ to the [110] direction, indicating a fourfold in-plane geometry.
This pattern is the same as the calculated bcc structure RHEED pattern (Fig. 11g).
Moreover, we compare the RHEED pattern of the bcc Fe [39] (Fig. 11b) and fcc Mn
(Fig. 11c) epitaxially grown on GaAs (001). From the similarity between Fig. 11b, d,
again, we can immediately conclude that the structure is bcc.
When the film thickness is beyond ∼2 nm, a new RHEED pattern develops
together with the bcc pattern, shown in Fig. 11e. If we consider the new phase
is hcp Co proposed earlier [36], the calculated pattern of the mixture of the bcc
and hcp structure (Fig. 11h) is consistent with the experimental result (Fig. 11e).
The growth geometry is determined to be (1210)[0001]Co //(001)[110]GaAs and
(1210)[0001]Co //(001[110]GaAs .
When the film thickness exceeds ∼6 nm, the RHEED pattern is dominated by
the hcp structure, as shown in Fig. 11f. Interestingly, the pattern remains the same
after rotating the electron beam 90◦ , contrary to the sixfold symmetry of the hcp
structure. This implies the fourfold symmetry pattern might actually come from the
two perpendicularly oriented hcp Co domains, with [0001]Co //(001)[110]GaAs and
16 Metallic Magnetic Thin Films 821
Fig. 11 RHEED patterns for different thin films grown on the GaAs (001) substrate, taken with
the incident electron beam along the substrate [110] direction: (a) clean GaAs (001), (b) 5.6-nm
bcc Fe, (c) 8.0-nm fcc Mn, (d) 1.5-nm bcc Co, (e) 3.5-nm bcc and hcp Co, (f) 15-nm hcp Co, and
(g–i) calculated diffraction patterns corresponding to (d–f), respectively. ◦ and • correspond to the
two hcp domains described in the text [38]. LICENSE #: RNP/20/APR/024982
822 D. Wu and X.-F. Jin
[0001]Co //(001[110]GaAs together [36]. The calculated pattern is shown in Fig. 11i
according to the two-domain structure, in good agreement with the experimental
result (Fig. 11f). In particular, the intensity of the second and fourth columns from
right to left are much stronger than they ought to be, owing to the overlap of the
two-domain diffraction.
The structure of the Co/GaAs (001) film is directly studied by HRTEM, as shown
in Fig. 12 [40]. The bilayer structure is clearly seen, with the bcc structure at the
bottom and the hcp structure at the top. The diffraction pattern corresponding to this
HRTEM picture does indicate that the top hcp Co film has a two-domain structure
with c axes perpendicular to each other [38]. The thickness of the Co bcc structure is
found to increase with increasing the growth temperature in the grown temperature
range studied (60–160◦ C) [41].
A 1.4-nm bcc Co/GaAs (001) film, capped with 3.0-nm Au layer, measured by
ex situ MOKE at room temperature, is shown in Fig. 13. The film exhibits strong
uniaxial anisotropy with the easy axis along [110] direction. In order to extract
the fourfold anisotropy field, rotating MOKE (ROTMOKE) measurements for the
same sample [42] are shown in Fig. 13b. The ROTMOKE curve is fitted to the
equation [43]:
where E is the free energy, V is the volume of the film, Ms is the saturation
magnetization, H is the magnetic field, θ is the angle between H and Co [110]
direction, and φ is the angle between magnetization and Co [110] direction. The
Fig. 12 Cross-sectional
HRTEM picture of the 29 nm
Co/GaAs (001) film prepared
◦
at 150 C [40]. LICENSE #:
4813040909381
16 Metallic Magnetic Thin Films 823
best fit yields the fourfold anisotropy field μ0 HK1 = 2 K1 /MS = −15.2 mT and
the uniaxial anisotropy field μ0 HKu = 2Ku /MS = 22.0 mT. Since the magnetic
moment of bcc Co is 1.53 μB [33], we deduce K1 = μ0 HK1 MS /2 = −6.5 kJ/m3 .
The negative K1 means that the easy axes of the fourfold anisotropy are along Co
<110> directions.
Furthermore, the anisotropy as a function of the growth temperature and
thickness was systematically investigated by ROTMOKE [41]. Figure 14 shows HK1
fitted from the ROTMOKE curves as a function of the Co film thickness for different
growth temperatures, 60, 120, and 160◦ C, and the thickness of the phase transition.
HK1 for Co thinner than 1.2 nm deposited at 60 ◦ C is negative, and the absolute
values increase monotonically with thickness, suggesting the bulk-like origin of the
fourfold anisotropy. When the Co is thicker than 1.2 nm, |HK1 | first decreases to zero
at 1.8 nm and then increases with increasing thickness (Fig. 14a). Above 1.2 nm, hcp
Co, which contributes a positive K1 [36] and starts to develop [38, 44], leading to the
increases of HK1 . For Co film grown at 120◦ C, K1 is negative for the bcc phase and
starts to increase when the hcp phase starts to develop. The bcc structure Co films
grown at 60–140◦ C always exhibit negative HK1 , as shown in Fig. 14d. Although
the bcc structure film grown at 160◦ C is obtained below 2 nm, no Kerr signal is
detected. It might be due to the strong reaction between Co and GaAs to form the
nonmagnetic bcc CoGaAs compound. Above 2 nm, HK1 or K1 is positive for the
mixture phases of the bcc and hcp structures (Fig. 14c).
824 D. Wu and X.-F. Jin
Fig. 14 HK1 as a function of Co thickness measured on the Co wedge samples grown at (a) 60 ◦ C,
(b) 120 ◦ C, and (c) 160 ◦ C. Each HK1 value is fitted from ROTMOKE experiments. The dashed
line denotes the structure phase transition thickness. (d) HK1 versus growth temperature. HK1 is
measured at the transition Co thickness. For Co grown at 160 ◦ C, there is no transition point [41].
The triangle data point is obtained from Refs. [38, 41]. LICENSE #: RNP/20/APR/024983
Ni/GaAs (001)
Unlike Fe and Co which have several structural phases in bulk, nickel only has
one bulk structure—fcc. It was reported that a very thin bcc Ni phase less than 6
atomic layers (or 3 unit cells) could be epitaxially grown on a Fe(001) substrate
[45, 46]. Above 6 ML, the structure is complicated [45]. The bcc structure Ni was
measured to be FM with a magnetic moment of 0.55–0.80 μB /atom [47, 48] or
0.4 ± 0.45 μB /atom by different groups [49]. However, TC was found to lower than
77 K in Ref. [45] and higher than 300 K in Ref. [49]. In the Ni/Fe (001) system,
the magnetic properties of bcc Ni can be strongly altered by Fe, considering the
strong hybridization and magnetic coupling at the Ni/Fe interface [45, 48–51] For
example, the enhanced Tc and induced magnetic moment of Ni could occur by the
strong interface coupling [52, 53]. Therefore, it is desirable to obtain bcc Ni on a
nonmagnetic substrate to investigate its intrinsic properties.
Theoretically, it was predicted that bcc Ni with a lattice constant of 0.2773 nm
at equilibrium is paramagnetic and a transition to an FM state occurs upon lattice
expansion beyond 0.2815 nm [54]. However, Guo and Wang found that the magnetic
phase transition occurs at 0.2730 nm [55].
We found that bcc Ni can be epitaxially grown on GaAs (001) [56, 57]. The
growth temperature of 170 K is critical to achieve the thickest bcc Ni films of
3.5 nm. Figure 15a shows a cross-sectional HRTEM image of Ni (3.5 nm)/GaAs
(001) with the electron beam along GaAs [110] direction. Ni is unambiguously
identified to have a bcc structure [40] with a lattice constant of 0.28 nm. The
orientation of the bcc Ni/GaAs (001) film is (001)[100]Ni //(001)[100]GaAs and
(001)[110]Ni //(001)[110]GaAs . XRD experiments confirm the structure to be bcc,
as shown in Fig. 15b. In addition to the GaAs (400) diffraction peak, a broad peak
16 Metallic Magnetic Thin Films 825
superimposed on top of the narrow GaAs (400) peak is clearly observed (inset of
Fig. 15b). This broad peak is identified to be the bcc Ni (200) diffraction from which
an in-plane lattice constant of 0.282 nm is readily derived. The absence of the fcc Ni
◦ ◦
diffraction peaks at ∼25.9 for (200) and ∼ 38.1 proves that the bcc phase is pure.
Figure 16a shows the MOKE signal at remanence measured from a Ni wedge
sample at 120 K as a function of the Ni film thickness [57]. The extrapolated dashed
line in Fig. 16a passes through the origin, indicating that there is no interfacial
dead layer. The vanishing MOKE signal below ∼1.2 nm is attributed to the reduced
Tc due to the finite-size scaling effect of Tc in ultrathin film [58]. In contrast, the
disappearance of the magnetic signal for the fcc Ni/Cu (001) film is around 0.6 nm
at 120 K [59]. To obtain Tc of bulk bcc Ni, Tc is fitted as a function of the bcc Ni
thickness (Fig. 16b) by the finite-size scaling law [58]:
Fig. 16 (a) MOKE signal at remanence as a function of the bcc Ni thickness measured at 120 K.
The inset shows a representative hysteresis loop. (b) Tc as a function of film thickness. The solid
line is a theoretical fit to Eq. (2) with Tc(∞) = 456 K, λ = 2.23, and c = 1.17 nm. (c) ROTMOKE
data as a function of the magnetization directions. The lines are the theoretical fitting with different
parameters [57]. LICENSE #: RNP/20/APR/024984
could suggest that the bcc lattice has some degree of in-plane shear strain, similar
to that of the thick bcc Fe layers on GaAs (001) [61]. In addition to the contrast in
the magnetic anisotropy between fcc Ni and bcc Ni, their electronic band structures
also show significant difference [57].
Py/GaAs (001)
The structure of bulk Py is fcc. Since both Fe and Ni grow epitaxially on GaAs
(001) in the bcc structure [57, 69], it is possible to grow the bcc structure Fex Ni1−x
alloys on GaAs (001). The Fex Ni1−x alloys were grown at 200 K by co-deposition
using MBE. In addition to the RHEED and LEED patterns suggesting the successful
growth of the bcc Py film, similar to the bcc Fe and Ni films [56], the grazing
incident XRD (GIXRD) proves the bcc structure of the Py film directly. Figure 17
presents a GIXRD spectrum of the Au (2 nm)/Fe0.25 Ni0.75 (5 nm)/GaAs (001)
sample with a fixed photon energy at 8.052 keV and an incident angle at 0.3◦ [70].
The absence of peaks at 25.9◦ and 38.1◦ for fcc Py (200) and Py (220), respectively,
excludes the existence of the fcc phase. The peak at 33.1◦ is composed of three parts:
(1) an extremely narrow peak at 33.155◦ from the GaAs (400) diffraction (blue line
in the inset); (2) a broad peak from the bcc Py (200) diffraction with an in-plane
lattice constant of 0.2825 nm (red line); (3) a very broad and shallow peak from
the fcc Au (220) diffraction (green line). We found similar results for samples with
all compositions, meaning that bcc structure of Fex Ni1−x alloys is realized over the
whole range of stoichiometry.
To compare the magnetic properties of fcc and bcc Py, samples with two
structures were prepared on one GaAs (001) substrate, as shown in the inset of
Fig. 18. Half of the substrate was first covered by a 3-nm fcc Au seed layer by
a shadow mask [71]. After removing the shadow mask, a thickness wedge of Py
was then deposited on the whole sample. Therefore, we had fcc Py/Au/GaAs (001)
[71] and bcc Py/GaAs (001) films with exactly the same stoichiometry on the same
sample.
Figure 18 shows the Kerr rotations at saturation for two structural Py as a function
of the film thickness measured at 110 K. The different slope of Kerr rotations are
attributed to the optical effect because the magnetic moment per atom is almost
identical for bcc and fcc Py: mbcc = 1.03 ± 0.09μB and mfcc = 1.07 ± 0.09μB
measured on the corresponding flat film by vibrating sample magnetometry (VSM).
828 D. Wu and X.-F. Jin
Fig. 19 Cubic magnetic anisotropy constant (K1 ) versus iron concentration measured from the
3-nm-thick bcc Fex Ni1−x composition wedge (see the carton) by ROTMOKE at 300 K, together
with the calculated K1 values are marked as red solid cycles. A set of representative hysteresis loops
for bcc Fe0.25 Ni0.75 is shown in the inset. Averaged magnetic moment per atom in bcc Fex Ni1−x is
also measured by VSM as a function of iron concentration together with a zoom around the “Invar
point” obtained by MOKE [70]. LICENSE #: RNP/20/APR/024985
for the magnetization [78]. The cubic magnetocrystalline anisotropy energies were
calculated through the torque method for bcc Fex Ni1−x in several (2 × 2 × 2)
supercells that preserve the cubic symmetry [79]. The results are presented as
dots in Fig. 19 for direct comparison with the experiment. It is obvious that the
theory reproduces well the general trend of the experimental data. The band-filling
dependence of K1 obtained from a rigid band scheme is presented in Fig. 20 for
several systems. It is clear to see that adding either a small amount of Fe to Ni
or vice versa causes a reduction in K1 as guided by the arrows. To elucidate the
element-specific contributions from Fe and Ni, we selectively switch off spin-orbit
coupling (SOC) from different elements in the bcc Py. Intriguingly, the SOC of
Fe only (denoted as Fe-SOC) gives a small negative contribution to K1 whereas
Ni plays the dominant role. Both Ni and Fe behave very differently from their bulk
forms. It seems that only the local Fe-Ni bonding is the most important factor for the
quenching of the magnitude of K1 , whereas signs of K1 of individual constituents
are not relevant.
Among the 3d transition metal alloys , the Mn-based alloys have attracted special
attention because of their potential applications in the magnetic recording industry
[80–82] The Cox Mn1−x alloy has shown interesting magnetic properties [83–85]
Bulk Cox Mn1−x is FM with an hcp structure for 0 < x ≤ 0.32 but is AFM with an
fcc structure for 0.32 < x ≤ 0.52. For x > 0.52; it is no longer possible to stabilize
the fcc state [86]. The metastable bcc Co and fcc Mn can be epitaxially grown on
GaAs (001) surfaces at room temperature [13, 38]. It provides us an ideal platform to
830 D. Wu and X.-F. Jin
epitaxially grow the Cox Mn1−x alloys on GaAs (001) to investigate the correlation
between their structure and magnetism.
Figure 21 presents the typical RHEED patterns of the Cox Mn1−x /GaAs (001)
films with different compositions with the incident electron beam along the [110]
direction [87]. The spot-like patterns indicate island growth mode and allow us
to determine the structure [14]. Figure 21a shows the RHEED pattern for a clean
GaAs (001) surface, which serves as an internal scale to measure the film lattice
constants. Figure 21b shows a typical RHEED pattern for the Cox Mn1−x films with
composition 0 < x ≤ 0.44. The rectangular-shaped pattern corresponds to a bcc
structure, which does not exist in the bulk and is similar to that of the Co/GaAs (001)
film. The in-plane lattice constants of Co60 Mn40 are estimated to be a = b = 0.29 nm
from the RHEED pattern (Fig. 21b). The out-of-plane lattice constant is determined
to be 0.289 nm by XRD.
For 0.78 ≤ x < 1, the RHEED pattern is square, as shown in Fig. 21c, suggesting
an fcc structure, similar to that of the Mn/GaAs (001) film. In comparison, no stable
bulk phases of Cox Mn1−x alloy can be obtained for x > 0.52. Similar to the above
analyses, the lattice constants are estimated to be a = b = 0.36 nm and c = 0.360 nm
by the RHEED pattern and XRD.
The structure is more complicated and shows thickness dependence for
0.44 ≤ x ≤ 0.78. A typical case is given in Fig. 21d–f, in which the RHEED
patterns of Co30 Mn70 thin films were recorded at different thicknesses. In the initial
stage at film thickness thinner than 5 nm, the film is bcc (Fig. 21d). As the film gets
thicker, a mixture of rectangular- and square-like diffraction patterns is observed
(Fig. 21e), indicating the coexistence of the fcc and bcc phases on top of the initial
bcc layer. When the film is thicker than ∼27 nm, the film becomes fcc (Fig. 21f).
The coexistence of the fcc and bcc phases is further confirmed by XRD [87]. The
thickness-dependent behavior in the intermediate range of composition is due to the
competition between the fcc structure as Co/GaAs (001) film and bcc structure as
Mn/GaAs (001) film. In the intermediate composition range, the bcc phase of the
Cox Mn1−x alloys has a much smaller lattice misfit with the substrate (∼ 1%) than
16 Metallic Magnetic Thin Films 831
Fig. 21 Representative RHEED patterns of Cox Mn1−x /GaAs (001) with different Mn composi-
tion. (a) Clean GaAs (001) surface; (b) bcc phase of Co60 Mn40 films; (c) fcc phase of Co10 Mn90
films; (d–f) thickness-dependent transition from bcc to fcc phase for the Co30 Mn70 film [87].
LICENSE #: RNP/20/APR/024986
the fcc phase (∼ 9%), resulting in the initial growth of the bcc phase. However, the
bcc phase does not exist in the bulk, indicating a relatively high-energy metastable
state. When the film gets thicker, it tends to form the fcc phase. It is very unlikely
that the bcc and fcc coexistence region corresponds to a phase separation of Mn-rich
fcc and Co-rich bcc phases; otherwise the film structure in the final stage of growth
would become much more complicated than the one we observed (Fig. 21f).
Based on the foregoing results, a structural phase diagram as a function of
composition is plotted in Fig. 22. Three regions are clearly seen, i.e., the Co-rich
bcc phase region marked I, the Mn-rich fcc phase region marked III, and the
intermediate region with the mixed bcc and fcc structures marked II.
832 D. Wu and X.-F. Jin
Fig. 22 Structural phase diagram for Cox Mn1−x /GaAs (001) films [87]. LICENSE #:
RNP/20/APR/024986
After the structure characterization, the Cox Mn1−x /GaAs (001) films were
carried out with the MOKE measurements. The films are in-plane anisotropy
if they are FM. Figure 23 shows the typical longitudinal MOKE loops for the
Cox Mn1−x /GaAs (001) films with different compositions after being normalized
for the film thickness. The film shows strong ferromagnetism for x < 0.44. No
hysteresis loop is observed for x > 0.78. The ferromagnetism is relatively weak
for 0.44 ≤ x ≤ 0.78.
Since the structure of the Cox Mn1−x /GaAs (001) films is thickness-dependent in
the intermediate composition, a wedge-shaped sample was fabricated and measured
by MOKE at room temperature to understand the correlation between the structure
and magnetism. The results of the Kerr intensity versus thickness for a Co52 Mn48
film are shown in Fig. 24. The data can be divided into three regions: i) a magnetic
dead layer (∼ 2 nm) is near the interface; ii) the linearly increasing Kerr intensity
(∼ 2–6 nm) region means an FM layer; iii) the saturated Kerr intensity region
(> 6 nm) means a non-FM layer on the top. The magnetic dead layer is caused by the
interface reaction between film and substrate, as is quite common in such systems.
The FM layer comes from the bcc-dominated Co52 Mn48 film. The non-FM layer
has an fcc-dominated structure. Furthermore, the fcc-Cox Mn1−x /Fe bilayer exhibits
an exchange bias effect, indicating the fcc structure Cox Mn1−x is AFM. Therefore,
we conclude that Cox Mn1−x film is FM whenever its structure is bcc, and it is AFM
whenever its structure is fcc. The magnetism is intimately correlated with a structure
16 Metallic Magnetic Thin Films 833
for the Cox Mn1−x alloys. This strong correlation realized in experiments between
the structure and magnetism of Cox Mn1−x alloys was further studied and confirmed
by a first-principles linearized augmented plane-wave (LAPW) calculation with the
local-spin-density approximation (LSDA) [87]. This correlation between structure
and magnetism is also found in Fex Mn1−x /GaAs (001) films [88].
Since bulk Fe has the bcc structure, the magnetic properties of fcc Fe attract
tremendous interest. Fcc Fe can only be prepared via precipitation in a Cu matrix
or epitaxially grown on a Cu substrate [31]. Because of the extremely low bulk
miscibility of either Cu in Fe or Fe in Cu, only ∼4% Fe dissolves into Cu (with
fcc structure) and ∼ 10% Cu into Fe (with bcc structure) near their respective
liquid points [89], and a long-standing challenge has been the goal of producing
metastable Fex Cu1−x alloys with higher concentrations by different approaches,
such as rapid quenching, vapor deposition, ion beam mixing, or mechanical alloying
[90–94]. However, the samples prepared by these methods are polycrystalline. A
834 D. Wu and X.-F. Jin
Fig. 24 Kerr intensity for a wedge-shaped Co52 Mn48 film at different thicknesses [87]. LICENSE
#: RNP/20/APR/024986
Similar to Cu/GaAs (001) film, the structure varies with the film thickness for
the Fex Cu1−x films with any particular x value. Figure 25e–h shows a representative
example of Fe0.25 Cu0.75 . The structure evolves from bcc to bct (closer to bcc), then
to bct but closer to fcc, and finally to fcc. The structural evolution for different
Fex Cu1−x films is summarized by the aspect ratio of a*/b* in Fig. 26. At the
same thickness of 6 nm, a*/b* changes from 1 (fcc) for Cu to 1.4 (bcc) for Fe
as increasing x.
The Fex Cu1−x /GaAs (001) films were covered by 2 nm Au to conduct ex situ
MOKE measurements. It is found that the ferromagnetic to non-ferromagnetic
836 D. Wu and X.-F. Jin
transition occurs at x ≈ 0.33. This result is quite different from the polycrystalline
samples, where the transition is at x ≈ 0.5 [97].
Considering that the structure of the Fex Cu1−x films is dependent on the film
thickness, the magnetization for different thickness was measured in the wedge
samples at room temperature. The result of Fe0.5 Cu0.5 is shown in Fig. 27a. The
straight line above 2 nm across origin indicates that there is no noticeable change of
effective magnetic moment per Fe atom. The deviation from the straight line below
2 nm is due to the finite size effect of Tc [58]. The SQUID measurements were
carried out at 5 K on the 6-nm Fex Cu1−x films to quantify the effective magnetic
moment per Fe atom, assuming that Cu does not contribute to the magnetization.
The results are shown in Fig. 27b. The effective magnetic moment per Fe atom
decreases with increasing x, consistent with the previous theoretical calculation
which is also plotted in the figure [98]. For the 6-nm-thick Fe0.33 Cu0.67 , the
magnetization is too small to be detected.
It is known that Fe/GaAs (001) has a fourfold anisotropy with the easy axis along
the <100> directions and a uniaxial anisotropy with the easy axis along the [110]
direction [69]. The total energy density of the system is
Here, the first term represents the Zeeman energy, α is the angle between the
easiest axis (ea) and H (see the inset of Fig. 28b), and θ is the angle between the
easiest axis and the magnetization; the second term is the uniaxial anisotropy energy,
and the third term is the fourfold anisotropy energy. In order to extract the anisotropy
field, we carried out the ROTMOKE measurements. The results are shown in
Fig. 28. The ROTMOKE curve (Fig. 28a) is fitted to Eq. (3) (solid line in Fig. 28a) to
yield the anisotropy field μ0 HKu = Ku /MS = 6.2 mT and μ0 HK1 = K1 /MS = 60.4
mT, respectively, for the Fe/GaAs (001) film. For the Fe0.50 Cu0.50 /GaAs (001) film,
16 Metallic Magnetic Thin Films 837
it is obvious that the ROTMOKE curve (Fig. 28b) cannot be fitted by considering
only the uniaxial anisotropy (dashed line in Fig. 28b). The curve is well fitted with
both uniaxial and fourfold anisotropies for μ0 HKu = 6.9 mT and μ0 HK1 = 4.7
mT as shown by the solid line in Fig. 28b. Although the fourfold anisotropy of
Fe0.50 Cu0.50 /GaAs (001) is much weaker than that of pure Fe, it still retains.
It is well-known that the magnetic long-range order does not exist in an isotropic
two-dimensional (2D) Heisenberg system at any finite temperature [99]. However, it
is hard to physically realize a 2D FM film without any anisotropy. Experimentally, it
might be realized in the vicinity of the spin reorientation transition (SRT) in ultrathin
magnetic films, because of the magnetocrystalline anisotropy, surface anisotropy,
and dipolar anisotropy could compensate at the SRT point in some cases. Therefore,
it is very interesting to study the correlation between SRT and the long-range
magnetic order. Indeed, a suppression of magnetization or a reduction of Tc within
the SRT region was reported in Fe/Cu (001), Fe/Ag (001), and Fe/Ni/Cu (001) [100–
102]. However, if it is a continuous SRT, the anisotropy never disappears within
the SRT region, where the magnetization only rotates between in-plane and out-of-
plane as Ni/Cu (001) [103, 104]. Interestingly, it was found that the SRT occurs at
87% Ni concentration in 9-ML Fex Pd1−x /Cu (100) and Tc is dramatically reduced
[105]. Therefore, the Fex Pd1−x alloy provides us a good system to investigate the
correlation between SRT and Tc [106].
A Fex Pd1−x composition wedge sample was epitaxially grown on Cu (001)
to explore the composition-dependent SRT [74]. The magnetic properties of the
sample were investigated through both MOKE and ac susceptibility measurements
after capping 3 ML Cu on the sample [52, 107–109]. Two representative hysteresis
loops of 9-ML sample measured by MOKE at room temperature were shown in
838 D. Wu and X.-F. Jin
Fig. 29a, one for Ni0.57 Pd0.43 with easy axis in-plane and the other for Ni0.91 Pd0.19
with a perpendicular easy axis. The remanent magnetization measured by the polar
MOKE as a function of the Ni composition is plotted in Fig. 29b. The remanent
magnetization increases gradually with increasing Ni concentration, suggesting that
the magnetization rotates continuously from in-plane to out-of-plane. The imaginary
part of the ac susceptibility Im(χ ) as a function of the Ni composition was also
shown in Fig. 29b. Im(χ ) shows a pronounced peak at the SRT position, which
is at 86% Ni concentration for 9-ML Fex Pd1−x /Cu (100), consistent with the
previous report [105]. This SRT can be understood by the competition between the
shape anisotropy and the magnetocrystalline anisotropy including magnetoelastic
anisotropy originating from the lattice distortion and the surface anisotropy, similar
to the Ni/Cu (001) system [104, 110, 111].
Tc of the 9-ML compositional Fex Pd1−x /Cu (100) film is determined by the
ac susceptibility measurement, as shown in an example in the inset of Fig. 30a.
The result of Tc and the susceptibility as a function of Ni composition is shown
in Fig. 30a. The reduction of Tc is not found at the SRT position where the
susceptibility exhibits a peak. Tc increases very slowly as a function of the Ni
composition before SRT, while it increases more sharply after SRT. This behavior of
the turning point of Tc at SRT indicates that the variation in anisotropy influences
the increasing behavior of Tc. To confirm the correlation between SRT and Tc, a
7-ML compositional Fex Pd1−x /Cu (100) film was fabricated and measured using
16 Metallic Magnetic Thin Films 839
the same approach. The results are shown in Fig. 30b. Again, the turning point of
Tc is at the SRT point, which is at a Ni concentration of 96% and no reduction in
Tc is observed in the region of SRT, unlike another report (Ref. [105]).
No reduction in Tc is observed around the SRT region in our experiments. One
reason could be that its anisotropy never really disappears, but the easy direction
of the magnetization rotates continuously within the transition [112]. The other
possibility could be that at the SRT point there still exists some residual perpendic-
ular anisotropy which is caused by variations in the perpendicular anisotropy across
the film surface [113]. Another interesting phenomenon in our experiments is that
increasing the perpendicular anisotropy may enhance Tc much more strongly than
the fourfold in-plane anisotropy. A simple Monte Carlo simulation was performed
840 D. Wu and X.-F. Jin
Acknowledgments One of the authors, XFJ, acknowledges the invaluable contribution of the past
co-workers of Prof. G. S. Dong and graduated students.
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Contents
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
Rocks, Solid Solutions, and Percolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 851
Principles of Oxide Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852
Iron Oxides and Hydroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863
Hematite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
Magnetite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 866
Maghemite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
Wüstite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
Iron Hydroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 868
Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
Spinels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
Garnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 871
Orthoferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 872
Hexagonal Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 873
Other Magnetic Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 875
3d Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 876
Perovskites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 878
Pyrochlores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 885
4d and 5d Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 887
4f Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 888
5f Oxides and Related Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
Related Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
Chalcogenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
Pnictides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 895
Silicates and Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 897
Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 897
Carbonates, Phosphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 903
J. M. D. Coey ()
School of Physics, Trinity College, Dublin, Ireland
e-mail: [email protected]
Abstract
Background
Terrestrial minerals are the source of the magnetic elements needed to make all
the alloys and compounds of interest in this handbook. The ores are culled from the
Earth’s surface or the topmost kilometer of the crust, where low-density compounds
of oxygen and other electronegative elements segregate, while denser siderophilic
materials tend to sink deep into the core, which is composed of 90% iron with a
little nickel – a composition similar to that of Ni-Fe meteorites. In fact, iron is the
most abundant element by weight in the whole Earth (35 wt%), but in the crust
it occupies fourth position (6 wt%), after oxygen, silicon, and aluminum, or sixth
position, after hydrogen and sodium if its concentration is expressed in atom percent
(2.1 at%). Crustal abundances in at% are shown in Fig. 1a). Rock-forming minerals
are therefore predominantly aluminosilicates, but two iron oxides, magnetite and
hematite, feature among them. These were the first magnetic materials known to
man, and they remain our primary source of iron, which provided the basis of
technology and weaponry for over 2000 years.
17 Magnetic Oxides and Other Compounds 849
a)
5 Fe
Log (abundance, ppm)
4
Mn
3
Cr Ni Ce
2 Nd
Co
Pr Sm Gd
1 Dy
Er Yb
Eu Ho
Tb
0 Pm Tm
-1
3d elements 4f elements
b)
Fig. 1 (a) Atomic abundances of the principal elements in the Earth’s crust and (b) abundances
of magnetic 3d and 4f elements, plotted on a logarithmic scale
Almost 1 atom in 40 in the crust is iron, and compared with other magnetic
elements, the crustal abundance of iron is 40 times that of all the others put together.
This 40/40 rule affords some perspective on the magnetism of natural oxides.
Abundances of the magnetic elements are compared on a log scale in Fig. 1b), where
it can be seen that there is about three orders of magnitude more Fe in the Earth’s
crust than either of the other ferromagnetic 3d elements Co and Ni (Table 1).
The magnetic elements, which have ions with unpaired electrons, are found
predominantly among the 3d and 4f series. The light rare earths are not particularly
rare – neodymium is as abundant as cobalt or zinc, but the abundances follow
an odd/even variation with atomic number that reflects the stability of the atomic
nuclei, superposed on a decline with increasing atomic number. The heavier 4f
elements become increasingly uncommon. Crustal abundance is a rough proxy
850 J. M. D. Coey
1.0 o o o o o o o o o o o o
o o o o o o o o o o o o
0.8 o o o o o o o o o o
o o o o o o o o o o o
Tc/Tc (x= 1)
0.6 o o o o o o o o o
Cluster
o o o o o o o o o o
0.4 o o o o o o o o o o o o
o o o o o o o o o o
0.2 xp Antiferro-
o
magnetico o o o o o o o
pair Isolated
o o o o o o o o o o o o
0.0 o o o o o o o o o o o
0.0 0.2 0.4 0.6 0.8 1.0
x
Fig. 2 (a) Schematic variation of the magnetic ordering temperature as a function of the
concentration x of magnetic ions in an oxide solid solution of magnetic and nonmagnetic cations
M and N, (Mx N1-x )Oη , where η is a small integer or rational fraction. The magnetic interactions
couple nearest-neighbor magnetic cations, and xp is the percolation threshold. The distribution of
ions illustrated in (b) well below the percolation threshold
for cost. The periodic table in Table 2 provides an indication of the costs of the
elements in five broad bands. It is truly serendipitous for magnetism that the most
abundant and cheapest magnetic element turns out to be the one that is ferromagnetic
with the highest magnetization and the one that forms 3d cations with the greatest
magnetic moments. The natural magnetic materials that feature in areas such as rock
magnetism or biomineralization are iron oxides.
Oxides exhibit a wide range of electric, magnetic, optical, and structural proper-
ties. They can be insulating, semiconducting, metallic, ferroelectric, piezoelectric,
ferromagnetic, half-metallic, ferrimagnetic, antiferromagnetic, or superconducting.
From a magnetic point of view, the dominant interaction in transition-metal oxides is
usually antiferromagnetic superexchange, the coupling of the spins of two 3d cations
separated by an oxygen anion, which leads to antiferromagnetic or ferrimagnetic
order. Ferromagnetism is less common in oxides, where it is often associated with
cation mixed-valence and orbital degeneracy, than it is in metals. See Chap. 2,
“Magnetic Exchange Interactions.”
17 Magnetic Oxides and Other Compounds 851
Table 2 Periodic table of the elements, showing their approximate costs per kilogram, after [19]
Oxide structures have great scope for accommodating cations of similar charge
and ionic radius, and their properties can be considerably modified thereby. In
some cases, there is an extended range or even complete solid solubility between
chemically and structurally similar end-members.
Pure, single-phase end-members are not the norm in nature. The relative abun-
dance of Al and Fe in the crust (Fig. 1) means that iron (and other magnetic cations)
are relatively sparse in aluminosilicate rocks, which are generally multiphase
aggregates that reflect the temperature, pressure, and chemical environment in which
the rock was formed. It may be possible to separate out one of the phases for
examination, by physical or magnetic means. Otherwise, the whole multiphase rock
or soil can be analyzed microscopically in order to characterize the natural mixture
of minerals present.
Iron is often an impurity in aluminosilicate minerals, replacing aluminum
if trivalent or an alkaline earth cation if divalent. Iron-rich end-members are
the exception. When the iron content in a solid solution is low, superexchange
interactions among ferrous or ferric cations separated by a single oxygen anion
are inhibited, and long-range magnetic order is impossible. The magnetically dilute
minerals then exhibit Curie-Weiss paramagnetism. Percolation becomes possible
when the iron concentration x on appropriate sites exceeds the percolation threshold
852 J. M. D. Coey
Oxides are ionic compounds where small, highly charged metal cations are embed-
ded in a lattice of larger oxygen anions that occupy 90% of the volume. Bonding is
predominantly ionic. Oxygen accepts two electrons to form the divalent O2− anion
with the particularly stable 2p6 closed shell, a configuration that is shared by 90% of
all the ions in the Earth’s crust. The extra electrons are transferred to oxygen from
the metals that form the positively charged cations; those listed in Table 2 are the
ones most commonly encountered in oxides and other magnetic compounds. These
cations are all smaller than the oxygen anion, for which the ionic radius is taken to be
140 pm. Other anions encountered in magnetic compounds include OH− (110 pm),
F− (133 pm), Cl− (181 pm), S2− (184 pm), and N3− (146 pm). The ionic picture is,
of course, oversimplified. The chemical bond between metal and oxygen has part-
ionic and part-covalent character, governed by the electronegativity of the metal
partner. Covalency is more pronounced in sites with a low coordination number and
for cations like Si4+ or V4+ with a high formal charge state, as well as for anions
such as S2− and N3− that are much less electronegative than oxygen or fluorine
(Table 3).
The crystal structures of most oxides may be regarded as a packing of a lattice of
large oxygen anions held together by electrostatic interactions with the small metal
cations in interstitial sites. The structures sometimes incorporate large cations that
17 Magnetic Oxides and Other Compounds 853
Table 3 Ionic radii of cations in oxides. Values in brackets refer to a low-spin state
Fourfold Sixfold Sixfold Eightfold
tetrahedral pm octahedral pm octahedral pm cubic pm
Mg2+ 57 V4+ 3d1 58 Ti3+ 3d1 67 Ca2+ 112
Zn2+ 60 Cr4+ 3d2 55 V3+ 3d2 64 Sr2+ 126
Al3+ 39 Mn4+ 3d3 53 Cr3+ 3d3 62 Ba2+ 142
Fe3+ 3d5 49 Mn2+ 3d5 83 Mn3+ 3d4 65 Pb2+ 129
Si4+ 26 Fe2+ 3d6 78 (61) Fe3+ 3d5 65 Y3+ 102
Co2+ 3d7 75 (65) Co3+ 3d6 61 (55) La3+ 116
Ni2+ 3d8 69 (56) Ni3+ 3d7 60 (56) Gd3+ 4f7 105
When the tetrahedral or octahedral site is undistorted, the free ion eigenfunctions
ψ0 , ψ±1 , and ψ±2 , with subscripts denoting the orbital magnetic quantum number
ml , are replaced by suitable linear combinations that reflect the cubic site symmetry.
They are:
√
ψxy = −i/ 2 (ψ2 − ψ−2 )
√
ψyz = i/ 2 (ψ1 + ψ−1 )
√
ψzx = −1/ 2 (ψ1 − ψ−1 ) (1)
√
ψx2−y2 = 1/ 2 (ψ2 + ψ−2 )
ψz2 = ψ0
Figure 4 compares the electron density for this basis set of d orbitals in an
octahedral environment with that of the d electrons in a spherical potential.
On inspecting the disposition of the oxygen electrons in the surrounding
octahedron, it is obvious that the xy, yz, and zx orbitals are degenerate – they
are labeled t2g orbitals. It is less obvious that the x2 – y2 and z2 orbitals, labeled
eg , are degenerate, but they are clearly higher in energy because the 3d electron
density is maximum near the negatively charged anions. The crystal field splitting
in octahedral coordination (where the suffix g is included to indicate the presence of
a center of symmetry) is illustrated in Fig. 5.
17 Magnetic Oxides and Other Compounds 855
Fig. 4 The 3d orbitals for electrons in a free ion (top row) and the orbitals for the ion in a cubic
crystal field (bottom row). Oxygen positions in a surrounding octahedron are marked by red dots
that represent -2e point charges
The splitting of the one-electron levels is only partly explained by the electro-
static potential created by the oxygen anions; about half of it should be attributed
to covalency associated with the different overlap of the t2g and eg orbitals with
the lower-lying 2p oxygen orbitals, which introduces a greater bonding-antibonding
splitting for the 2p-eg σ-bonds than the 2p-t2g π-bonds. This is the ligand field effect.
The combined ionic and covalent effects result in a total splitting , which is about
1 eV in octahedral sites [5].
The crystal field splitting is reversed in pure cubic coordination, where the eg
orbitals are lowest. The splitting is smaller and also reversed in tetrahedral sites,
with the e orbitals lower and the t2 orbitals higher. The suffix g is dropped because
a tetrahedron has no center of symmetry (Fig. 6).
The influence of a distortion of the cubic site is to lift the degeneracy of the
one-electron energy levels, as shown in Fig. 7. The splitting preserves the center of
gravity of each set of orbitals.
Whenever a set of orbitals is not fully occupied, the crystal field may lower the
energy of the ion by an amount known as the crystal field stabilization energy cfse ,
which can dictate the site preference of ions in structures where there is a choice of
856 J. M. D. Coey
Fig. 6 Energy splitting of the one-electron states in cation sites with octahedral, tetrahedral, and
cubic coordination due to the crystalline electric field
octahedral or tetrahedral site occupancy. For example, the energy of Cr3+ (3d3 ) in
octahedral sites is 3 × (−2/5) O = −1.2 O , whereas for Fe3+ (3d5 ) it is zero.
Cr3+ therefore has a strong octahedral site preference. Furthermore, a distortion of
the environment can provide an additional stabilization. These considerations can
outweigh purely steric effects.
The Jahn-Teller effect is the tendency of some ions to spontaneously distort their
local environment in order to gain some extra crystal field stabilization energy. A 3d3
ion in an octahedral site gains nothing from a distortion of the oxygen octahedron
because of the center of gravity rule, but a 3d4 ion will tend to induce a local
tetragonal deformation which splits the eg levels, lowering the energy of either the
occupied dz2 or dx2–y2 orbital (Fig. 7). The Jahn-Teller effect is strongest for d4 and
d9 ions in octahedral coordination and d1 and d6 ions in tetrahedral coordination.
Two other important electronic effects encountered in 3d oxides are charge order
and orbital order [62]. Here interionic coulomb interactions play a role. Charge
17 Magnetic Oxides and Other Compounds 857
z z
x x x
x x x
z z z
αt
Δ cfse
Δ0
δt
order arises when a particular lattice site can be occupied by an ion in one of
two different charge states. Examples are Mn3+ and Mn4+ or Fe2+ and Fe3+ . The
average 3d occupancy is nonintegral, but the electrons may settle in an ordered
pattern on the cation sites in a charge-ordered state with some lattice distortion.
Otherwise, the surplus 3d electrons rapidly hop or tunnel among the d3 or d5
ion cores, a phenomenon known as mixed valence that occurs, for example, in
mixed-valence manganites such as (La0.7 Sr0.3 ){Mn3+ 0.7 Mn4+ 0.3 }O3 or magnetite
[Fe3+ ]{Fe2+ ,Fe3+ }O4 , where the brackets denote different crystallographic sites.
The average 3d occupancy on octahedral sites {} in these examples is 3.7 or 5.5,
respectively.
Orbital order arises when the 3d occupancy is integral and single-valued, but the
electron occupies a degenerate orbital. An example is Mn3+ (t2g 3 eg 1 ). A lattice
distortion such as tetragonal compression and expansion on alternate sites can lead
to alternate occupancy of dz2 and dx2-y2 orbitals, in a variant of the Jahn-Teller
effect. The ordered electronic state generally reverts to a disordered state at a high-
temperature phase transition, where the entropy of disorder Rln2 per mole that is
released is comparable to the entropy Rln(2S + 1) released in the vicinity of a
magnetic order-disorder phase transition.
858 J. M. D. Coey
Coulomb interactions among electrons in the single electron states are critical,
both within and between cations. Although the one-electron picture is rather easy
to grasp and relate to energy-band calculations, it does no justice to these many-
electron interactions in 3d ions, especially for high-spin 3d ions with 2, 3, 7, or 8
electrons, which are in an F-state. Ions with five electrons are in an S state, which
corresponds to a half-filled 3d shell with spherical symmetry, while those with one,
four, six, or nine electrons are in an D-state, which maps onto a t2 or e one-electron
state. Here S, D, and F refer to the values 0, 2, or 3 for the total orbital angular
momentum L of the free ion allowed by Hund’s second rule, discussed below. The
excited states of the 3dn shell which are probed in optical transitions have been
calculated from crystal field theory, and they are represented on Tanabe-Sugano
diagrams [101, 108]. In magnetism, it is usually sufficient to consider only the
ground state.
The intra-atomic interactions give rise to Hund’s rules for the spin and orbital
moments of the many-electron ions. The first rule gives the net spin S, which is the
maximum value, consistent with the Pauli principle that no two electrons can occupy
the same quantum state with the same spin. It is simply obtained by populating
the lowest orbitals with the available electrons. The interaction is represented by
exchange coupling JH of a pair of electrons in different orbitals with the same spin,
written in terms of an atomic Hamiltonian
1
HH = −JH α=β + 2s iα .s iβ (2)
2
where typical values of the intra-atomic exchange JH are 0.8–0.9 eV for 3d electrons
and 0.6–0.7 eV for 4d electrons. Values for the more compact 4f shell are higher.
Here, s is the spin of an electron in a particular orbital at site i and the sum is over all
electron pairs on the site. Two examples, for d4 and d6 , are shown in Fig. 8a and b.
The energy contribution to (2) is JH for a ↑↑ pair and zero for a ↑↓ pair, so we have
-6JH for d4 and -10JH for d6 . Hund’s first rule implies that the five ↓ orbitals lie
above the five ↑ orbitals, which is normally the case unless the crystal/ligand field
splitting is large or the on-site exchange is weak when it is possible to have a low-
spin state, where in octahedral coordination, for example, the t2g ↓ orbitals are filled
before the eg ↑ orbitals and Hund’s first rule no longer applies. This is illustrated
in Fig. 8c and d, where the total spin moments are, respectively, S = 1 and S = 0.
Low-spin states in oxides are sometimes found for Co3+ in octahedral coordination,
which has S = 2 (t2g 3↑ eg 2↑ t2g 1↓ ) in the high-spin state and S = 0 (t2g 3↑ t2g 3↓ ) in
the low-spin state. They are more common in more covalent compounds, where the
ligand field is larger.
Hund’s second rule maximizes the orbital angular momentum consistent with the
value of S for the ion. The possibilities in Table 4 are a D-state with L = 2(d1 , d4 ,
d6 , d9 ), an F-state with L = 3(d2 , d3 , d7 , d8 ), or an S-state with L = 0 (d5 ). The
17 Magnetic Oxides and Other Compounds 859
Fig. 8 Electronic configurations of an ion in octahedral coordination having four or six electrons.
In (a) and (b), the usual high-spin states are illustrated, whereas (c) and (d) show the low-spin
states that arise when the crystal field splitting cf exceeds the intra-ionic Hund’s rule exchange
splitting H
Table 4 Ground state terms for 3d and 4f ions, 2S + 1 LJ deduced from Hund’s rules
3d1 3d2 3d3 3d4 3d5 3d6 3d7 3d8 3d9
2D 3F 4F 5D 6S 5D 4F 3F 2D
3/2 2 3/2 0 5/2 4 9/2 4 5/2
4f1 4f2 4f3 4f4 4f5 4f6 4f7 4f8 4f9 4f10 4f12 4f12 4f13
2F 3H 4I 5I 6H 7F 8S 7F 6H 5 4I 3H 2F
5/2 4 9/2 4 5/2 0 7/2 6 15/2 I8 15/2 6 7/2
nomenclature here is based on free ions, but it is retained for ions in solids, even
though the orbital moment is almost completely quenched by the crystal field.
The third rule invokes spin-orbit coupling, a relativistic interaction of great
interest in magnetism, represented by the Hamiltonian:
4s(T)
conduction band
3dn±1
U W
3dn
3dn+1+ L
U W
2p6(O) 3dn
valence band
Fig. 9 Schematic density of states for a 3d oxide, showing the charge-transfer process that leads
to a Mott insulator in an early transition-metal oxide and a charge-transfer insulator in a late
transition-metal oxide. The oxide is insulating if the excited state cannot be accommodated within
the bandwidth
of them associated with each cation site. The 3d levels, illustrated schematically
in Fig. 9, lie in the gap between a broad, full 2p(O) valence band and a broad,
empty 4s(T) conduction band, where T is the 3d transition metal. The 3d levels
lie near the top of the bandgap for cations like Ti3+ or V3+ at the beginning of
the series and move toward the bottom of the gap for cations like Ni2+ or Cu2+ at
the end. The 3d orbitals inevitably overlap to some extent, and in the tight-binding
approximation with interatomic hopping integral t, this means that they form a
narrow band of width W = 2Zt, where Z is the coordination number. The bandwidth
decreases as the nuclear charge increases across the 3d series. Elementary band
theory unphysically predicts that any partially filled band, however narrow, will
always be conducting, because the theory neglects electronic correlations. Oxides
are not usually metals, despite a 3d bandwidth of 2 eV or more, for reasons
explained by Mott [75]. In a metal, the average 3dn configuration has to coexist with
fluctuating 3dn ± 1 configurations in order for conduction to take place. The energy
cost of transferring an electron from one site to the next is the coulomb energy
Udd , which is the difference between the ionization energy and the electron affinity
of a 3dn ion. When this exceeds W, Udd /W > 1, conduction cannot occur, and the
oxide is known as a Mott insulator (or a Mott-Hubbard insulator). The d-d coulomb
correlations transform what would otherwise be a metal into an insulator, because
there is no place in the band to accommodate the correlation energy.
For the heavier 3d ions, an easier charge-transfer process is from a filled oxygen
2p6 shell to an adjacent metal cation, creating a 2p5 configuration with a ligand
hole and a 3dn + 1 cation configuration with an excess electron. This process costs
an energy Upd , and when Udd > Upd > W, the oxide is known as a charge-transfer
insulator.
17 Magnetic Oxides and Other Compounds 861
Here the first term transfers an electron from site i to a neighboring site j, without
flipping the spin. The second term is the on-site coulomb repulsion between two
electrons of opposite spin on the same site. The nearest-neighbor interaction is
antiferromagnetic because the wave function cannot spread out to neighboring sites,
unless the spins are antiparallel. The coupling energy between the spins on adjacent
sites is of order t2 /U.
Modern electronic structure calculations, especially those based on density
functional theory, have been good at predicting the magnetization and magnetic
ordering temperature of metals, but they are less successful with oxides and other
insulators, where the coulomb interaction parameter U is often has to be chosen to
match the observed bandgap. Numerical calculations dispense with the simplified
models that have helped us to develop an intuitive physical understanding of the
many-electron ground state in terms of a handful of physical parameters that
quantify the exchange, spin-orbit, and crystal field interactions that really call the
shots in this area of magnetism.
Oxides are rarely perfectly stoichiometric, so exactly integral d-band occupancy
is unlikely. There will inevitably be spatial charge fluctuations associated with
atomic defects, but they do not normally spoil the insulating state. Local lattice
deformations arise because the 3d electrons or holes interact strongly with their
ionic environment and create lattice polarons with a large effective mass that are
effectively immobile. Furthermore, if an electron should hop to an unoccupied
neighboring site in a 2D or 3D antiferromagnetic array, it leaves a hole behind
and flips a spin with each subsequent hop, creating a ferromagnetic interaction
while leaving a trail of magnetic defects behind it. The energy can be mini-
mized by the electron returning to its starting point. A small excess of electrons
or holes in the half-filled Hubbard band does not therefore make the model
conducting.
Direct overlap of the 3d orbitals of cations on neighboring sites to form the
3d band is relatively small, but the mixing of 3d states with the 2p states of
neighboring oxygen anions is more significant. In these circumstances, the exchange
interactions coupling the spins of next-neighbor cations are indirect, superexchange
interactions. These were systematically investigated by Goodenough and Kanamori
[50] in the 1960s. Their rules were simplified by Anderson [1] and the interactions
are discussed in Chap. 2, “Magnetic Exchange Interactions.” The coupling is
usually antiferromagnetic, except if the M-O-M bond angle is close to 90◦ , when
weak ferromagnetic interactions can occur. The antiferromagnetic interactions lead
to either antiferromagnetic or ferrimagnetic order, depending on the lattice structure,
but they may be frustrated by the lattice topology.
862 J. M. D. Coey
H = −2JS i .S j (5)
HDM = −D. S i × S j (6)
where the vector D must lie along a uniaxial symmetry axis, was discovered in
response to the problem of canted antiferromagnetism in hematite [74] and some
other antiferromagnetic insulators.
Finally, Fig. 10 provides an overview of the magnetic ordering temperatures in
oxides. The histogram illustrates the distribution of Curie and Néel temperatures for
Fig. 10 Magnetic transition temperatures for oxides. Ferromagnets are shown in blue, ferrimag-
nets in pink, and antiferromagnets in red. Data are based on [33]
17 Magnetic Oxides and Other Compounds 863
Iron oxides and hydroxides constitute the most important group of magnetic
minerals [35]. Most important are the famous magnetic rock-forming oxides
magnetite and hematite. Then there is a series of crystalline or partly amorphous iron
oxyhydroxides and hydroxides that are found in soils and sediments. A summary of
the structural and intrinsic magnetic properties of the iron end-members of whole
group is given in Table 5; substitution of other magnetic or nonmagnetic cations
(especially Al3+ ) in the iron end-members will modify these values. Variability is
ubiquitous in natural specimens; no two examples of a mineral with the same name
are ever exactly the same.
The crystal structures of the main binary iron oxides and hydroxides are
illustrated in Fig. 11. We first present the structural and magnetic properties of
each in turn and then discuss structurally related binary oxides with other magnetic
cations. More complex, ternary oxides are treated in a following section.
Fig. 11 Crystal structures of iron oxides (a) hematite, (b) magnetite, (c) maghemite, (d) wüstite
and hydroxides, (e) goethite, (f) akagaénite, (g) lepidocrocite, (h) feroxhyte, and (i) amakinite.
Key: Red O2- ; light brown Fe3+(oct) ; dark brown Fe3+(tet) ; green mixed iron valence; blue Fe2+ ;
violet H+ ; Green Cl- . In maghemite 1/6 of the octahedral sites are unoccupied
Hematite
property associated with spin canting, and not parasitic ferromagnetism due to traces
of magnetite impurity. The anisotropy energy K1 at low temperatures is 9 kJm−3 ,
and hematite exhibits a spin flop transition in 6.9 T at 4 K. Because of the weakness
of the net magnetization, the anisotropy field μ0 Ha = 2 K1 /Ms is rather large and
powder samples often exhibit coercivity at room temperature.
Magnetite
Magnetite, Fe3 O4 , is the most famous magnetic mineral of them all and the other
major rock-forming iron oxide. It is a black ferrimagnetic conductor that is very
common in igneous rocks, and it was the main component of lodestones, the
original, natural permanent magnets that became magnetized by lightning strikes
on rocky outcrops. Ti-substituted magnetite is a common natural variant, and it
is our main source of information on paleomagnetism, the history of the Earth’s
magnetic field. Magnetite is important as iron ore, as a black pigment, toner (ink),
and in ferrofluids. Biogenic magnetite is produced by bacteria, pigeons, and other
creatures. The oxide can be a nuisance in sensitive magnetization measurements as
it is a widespread magnetic contaminant present in particulate air pollution.
The inverse spinel structure of magnetite (spinel is the mineral MgAl2 O4 )
is based on an face-centered cubic array with 32 oxygen ions, space group
Fd3m, Z = 8, where one-eighth of the tetrahedral interstices (8a, A-sites) are
occupied by ferric iron and one-half of the octahedral interstices (16d, B-sites)
are occupied by an equiatomic mixture of ferrous and ferric iron (Fig. 11b).
This cation distribution, with trivalent cations on A-sites, is known as the inverse
distribution. The cubic lattice parameter is a0 = 840 pm. Spinel itself has the
less common normal distribution, with the divalent Mg2+ cations on A-sites and
the trivalent Al3+ cations on B-sites. The chemical formula of magnetite can be
written as [Fe3+ ]{Fe2+ Fe3+ }O4 ; here [] denotes the A-sites, and {} denotes the
B-sites where there is rapid Fe2+ -Fe3+ electron exchange. The octahedral and
tetrahedral sublattices are coupled antiparallel by superexchange via 127◦ A-O-B
bonds, giving a ferrimagnetic structure with a net moment of about 4 μB and a room-
temperature magnetization of 92 Am2 kg−1 or 480 kAm−1 . The Curie temperature
is 860 K. The mobile electron associated with Fe2+ on the octahedral sites occupies
a one-sixth-filled minority-spin t2g band and the average B-site configuration is
(t2g 3 eg 2 )↑ (t2g 0.5 )↓ with
n = 5.5, so magnetite was expected to be half-metallic
with a spin gap in the majority density of states. There is limited evidence for an
exceptionally high-spin polarization at room temperature [81]. The 3d conduction
electrons interact electrostatically with the oxygen anions to form small polarons
with large effective mass, which move among the B-sites by thermally activated
hopping [117].
Magnetite undergoes the charge-ordering Verwey transition at 120 K [110]. This
is transition where the conductivity decreases abruptly by a factor ∼100 on cooling
and the symmetry of the crystal is lowered from cubic to monoclinic. Verwey’s
original model of regular charge ordering of Fe3+ and Fe2+ ions on octahedral sites
[108] was oversimplified, and a highly complex ordering of fractional charges in
17 Magnetic Oxides and Other Compounds 867
these sites described by the superposition of 168 atomic displacement waves with
iron trimer motifs has been established [92].
The magnetocrystalline anisotropy of magnetite K1c is −14 kJm−3 at room
temperature and K2c is −3 kJm−3 . However, K1c changes sign on cooling to
135 K, where the easy axis switches from
111 to
100. The room-temperature
magnetostriction constants are λ111 = 78 10−6 and λ100 = −20 10−6 and the
polycrystalline average λs = 3/5λ111 + 2/5λ100 = 39 10−6 .
Maghemite
Wüstite
The most reduced iron oxide is wüstite – FeO – a rare mineral that crystallizes
in the cubic halite (NaCl) structure, space group Fm3m with Z = 4 (Fig. 11d).
The lattice parameter is a0 ≈ 431 pm; ferrous iron occupies octahedral sites, but
the lattice is subject to a slight rhombohedral distortion to lower the energy of the
Fe2+ 3d6 cations. The oxide is generally nonstoichiometric, with an Fe/O ratio in the
range 0.88–0.96. Some ferric iron, needed for charge neutrality, occupies octahedral
sites and some tetrahedral sites in the halite structure that have nearby octahedral
vacancies [53].
The ferrous cation sites form a face-centered cubic lattice where antiferromag-
netic J1 interactions of a cation with its 12 nearest-neighbors are partly frustrated,
868 J. M. D. Coey
but the J2 interactions with the six second-neighbors are straightforwardly anti-
ferromagnetic, with 180◦ Fe-O-Fe bonds. The type II antiferromagnetic structure
is composed of alternating ferromagnetic (111) planes, with a Néel temperature
of 198 K. The direction of sublattice magnetization is
111. The two exchange
parameters can be deduced from measurements of the Néel temperature TN and the
paramagnetic Curie temperature θ .
Iron Hydroxides
There is a series of iron hydroxides. The least hydrated are the four oxyhydroxides
with the chemical formula FeOOH, equivalent to Fe2 O3. H2 O. The former empha-
sizes the presence of OH− anions in the crystal structure.
exhibits a varying degree of crystallinity and hydration [91]. Three categories are
distinguished, a “six-line” ferrihydrite, a “two-line” ferrihydrite, and an essentially
amorphous ferric gel. Ferrihydrite is a poorly crystallized hydrated ferric oxide
with notional composition 5Fe2 O3. 9H2 O. The better-crystallized variety shows
six broad X-ray reflections and orders magnetically below 100 K with a small
uncompensated moment. The two-line version shows just two very broad reflections
corresponding to lattice spacings of 250 and 150 pm and behaves similarly. The
ferric gel exhibits no clear Bragg reflections. Below 10 K, spins freeze in a
speromagnetic structure with antiferromagnetic nearest-neighbor correlations but
essentially random orientations of more distant neighbors leading to a small net
magnetization [24]. Superparamagnetic behavior is observed up to about 100 K.
The structures can be modeled as a network of edge- or corner-sharing octahedra.
A related synthetic amorphous magnet is FeF3 , where the structure is an
octahedral random network of corner-sharing FeF6 octahedra and the cations form
odd- and even-membered rings. The spins freeze below 30 K in a speromagnetic
spin structure, although the pairwise antiferromagnetic superexchange bonds (frus-
trated in the odd rings) would, if unfrustrated, give much higher antiferromagnetic
ordering temperature.
Ferrous Hydroxide
The natural ferrous hydroxide amakinite Fe(OH)2 has the hexagonal CdI2 structure
of brucite Mg(OH)2 and pyrochorite Mn(OH)2 . It is a layered structure based on a
hexagonal close-packed arrangement of OH ions, where the divalent cations fill all
the octahedral sites in alternate layers. Amakinite orders magnetically at 34 K, in
a planar antiferromagnetic structure of ferromagnetic planes. Green rust is a poorly
crystallized variant that is unstable in air. The Néel temperature of pyrochorite is
12 K, but the planes in that case have a spiral magnetic structure.
Ferrites
There are some very important families of synthetic stoichiometric insulating oxides
of ferric iron and another cation, known collectively as ferrites. These include
compounds with the spinel, garnet, orthoferrite, and hexaferrite structures. A few
natural examples exist, but ferrites are generally pure synthetic materials, prepared
by standard ceramic techniques. The vast majority of bulk magnetic oxides used for
practical purposes are hard or soft ferrites. The subject was first summarized by Smit
and Wijn [96] and other books include Valenzuela [104] and Dionne [38]. Many of
the original numerical data are to be found in Landholdt-Börnstein [9].
Spinels
The family with the cubic spinel structure, space group Fd3m, includes ZnFe2 O4 ,
MgFe2 O4 , MnFe2 O4 , Fe3 O4 , CoFe2 O, NiFe2 O4 , and Li0.5 Fe2.5 O4 . Only the first of
870 J. M. D. Coey
these has the normal cation distribution with iron on octahedral B-sites and zinc on
tetrahedral A-sites, whereas the others are inverse with Fe3+ on tetrahedral sites,
which leads to high-temperature ferrimagnetic ordering. Lithium ferrite has the
highest Curie temperature (also known as the ferrimagnetic Néel temperature) of
943 K. The extrapolated Curie temperature of maghemite is even higher, but it is
unattainable because γFe2 O3 converts to αFe2 O3 first. Cobalt ferrite has by far the
greatest magnetocrystalline anisotropy and magnetostriction, with [100] easy axes,
whereas all the others have [111] easy axes. These outstanding values arise from an
inverse cation distribution with Co2+ 3d7 ions on B-sites, which have trigonal 3m
point symmetry. These B-site ions are in a high-spin state t2g 5 eg 2 with S = 3/2 and a
spin moment of 3 μB . They can also have a significant unquenched orbital moment
of ∼0.6 μB , which is responsible for the strong cubic anisotropy K1c ≈ 290 kJm−3 .
Although the moment of an isolated Co2+ ion aligns along a local
111 trigonal
axis, the resultant bulk anisotropy lies along
100 [63]. The net moment is about
3.6 μB per formula at room temperature, and the magnetization of bulk samples is
455 kAm−1 or 86 Am2 kg−1 (455 emu/g or 86 emu/g), based on the X-ray density
of 5290 kgm−3 . The ferrimagnetic Néel temperature of CoFe2 O4 is 790 K, so the
magnetization values at T ≈ 0 are slightly higher.
Another consequence of the unquenched orbital moment on the Co2+ is an
exceptionally large magnetostriction. Values of λ100 for CoFe2 O4 crystals range
from −250 to −650 10−6 , depending on their precise composition. The value
of the other cubic magnetostriction constant λ111 is about +170 10−6 , and the
polycrystalline averages λs = (2λ100 + 3λ111 )/5 are negative, but quite variable.
A consequence of the magnetostriction is a slight distortion of the unit cell from
cubic Fd3m to tetragonal I41 /amd, with a tetragonality (a – c)/c ≈ 0.1%.
Copper ferrite, CuFe2 O4 , has a mostly inverse cation distribution that depends
on the preparation procedure. At temperatures below 700 ◦ C, the spinel structure is
tetragonally distorted with c/a = 1.06, but it is cubic when prepared above 800 ◦ C.
The anisotropy changes sign at 350 K, and there is a complex sequence of magnetic
phase transitions below room temperature.
Zinc ferrite has the normal cation distribution. The only magnetic species is
Fe3+ on octahedral sites, which form a network of corner-sharing tetrahedra in
the spinel structure. When the B-B interactions are antiferromagnetic, as they are
in ZnFe2 O4 , the exchange bonds are fully frustrated, which explains the low-spin
freezing temperature Tf , < 10 K. Magnetic properties of spinel ferrites are discussed
in detail in references [10, 64], and salient data on ferrimagnetic end-members are
summarized in Table 6. Mineral names are included, where they exist.
A related series of ferrites with formula FeM2 O4 are of less interest magnetically.
Chromite, FeCr2 O4 , is the principal natural source of chromium for stainless steel.
It orders magnetically at about 70 K, with a small magnetization of ∼0.08 MAm−1 .
Ulvöspinel, TiFe2 O4 , is an inverse spinel with a0 = 840 nm with formal
valences Ti4+ and Fe2+ . It orders antiferromagnetically at 120 K. There is a huge
range of natural and synthetic solid solutions with the spinel structure. Natural
titanomagnetites Fe3-x Tix O4, solid solutions between magnetite and ulvöspinel with
x ∼ 0.6, are important for palaeomagnetism, because fine grains of this mineral
17 Magnetic Oxides and Other Compounds 871
are the main carriers of natural remanence in rapidly cooled basaltic lavas used for
paleomagnetic studies [39]. Titanohematites, solid solutions between hematite and
ilmenite FeTiO3 , are also of interest in this context.
Optimized nickel-zinc ferrite and manganese-zinc ferrite are widely used as
cores in high-frequency inductors. The properties can be tuned by tailoring the
composition, microstructure, and porosity. Manganese-zinc ferrites offer initial
permeabilities of up to 10,000 and low coercivity; they may be used at frequencies
up to about 1 MHz. Nickel-zinc ferrites have lower permeability, generally <1000,
and lower magnetization but high resistivity ρ of up to 106 m, which allows them
to be used at radiofrequencies of 300 MHz or more.
Garnets
Garnets are oxides with formula A3 B2 C3 O12 that crystallize in the Ia3d space
group with a large cubic cell, Z = 8, having three cation sites 24c, 16a, and 24d
with eightfold, sixfold, and fourfold oxygen coordination. Natural garnets include
pyrope Mg3 Al2 Si3 O12 , grossular Ca3 Al2 Si3 O12 , andradite Ca3 Fe3+ 2 Si3 O12 , and
almandine Fe2+ 3 Al2 Si3 O12 . The latter two order magnetically below 10 K. Some
garnets are red or green gemstones.
The garnets are well known in magnetism because of the series of R3 Fe5 O12
compounds that adopt this structure when R3+ is yttrium or a tripositive 4f ion
from Sm to Yb. Yttrium iron garnet Y3 Fe5 O12 (commonly known as YIG) is a
green ferrimagnetic insulator with a bandgap of 2.8 eV and a Curie temperature of
560 K. The net uncompensated 24d-site moment leads to a room-temperature mag-
netization of 27.6 Am2 kg−1 or Ms = 144 kAm−1 . Anisotropy (K1 = −2 kJm−3 )
and magnetostriction (λ100 = 1 ppm, λ111 = −3 ppm) are both very small,
which ensures outstanding radiofrequency magnetic properties and a very narrow
872 J. M. D. Coey
Orthoferrites
Fig. 13 Temperature dependence of the magnetic moment per formula unit of some rare-earth
garnets
Hexagonal Ferrites
Fig. 14 (a) The magnetic structure of SrF12 O19 , showing the 2b bipyramidal site, (b) the principal
superexchange paths, and (c) the principal contributions to the uniaxial anisotropy
M – ferrites, have composition AFe12 O19 , where A is a large divalent cation [63].
Processing routes for both sintered and polymer-bonded hexagonal ferrites are well-
established [97]. Both BaFe12 O19 and SrFe12 O19 are produced in huge quantities,
of order a million tons per annum corresponding to more than 100 g on average for
everyone on Earth.
The magnetoplumbite structure is illustrated in Fig. 14a). It can be regarded as an
hexagonal packing of O2− and A2+ ions in a tall unit cell with space group p63 /mmc
having a ≈ 590 pm, c ≈ 2300 pm, and Z = 2. There are five types of interstitial sites
for ferric ions, three with octahedral symmetry (12k, 4f2 , and 2a), one tetrahedral
(4f1 ), and one fivefold coordinated trigonal bipyramidal site (2b). The structure
can be regarded as a stacking of alternate (111) slices of spinel (S blocks, Fe6 O8
containing 2a, and half the 12k octahedral sites and the 4f1 tetrahedral sites) and
triple layers of hexagonal close-packed oxygen (R blocks, AFe6 O11 , containing the
2b sites, and the remaining octahedral sites), where one in four of the oxygen in the
middle layer is replaced by A2+ . The stacking in the unit cell is SRS*R*, where *
indicates rotation by π around the hexagonal c-axis. A large family of related hexag-
onal oxides is obtained by different stackings of R, S, and T = A2 Fe8 O14 blocks.
The main superexchange paths are indicated on Fig. 14b), together with the
values of the exchange constants [94]. The strongest couplings tend to coincide with
the straightest bond angles. The ferrimagnetic structure is 12 k↑;2a↑;2b↑;4f1 ↓;4f2 ↓.
Since Fe3+ has a spin moment of 5μB and there are Z = 2 formula units in the unit
17 Magnetic Oxides and Other Compounds 875
cell, the net moment per formula unit at T ≈ 0 is (8 – 4) × 5μB = 20μB . The net
exchange coupling of 12k iron to its neighbors is weakest, and this iron moment has
the strongest temperature dependence (Fig. 14c).
The M, W, and X ferrites have easy c-axis anisotropy. The Y and Z ferrites are
easy-plane when M = Co. The magnetic properties are presented in detail in [63]
and summarized in Table 9. Properties of the three M-ferrites are quite similar.
The anisotropy field at room temperature is around 1.8 T, more than three times
the polarization μ0 Ms . Cobalt-substituted Y and Z ferrites can exhibit very little
coercivity, and they are useful for microwave applications.
Strong magnetic anisotropy is not normally expected from Fe3+ 3d5 ions, which
have a 6 S ground state with a spherical half-filled shell. However, in highly distorted
sites, the crystal field can mix in nonspherical 4 F excited states, leading to an
effective spin Hamiltonian DSz 2 ; the 2b trigonal bipyramidal sites and 12 k distorted
octahedral sites in M ferrites contribute about half of K1 , and there is a contribution
of opposite sign from the anisotropic magnetic dipole field (Fig. 17c) [94]. The iron
on 2b sites is hopping rapidly between two the tetrahedral positions that make up
the bipyramid [78].
A long search for cation substitutions to increase the magnetization or anisotropy
of M ferrites has led to a slight improvement by replacing some Sr2+ + Fe3+ by
La3+ + Co2+ . The magnetization Ms in oxide ferrimagnets is unavoidably limited
by their partly compensated ferrimagnetic structure and the fact that most of the
volume is composed of nonmagnetic oxygen ions. These drawbacks are partially
compensated by the fact that larger moments are available from ionic cations than
from metallic atoms. An extensive review [89] discusses cation substitutions in
hexagonal ferrites and the synthesis and ceramic processing of these materials.
Crystallite orientation is a critical step for easy axis (hard magnet) or easy-plane
(microwave ferrite) materials.
This section discusses magnetic oxides where the magnetic cation is not iron. The
materials are generally synthetic, not natural in origin.
876 J. M. D. Coey
3d Oxides
Monoxides
There is a series of isostructural antiferromagnetic insulating monoxides MnO, FeO,
CoO, and NiO with the NaCl structure (Fg 1d), which all have magnetic structures
of alternating ferromagnetic (111) planes. MgO is a nonmagnetic analogue. MnO
(manganosite) was the first material where antiferromagnetic order was identified,
from a series of magnetic Bragg neutron reflections that appeared below the Néel
temperature of 118 K. CoO, with high-spin Co2+ on the octahedral sites, has its
Néel temperature close to room temperature. The lattice has a slight tetragonal
distortion. NiO has the highest Néel temperature of 525 K, and the structure, like
that of FeO (wüstite), has a slight trigonal distortion. NiO is a green charge-transfer
insulator with a bandgap of 4 eV when stoichiometric [65], but it becomes a black
p-type polaron conductor when cation-deficient due to holes in the oxygen 2p band.
Stoichiometric NiO was used for exchange bias of early spin valves.
The magnetic properties of the cubic antiferromagnetic monoxides, including
wüstite, are summarized in Table 10. The nearest-neighbor superexchange inter-
action J1 with the 12 nearest-neighbor cations on an fcc lattice is frustrated, but
the interaction J2 with the six second-neighbor cations which lie on a simple cubic
lattice, with a 180◦ M-O-M superexchange bond, favors antiferromagnetic order.
CuO (tenorite) has a monoclinic structure with space group C2/c and a = 469 pm,
b = 343 pm, c = 5i3 pm, and β = 99.5◦ It orders magnetically at 230 K in a helical
structure, but it becomes a commensurate antiferromagnet below 213 K, where it is
also ferroelectric. It is the first binary multiferroic [111].
Sesquioxides
Ti, V, and Cr form sesquioxides which, like hematite, crystallize in the corundum
structure. Ti2 O3 is diamagnetic, with a small bandgap of only 0.2 eV between
the lower and upper Hubbard bands. The Ti3+ 3d1 electrons are thought to form
pair bonds, rather than ordering antiferromagnetically. V2 O3 exhibits a spectac-
ular first-order insulator-metal transition at the Néel temperature (150 K), where
Table 11 Magnetic properties of sesquioxides with the corundum, spinel, or bixbyite structures
Mineral Lattice
Oxide name parameters (pm) TN (K) Magnetism Other information
Ti2 O3 Tistarite R3c 514; 1366 – Diamagnetic p-type,
gap = 0.2 eV
V2 O3 Karelianite R3c 503; 1362 150 Antiferro Monoclinic below
TN
Metal-insulator
transition
Cr2 O3 Eskolaite R3c 496; 1359 306 Antiferro Magnetoelectric
αMn2 O3 Bixbyite Ia3 941 80 Antiferro First-order
transition at 25 K;
stabilized by iron
γMn2 O3 579; 940 39 Ferrimagnet
αFe2 O3 Hematite R3c 504; 1375 960 Canted af Morin transition at
265 K
γFe2 O3 Maghemite P41 32 835 985 Ferrimagnet Converts to
hematite on heating
the conductivity can change by as much as ten orders of magnitude [75]. The
low-temperature structure is monoclinic. Cr2 O3 has a different antiferromagnetic
stacking + − + − below its Néel point TN = 306 K compared to +– – +
for αFe2 O3 , and there is no spin reorientation. The signs refer to the direction of
magnetization of the four magnetic sublattices marked by the four cations along the
c-axis in Fig. 11a). Cr2 O3 is weakly magnetoelectric; a single antiferromagnetic
domain state produced by cooling below TN in parallel electric and magnetic
fields exhibits a small electrically induced magnetic moment. The effect is caused
by relative displacements of Cr3+ and O2− , in the electric field, which slightly
modifies the crystal field. The magnitude of the magnetoelectric coefficient α = μ0
M/E ≈ 1psm−1 . Mn2 O3 can crystallize in two different cubic structures; one is the
bixbyite structure, and the other is a tetragonal structure related to spinel. Properties
of these compounds are summarized in Table 11.
Related oxides have an ordered arrangement of different metal cations on the
cation sublattices. These include a series of titanates MTiO3 , which are low-
temperature antiferromagnets; an example is ilmenite, FeTiO3 , where the formal
cation valences are Fe2+ and Ti4+ . Only the former has a magnetic moment, and
the compound orders antiferromagnetically at 40 K.
Dioxides
A series of 3d dioxides crystallize in the rutile structure. TiO2 itself exhibits
temperature-independent paramagnetism, but it does not order magnetically. VO2 ,
a material of potential interest for oxide electronics, exhibits a metal-insulator
transition at 341 K. It has the rutile structure above the transition and a distorted,
monoclinic structure below, but it too is not thought to order magnetically. CrO2 is
the only example we have of a ferromagnetic binary metal oxide. It is half-metallic,
878 J. M. D. Coey
with a gap in the minority-spin density of states. CrO2 can be grown in the form
of 300 nm acicular nanoparticles with an aspect ratio of 8:1. It was widely used
for magnetic videotapes, which could be easily duplicated by thermal imprinting,
thanks to the convenient Curie temperature at TC = 390 K. It cannot be increased
by cation substitution. MnO2 is an antiferromagnetic insulator with a low Néel
temperature (Table 12).
Mixed-Valence Oxides
The mixed-valence manganese oxide Mn3 O4 (Hausmannite) is a spinel-type oxide
containing a mixture of Mn2+ 3d5 and Mn3+ 3d4 ions. Here the crystal field
stabilization energy favors B-sites for Mn3+ and a normal cation distribution. There
is no electron hopping, and the unit cell with Z = 4 is tetragonally distorted. The
oxide orders ferrimagnetically at 41 K, with [010] as the easy axes, and there is
a noncollinear, canted magnetic structure driven by local anisotropy at the Jahn-
Teller-distorted B-sites.
Co3 O4 has an undistorted cubic spinel structure with a normal cation distribution
and a0 = 808 pm. The Co3+ 3d6 on octahedral sites is in a low-spin state, where
it has no moment, and the Co2+ 3d7 is also in a low-spin state. The oxide orders
antiferromagnetically at 40 K (Table 13).
Perovskites
A large family of magnetic oxides ABO3 have structures related to cubic perovskite,
CaTiO3 . Here A is often a rare-earth or alkaline earth cation coordinated by 12
17 Magnetic Oxides and Other Compounds 879
Fig. 15 The cubic perovskite ABO3 and double perovskite A2 BB’O6 structures
Usually, these compounds are orthorhombic with space group Pbnm. The R-O-R
superexchange is very weak, as can be seen from the Néel temperatures of the rare-
earth sesquioxides in Table 19, which amount to only a few kelvins.
The orthotitanates with Ti3+ 3d1 are all Mott insulators; t is small, and there
are large rotations of the TiO6 octahedra. Compounds with a heavy rare earth or
yttrium exhibit orbital ordering of the occupied dyz and dzx orbitals, and they are
ferromagnetic; TC = 30 K for YTiO3 , for example, with a moment of 0.83 μB per
formula. The compounds of the light rare earths, with larger tolerance factors, are
simple G-type antiferromagnets where each Ti is antiparallel to all six Ti neighbors,
with a moment of 0.45 μB and TN = 146 K for LaTiO3 , for example; orbital order
is less pronounced.
The rare-earth orthovanadates form across the whole series from La to Lu,
with Néel temperatures in the range 100–140 K, decreasing with decreasing lattice
parameter and superexchange bond angles. Orbital order of the dyz and dzx orbitals
of the V3+ t2g 2 ions sets in at a temperature that is 10–70 K greater. The heavy
rare-earth ions order magnetically at temperatures of about 10 K or less.
Néel temperatures for the orthochromites are higher, 110–280 K, but the trend is
similar. There is no orbital order for Cr3+ ions, which have a half-filled t2g shell.
The rare-earth manganites are different. They involve the strong Jahn-Teller Mn3+
t2g 3 eg 1 ion and can crystallize either in the orthorhombic perovskite structure, with
a noncommensurate antiferromagnetic structure and a Néel point at about 40 K and
rare-earth ordering below 10 K, or else in a high-temperature hexagonal structure
with space group P63 cm, for yttrium and heavy rare earths where the Mn and R
cations are coordinated by five or seven oxygen anions, respectively. The Mn3+
ions form trimers, and the exchange is strongly frustrated, but antiferromagnetism
sets in at 70–110 K, with a spin liquid at higher temperatures. The compounds are
magnetoelectric and multiferroic, with a ferroelectric transition at 800–900 K.
The rare-earth orthoferrites with space group Pbnm (Table 8) have the highest
Néel temperatures, which decrease toward the end of the series with the lanthanide
contraction, similarly to the V and Cr perovskite series. Here the variation is from
740 K for La to 623 K for Lu, reflecting the decrease of the Fe-O-Fe superexchange
bond angle. They all have canted antiferromagnetic structures with a weak net
magnetization of order 10 kAm−1 , due to the D-M interaction, Eq. 6. The canting
angle is about 0.5◦ . The orthoferrites used to be of interest as materials for bubble
memory [42]. They exhibit fast spin dynamics associated with the antiferromagnetic
resonance mode and very high domain-wall velocities. They are also of interest as
potential ferroelectrics.
The cobalt in the RCoO3 series is nonmagnetic on account of the low-spin Co3+
state 3d6 t2g 6 in octahedral coordination.
All the nickelates, with the exception of LaNiO3 , which is a rhombohedral R3c
metal, have an insulating antiferromagnetic ground state and undergo a metal-
insulation transition at higher temperature. For Pr and Nd, where the transition is
first-order, this coincides with the Néel temperature but the transitions are distinct
for the others, as shown in Fig. 16. Néel temperatures range from 130 to 225 K. In
the insulating state, the orthorhombic structure undergoes a monoclinic distortion
17 Magnetic Oxides and Other Compounds 881
Fig. 16 Phase diagram of the rare-earth nickelates RNiO3 , plotted as a function of tolerance
factor, showing also the average Ni-O-Ni bond angle (after [16])
Table 14 Orthorhombic unit cell volumes v (pm3 ) and magnetic ordering temperatures (K) of RMO3 compounds
M|R Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
V v 224 241 239 237 235 232 229 227 226 223 223 221 220 218
TN 114 143 135 142 139 133 123 111 110 112 110 101 102
Cr v 214 233 232 230 228 223 221 220 217 215 214 213 211 210 209
TN 141 282 257 239 224 193 181 170 158 146 141 133 124 118 112
Mn v 225 243 240 239 233 232 233 229 228 226 224 223 222 221
TN 42 139 95 85 47 43 46 42 41
Hex TN 72 57 76 80 82 88 90
Fe v 225 243 239 234 233 232 230 228 226 224 223 222 220 219
TN 643 740 709 690 674 664 663 650 645 643 640 631 631 623
Ni v 212 222 221 219 218 217 214 212 210 206 207 207
TN 145 130 200 225 205 180 163 148 144 144 138 130
J. M. D. Coey
17 Magnetic Oxides and Other Compounds 883
earth cation and A is a divalent alkaline earth ion, Ca or Sr [27]. We comment briefly
on the magnetic aspects here.
There are four basic types of magnetic order in perovskites: the F, A, C, and G
types. F is ferromagnetic, A is a planar antiferromagnet composed of ferromagnetic
planes stacked antiferromagnetically, C is composed of ferromagnetic chains
antiferromagnetically aligned, and G is a straightforward antiferromagnet where
all the magnetic nearest-neighbors of a magnetic ion are aligned antiparallel to
it. Symmetry-allowed magnetic modes may combine different types of magnetic
order, with the moments along the principal axes. For example, Gz may combine
with Fx . The end-member LaMnO3 is an A-type antiferromagnetic insulator, with
TN = 150 K. On doping with Sr or Ca, the oxides first become í-type insulators
and then F-type metals. Optimal doping is at x ≈ 0.3, where the compounds
have the highest Curie temperatures, which do not exceed 400 K however (370 K
for (La0.7 Sr0.3 )MnO3 ; 300 K for (La0.7 Ca0.3 )MnO3 ). These materials are thought
to be half-metallic, and they exhibit the remarkable phenomenon of colossal
magnetoresistance just below the Curie temperature, especially when they are in thin
film form. A huge peak in the resistance, related to the difficulty of electron hopping
among the Mn4+ cores when the spins begin to become disordered, is dramatically
reduced when the Mn spins are aligned by a large applied magnetic field (Fig. 17).
On further doping, toward x = 0.5, the Mn3+ and Mn4+ ions tend to order on
alternate sites, and the oxides become insulators again, adopting C-type antiferro-
magnetic order. Not only is there charge order, but the eg electrons of the Mn3+
3d4 ions undergo orbital order, with correlated Jahn-Teller distortions on nearby
sites. The CE type of charge, orbital, and spin order that may arise near x = 0.5 is
illustrated in Fig. 18. When x = 0.67, other types of stripes of charge and orbital
order can appear, and when x ≈ 1, the antiferromagnetism becomes G-type. The
rich phase diagrams of the mixed-valence manganites reflect the complex balance
Fig. 17 Colossal
5
magnetoresistance of 0T
(La0.7 Ca0.3 )MnO3 in a field 10 T
of 10 T
4
Resistivity (Ω mm)
0
0 50 100 150 200 250 300 350
Tempetature, T (K)
884 J. M. D. Coey
O’ sro
R rhombohedral, T R T
tetragonal, M monoclinic, H 200 T H
hexagonal. ‘ charge order, ‘’ M
orbital order. A, C, and G C G
refer to the antiferromagnetic A
O’ sro
structures; C, canted; sro,
c A O’’ O
short range order
0
0.0 0.2 0.4 0.6 0.8 1.0
concentration x
of coulomb, elastic, and magnetic interactions in these materials. The diagram for
(La1-x Srx )MnO3 is shown in Fig. 19 [54].
It must be admitted that the purely ionic picture of a highly polar electronic
structure in these and other 3d oxides is greatly oversimplifies – the Mn-O bonds
are substantially covalent, and the charge transfer from cation to anion is much less
than the formal charge states suggest. Nevertheless, the magnetic properties of the
manganese ions are well described by the quantum numbers S = 3/2 or S = 2 despite
the integrated charge in the vicinity of the cations being closer to 1 or 2, rather than
3 or 4.
but the tolerance factor influences the structure, much as it does for the single
perovskite oxides. There are about a thousand known compounds, and a quarter
of them order magnetically. Most are insulating and antiferromagnetic with Néel
temperatures below 50 K, but tens of them are ferromagnetic or ferrimagnetic at
relatively high temperature, and some of these are half-metallic [87, 107]. Magnetic
ordering temperatures are sensitive to the degree of atomic order on the cation
sites. Perhaps the best-known example is Sr2 FeMoO6 , which is half-metallic with
TC = 436 K. Ferromagnetic exchange is promoted by the Mo, formally in a 4d1
state. More examples are listed in Table 15. Compounds with Re or Os often order
at the highest temperatures, but the spin-orbit coupling of the heavy metal tends to
mix the spin channels and compromise the half-metallicity.
There are very many layered perovskites, composed of slabs of the basic
ABO3 structure, with an intercalated motif. YBa2 Cu3 O6 , the end-member of the
famous series of high-temperature cuprate superconductors, is antiferromagnetic,
with TN = 420 K, and a magnetic moment of 0.5 μB on the Cu2+ sites, where
the 3d electron is in a highly anisotropic x2 - y2 orbital. Residual antiferromagnetic
correlations are thought to play a role in the superconductivity of the compounds
with more oxygen.
Pyrochlores
Fig. 20 Crystal structures (a) fluorite-type AO2 and (b) pyrochlore A2 B2 O7 ; (c) shows the
connectivity of the A-site tetrahedra, each with an oxygen ion at the center
4d and 5d Oxides
Sr3 Ru2 O7 are, respectively, a p-wave, spin triplet superconductor with Tsc ≈ 1 K
[68] and a quasi-two-dimensional metal close to a quantum critical point, with a
metamagnetic spin-density wave transition [66].
5d and 5f compounds exhibit the strongest spin-orbit coupling. The spin and orbit
are coupled together for the individual electrons, to form j = l ± ½ states. The 5d
states are extended and tend to form broad bands, with relatively weak correlations.
The crystal field in octahedral sites exceeds the on-site JH that leads to Hund’s rules
in 3d ions. They are therefore in a low-spin state, where the t2g orbitals will be
occupied before the eg orbitals, in octahedral coordination. The t2g manifold has an
effective orbital quantum number l = 1, so the one-electron j-states are j = ½ and
j = 3/2. The possible mj states for the six electrons are a lower j = 3/2 quartet and
an upper j = ½ doublet, as illustrated in Fig. 20. The t2g wave functions are then
mixtures of the xy, yz, and zx states, where the spin-orbit interaction mixes the spin
and orbital character. For example, Ir3+ (t2g 6 ) has fully occupied t2g orbitals, and
it is in a nonmagnetic low-spin state in SrIrO3 , which is a nonmagnetic semimetal,
whereas for Ir4+ (t2g 5 ), the j = 3/2 states are fully occupied, and one electron is in a
j = ½ state, with wave function:
1 1 √
| , + = 1/ 3 (| xy, ↑ + | yz, ↓ + i | zx. ↓)
2 2
1 1 √
or | , − = 1/ 3 (− | xy, ↓ + | yz, ↑ − i | zx. ↑) (8)
2 2
4f Oxides
The rare earths normally adopt a trivalent ionic configuration, but Eu and Yb
are exceptions, preferring the stable closed (sub)shell configurations 4f7 and 4f14 ,
17 Magnetic Oxides and Other Compounds 889
respectively, that correspond to the divalent ionic configuration. For similar reasons,
Ce tends to adopt a quadrivalent 4f0 configuration.
EuO crystallizes in the cubic NaCl structure (Fig. 11d), with a0 = 516 pm.
It is a ferromagnetic insulator with a bandgap of 1.2 eV and TC = 69 K. The
bandgap decreases by 0.2 eV at TC due to spin splitting of the empty 5d conduction
band. When nonstoichiometric (cation deficient) or doped with a trivalent rare
earth such as Gd, the Curie temperature of EuO is increased substantially by the
presence of 5d conduction electrons. A metal-insulator transition appears at TC ,
where the conductivity can change by up to 14 orders of magnitude; the transition is
accompanied by colossal negative magnetoresistance of up to 108 % per tesla. The
carriers are magnetic polarons [86].
The isostructural europium monochalcogenides (Table 18) exhibit a systematic
variation of magnetic order governed by the relative strengths of the J1 and J2
interactions. Unlike the nearest-neighbor interaction in the 3d monoxides (§ 5.1.1),
J1 is positive, and it competes in the chalcogenides with a negative J2 coupling
cube-corner cations via 180◦ superexchange bonds.
Rare-earth sesquioxides R2 O3 crystallize in the cubic bixbyite structure, with
Z = 16. The magnetic coupling between rare-earth ions is weak, and none of them
order antiferromagnetically above 5 K (Table 19). The hydroxides R(OH)3 have
similarly low Néel temperatures.
There are some 4f mixed-valence compounds. Eu3 O4 is antiferromagnetic below
5.0 K, but it undergoes a metamagnetic transition in a low magnetic field. Eu3 S4 is
cubic at room temperature, but it undergoes a charge ordering transition at 160 K
and orders ferromagnetically at 3.1 K.
The actinides in the first half of the series, from Pa to Bk, are sufficiently stable
to allow magnetic measurements to be made on their compounds. The moment
is mainly orbital in character. The elements form a series of dioxides (Table 20)
with the cubic CaF2 fluorite structure shown in Fig. 20a. The actinides also
890 J. M. D. Coey
form monoxides and chalcogenides, as well as pnictides, all with the cubic NaCl
structure (Table 21). US has the largest cubic anisotropy of any known material,
K1 c = 43 MJm−3 . The spin-orbit coupling is very strong, and the 5f one-electron
states have l = 3 and s = ±1/2, giving j = 5/2 or 7/2. The j = 5/2 states are split in
the cubic crystal field into a lower doublet and an upper singlet, so that occupancy
by one, two, three, five, or seven electrons leads to atomic moments that can order
magnetically, whereas the atoms with four and six electrons are nonmagnetic [85].
The data summarized in Tables 20 and 21 bear this out.
Cubic actinide compounds often exhibit 3k antiferromagnetic structures, charac-
terized by propagation vectors with Fourier components along all three equivalent
cubic directions. The spins are then aligned along the four <111> directions.
Related Compounds
There are many other families of 3d transition-metal compounds that are more or
less ionic than the oxides. It is useful to review a few of them, so as to place the
oxide magnetism in a broader context.
Halides
The most electronegative anion, F− , forms the strongest ionic bonds with transition
metals. The 3d difluorides have the tetragonal rutile (TiO2 ) structure, illustrated
in Fig. 18b). The difluorides listed in Table 22 are all antiferromagnets, with
17 Magnetic Oxides and Other Compounds 891
relatively low Néel temperatures in the range 38–78 K. The trifluorides crystallize
in a rhombohedrally distorted ReO3 structure, which resembles the ideal perovskite
structure of Fig. 15a) without the A-site cation in the center of the unit cell. The
lattice parameter ac in the table pertains to a cubic ReO3 -type unit cell. The Néel
temperatures with almost straight, unfrustrated M-O-M bonds range up to 363 K, for
FeF3 , indicating weaker superexchange than in comparable oxides such as YFeO3 .
As in the orthoferrites, the symmetry permits a Dzyaloshinskii-Moriya interaction
and canting of the antiferromagnetic sublattices in trifluorides when the moments
lie perpendicular to rhombohedral c-axis [73]. Ferric fluoride has the largest low-
temperature iron sublattice moment and the largest 57 Fe hyperfine field, 62.2 T, of
any ferric iron due to the strongly ionic character of the bonding. The comparable
value for aFe2 O3 is 54.2 T. [52]. FeF3 can also crystallize in a highly frustrated
pyrochlore-like structure, where the Néel temperature is only 22 K.
Tetragonal K2 NiF4 is an insulator with Ni2+ , S = 1, and a model two-
dimensional magnetic material because the interlayer exchange interactions cancel.
Rb2 CoF4 is an almost-ideal two-dimensional Ising antiferromagnetic, thanks to the
strong uniaxial anisotropy experienced by Co2+ .
Unlike the fluorides, which have three-dimension crystal structures similar to
rutile or perovskite, the other transition-metal halides have hexagonal layered
structures [71] because of the large size of the anions. The ionic volumes of Cl− ,
B− , and I− are three to five times larger than that of F− . The crystal structure type is
either CdI2 (Fig. 11i) or CdCl2 (Fig. 21d). The hexagonal layers are the same in each
case, but the packing is ABABAB . . . . in the CdI2 case and ABCABC . . . . . . in
CdCl2 . All order antiferromagnetically in collinear, triangular, or helical structures,
mostly at temperatures of order 10 K although |θp | is an order of magnitude greater
for the Ti and V compounds. The in-plane exchange interactions are competing or
frustrated. Magnetic order in monolayers of the vanadium compounds may set in at
higher temperatures than in the bulk [112] (Table 23).
Trihalides form R3̄ layer structures with a honeycomb lattice that can be readily
exfoliated. The layers are ferromagnetic in CrX3 with X = Cl, Br and I. CrCl3
is a planar antiferromagnet with TN = 14 K and easy-plane anisotropy, whereas
CrBr3 and CrI3 are ferromagnetic with strong easy c-axis anisotropy and TC = 33
K and 61 K respectively. Exfoliated monolayers of CrI3 have Tc = 45 K. FeCl3
is helimagnetic below 9 K, and magnetically-ordered layers can be intercalated
into graphite. The rare earths form trifluorides with very low Curie temperatures.
GdF3 , with TC = 1.2 K, for example, is an excellent potential low-temperature
magnetocaloric material.
892 J. M. D. Coey
Fig. 21 The crystal structures of (a) FeS2 (pyrite), (b) FeF2 (rutile),)(c) FeF3 (ReO3 -type), and
(d) FeCl2 (CdCl2 )
Chalcogenides
The elements in column 16 of the periodic table, S, Se, and Te, known as chalcogens
form increasingly covalent bonds in their transition-metal chalcogenides. Some
crystal structures are common to oxides and chalcogenides, but others, such as the
pyrite (FeS2 ) or nickeline (NiAs) structures, never form with oxides. Transition-
metal sulfides exhibit a wide variety of magnetic and electrical properties [84].
The main iron-sulfur minerals are pyrite and pyrrhotite. Pyrite, FeS2, also known
as fool’s gold, is often found as large brassy cubic crystals. The sulfur is present
in the structure as disulfide S2 2− pairs, and the ferrous iron, with formal charge
17 Magnetic Oxides and Other Compounds 893
Fig. 22 Structures of transition-metal sulfides. (a) FeS2 (pyrite), (b) NiS (NaAs-structure),
(c) Fe7 S8 (pyrrhotite), and (d) CuFeS2 (chalcopyrite)
2+, is in an S = 0 low-spin state with no magnetic moment. FeSe2 and FeTe2 are
similarly nonmagnetic. CoS2 is an itinerant ferromagnet with Tc = 120 K. Other
pyrites are antiferromagnetic. Properties are collected in Table 22, and the structure
is illustrated in Fig. 22a) (Table 24).
Chalcopyrite, CuFeS2 , is an important copper ore mineral. It is a tetragonal
antiferromagnetic semiconductor with a = 529 pm and c = 1042 pm; the structure
(Fig. 22d) is related to zinc blende (ZnS). Sulfur is unpaired S2− . The Néel
temperature of 815 K is exceptionally high, and the Fe3+ moment is reduced to 3.85
μB by covalent mixing with sulfur. Bornite, Cu5 FeS4 , another copper-iron sulfide
mineral, is antiferromagnetic below 76 K. Cubanite CuFe2 S3 is an orthorhombic
mixed-valence iron mineral, a canted antiferromagnet with a weak ferromagnetic
moment of just 1 Am2 kg−1 , which transforms to a cubic structure at 490 K.
An important group of magnetic chalcogenides, listed in Table 25, crystallize in
a variant of the hexagonal NiAs (nickeline) structure (a = 344 pm, c = 571 pm;
Fig. 21b)). The compounds are usually substoichiometric, with ordered or disor-
dered cation vacancies. Cr2 S3 , with ordered Cr vacancies, is ferrimagnetic below
130 K. CrSe is a noncollinear antiferromagnet, but CrTe is a ferromagnet. Both of
894 J. M. D. Coey
them order magnetically close to room temperature. Thin films of CrTe grown on
SrTiO3 substrates (111) show evidence of a topological Hall effect [118].
Pyrrhotite, Fe7 S8 , is a rock-forming mineral and the second most common
strongly magnetic mineral, after magnetite. The iron vacancies in the monoclinic
structure are ordered on alternate planes (Fig. 22c), giving a ferrimagnetic structure,
with moments along the c-axis, and substantial uniaxial anisotropy.
Antiferromagnetic FeS (troilite) has no cation vacancies, but the Fe forms
triangles in a variant of the NiAs structure, stable below a transition at Tα = 413 K.
Hexagonal NiS is a planar antiferromagnet, with a first-order transition to a Pauli
paramagnetic state at 260 K. A trigonal polymorph, Millerite, is a nonmagnetic
metal.
MnS exists in three polymorphic forms; all are antiferromagnetic, with 12
nearest-neighbor manganese atoms [34]. The Mn is octahedrally coordinated by
sulfur in alabandite, αMnS, which has the cubic halite (NaCl) structure. In βMnS
and γMnS, the Mn is tetrahedrally coordinated by sulfur, and the sulfides have the
cubic zinc blende structure or the hexagonal wurtzite structure, respectively. Néel
temperatures are 154 K, 100 K, and 80 K, respectively.
An important family of cubic magnetic chalcogenides are the synthetic sulphos-
pinels that were intensively studied in the 1970s. Most of them have a normal
cation distribution with Cr3+ or Rh3+ on B-sites, which have a strong preference
for d3 ions. The structure was illustrated in Fig. 11c). Natural sulphospinels are
rare and include carrollite, CuCo2 S4 , greigite Fe3 S4 which is the sulfide analogue
of magnetite that is produced by some magnetotactic bacteria, and nonmagnetic
linneite Co3 S4 . Of these, only greigite orders magnetically, at 580 K. A large
number of synthetic compounds have been prepared [105]. The structural and
magnetic properties of the sulphospinel family are summarized in Table 26.
Note that the Rh3+ and the Co3+ in B-sites are in a low-spin t2g state with S = 0,
so any magnetic order depends on the A-site cations. As with the oxide spinels,
there are numerous interesting solid solutions between the various end-members.
One example is Fe0.5 Rh0.5 Rh2 S4 , which orders antiferromagnetically at 145 K,
despite Fe3+ , the only magnetic ions, being separated by 985 pm. Another example
17 Magnetic Oxides and Other Compounds 895
is CoRh2 S4 , which has Co2+ on A-sites where the superexchange path involves
two anions (or low-spin Rh3+ ), yet the Néel temperature is 400 K. Superexchange
interactions can be remarkably long-range in a covalent matrix.
Notable among the sulphospinels are the materials which, like EuO, are ferro-
magnetic semiconductors. The Curie temperatures of p-type CuCr2 S4 and CuCr2 Se4
are well above room temperature. A series of chalcogenide layer compounds
including CrSi2 Te6 and Cr2 Ge2 Te6 with van der Waals interlayer bonding can be
exfoliated, like CrI3 , to yield ferromagnetic monolayers. Their Curie Temperature
is ≈ 60 K [48].
Pnictides
The elements in column 15 of the periodic table, N, P, As, Sb, and Bi, are known
as pnictogens and form pnictides with transition elements. The bonding tends to be
metallic rather than ionic, but we consider them briefly here. The iron nitrides are an
important group of magnetic compounds. Nitrogen is one of the few elements in the
periodic table that is small enough to fit into the interstices of a metallic 3d lattice.
Since exchange, especially in iron metal, is highly sensitive to interatomic spacing,
there can be big changes in magnetism whenever nitrogen enters the structure. A
nice example is Fe4 N, where the nitrogen occupies the cube center position and
expands the fcc structure of γ-iron. Fcc iron is at the limit for the appearance of
896 J. M. D. Coey
magnetism, but Fe4 N is a strong ferromagnet, with TC = 769 K. The cube corner 1a
site and face center 3c sites are now inequivalent, and 1a → 3c charge transfer leads
to a buildup of moment on 1a sites (3.0 μB ) at the expense of 3c sites (2.0 μB ).
The magnetization Ms is still less than it is for αFe (a0 = 286.6 pm), because of
the lattice expansion caused by interstitial nitrogen. The properties of this and other
Fe-N phases are summarized in Table 27 [25].
Tetragonal α”Fe16 N2 is a remarkable iron compound, where the magnetization
actually exceeds that of αFe. The uniaxial anisotropy is approximately 1 MJm−3 , a
value that is much too large for a soft magnet but insufficient for a dense permanent
magnet that would not have to rely, like alnico, on shape anisotropy to retain a
permanently magnetized state [95].
An interesting series of Mn pnictides, Table 28, includes MnAs, MnSb, and
MnBi, which all crystallize in the NiAs structure (Fig. 22b). MnN and MnP
crystallize in an orthorhombic variant. MnBi exhibits uniaxial anisotropy K1 = 0.9
MJm−3 and good magneto-optic properties due to strong spin-orbit coupling on Bi.
In this case, the anisotropy is just sufficient to make a permanent magnet [95].
The rare-earth nitrides RN are ferromagnetic, with a maximum Curie temperature
Tc = 70 K for GdN. All the others have lower Curie temperatures varying as the de
Gennes factor of the rare-earth ion.
17 Magnetic Oxides and Other Compounds 897
Silicates
The aluminosilicate minerals, which make up the bulk of the Earth’s crust, are
traditionally classified in terms of the connectivity of the SiO4 tetrahedral units
that are the common feature of all silicate structures. According to the mineralogists
clasification, the tetrahedral units may form a three-dimensional network in tectosil-
icates such as quartz, two-dimensional layers in phyllosilicates such as mica, double
or single one-dimensional chains in the inosilicates such as amphibole or pyroxene,
rings in cyclosilicates such as tourmaline, and isolated single or double tetrahedral
groups in silicon-poor nesosilicates such as olivine or sorosilicates such as epidote.
The other structural elements in aluminosilicates – octahedrally coordinated metals
(aluminum, iron) and alkali or alkaline earth cations in larger sites – form networks
that are interspersed with those of the silica tetrahedra [58].
Here we focus on the iron-rich silicates that are end-members of the rock-forming
solid solution series. A classification based on the connectivity of the octahedral
units, which often share edges or corners, is more appropriate for discussing the
magnetism [23]. The illustrations of structures in this section therefore show the
metal cation connectivity, as well as the silica frameworks (blue tetrahedra in
Fig. 23). Edge-sharing octahedra give rise to weak ferromagnetic superexchange,
but no silicate is known to order ferromagnetically, and none of them order
antiferromagnetically above 160 K. The relatively low density of magnetic ions
and the reduced dimensionality of the basic magnetic sheets, ribbons, or chains all
contribute to the low magnetic ordering temperatures.
Magnetic order in the iron end-members of the main structural families will
now be reviewed, and a summary is provided in Table 29. Olivines, with isolated
SiO4 tetrahedra, are framework structures from a magnetic viewpoint. In the
orthorhombic structure, space group Pnma, there are two octahedral iron sites,
M1 chains along b and M2 sheets in the ac plane (Fig. 23a). The orthorhombic
ferrous olivine fayalite Fe2 SiO4 orders antiferromagnetically at 65 K. The magnetic
structure is one of ferromagnetic M1 chains with moments slightly canted with
respect to b, coupled antiparallel to each other, and to the M2 neighbors. The
Fig. 23 Silicate crystal structures. (a) Olivine, (b) trioctahedral 1:1, (c) dioctahedral 2:1, with
intercalated ions, and (d) amphibole
898 J. M. D. Coey
crystal field acting on the Fe2+ favors different directions at the two sites, leading
to alternate spin canting at both sites.
Laihunite is an iron-deficient ferric olivine where half the M1 sites are vacant,
and the ferric iron in the M2 planes orders antiferromagnetically at 160 K. The
remaining ferrous ions in the M1 chains are crazy spins that are initially decoupled
from the magnetic order because they have equal numbers of neighbors on the two
M2 antiferromagnetic sublattices and cannot decide which way to turn.
Natural olivines are generally solid solutions; the forsterite (Mg2 SiO4 )-fayalite
series is a good example. Synthetic olivines with Mn, Co, or Ni also have canted
antiferromagnetic structures, but with lower Néel temperatures than fayalite [44]
(Table 29).
Sheet silicates are layered materials from the point of view of both the silicon
and the metal cations. The family includes rock-forming minerals like mica and
17 Magnetic Oxides and Other Compounds 899
clay minerals with a particle size below 2 μm that are plentiful in sediments and
soils. There are two main families, the 1:1 minerals, with an octahedral/tetrahedral
bilayer, and the 2:1 minerals, with a tetrahedral/ octahedral/tetrahedral sandwich
trilayer (Fig. 23b, c). The octahedral sites form a triangular lattice and are all
occupied by divalent cations in the trioctahedral minerals, but only two-thirds of
them are occupied by trivalent cations in the dioctahedral minerals, either at random
or forming a honeycomb lattice. Various stacking sequences of the layers with
different c parameters are possible, and interlayer van der Waals interactions are
weak, so it is possible to intercalate water, large monovalent cations, or various
organic molecules in the interlayer space. These silicates form a very interesting
group of two-dimensional materials, not least because of their vital role in soils.
We look first at the divalent, ferrous trioctahedral materials. Greenalite
{Fe2+ 3 }[Si2 ]O5 (OH)4 , the ferrous mineral related to serpentine, is a 1:1 mineral that
orders at 17 K as a planar antiferromagnet with in-plane ferromagnetic octahedral
sheets very weakly coupled by long-range interlayer antiferromagnetic interactions.
The mineral exhibits ferromagnetic hysteresis below TN , due to a spin flop. The 2:1
counterpart is minnesotaite {Fe2+ 3 }[Si4 ]O10 (OH)2 , which behaves similarly. It is
a planar antiferromagnet with TN = 27 K. A neutron diffraction pattern showing
antiferromagnetic reflections is shown in Fig. 24. The interplane exchange is very
weak, but the intraplane exchange is ferromagnetic, with θp = 17 K. The in-plane
magnetization in the octahedral sheets is explained by a trigonal crystal field acting
on the Fe2+ , which splits the 5 T2g triplet giving a 5 A1g ground state in the cubic
crystal field that is split further by a trigonal component to give a lowest Sz = 0
singlet (Fig. 25). This singlet implies easy-plane magnetic anisotropy in the plane
perpendicular to Oz. Biotite, a more chemically disordered 2:1 silicate that often
appears with magnetite inclusions, exhibits spin freezing only below 7 K.
Cronstedite {Fe2+ 2 Fe3+ }[SiFe3+ ]O5 (OH)4 is an unusual mixed-valence triocta-
hedral 1:1 layer mineral, which exhibits the highest conductivity of any silicate. It
orders antiferromagnetically at 12 K, although the paramagnetic Curie temperature
θp is positive, as it is for all the other ferrous trioctahedral silicates, because of the
ferromagnetic Fe2+ -O-Fe2+ superexchange.
Turning now to the ferric dioctahedral sheet silicates, pyrophyllite, with an
ordered honeycomb occupancy of two-thirds of the octahedral sites, orders anti-
ferromagnetically below 18 K, whereas nontronite, which has a similar value of
θp = −20 K but a more disordered cation distribution with a proportion of triangles,
shows spin freezing only below 2 K. Frustration can become an issue in the
trioctahedral minerals with random octahedral site occupancy (Fig. 26).
Next, we come to a large group of silicates with ribbons or chains of metal
cations, including the amphibole and pyroxene groups. There are resemblances
with the 2:1 sheet silicates, where the ribbons can be regarded as strips of a 2:1
layer in a base-centered lattice, with silica tetrahedra between them; the inter-
ribbon exchange coupling should be much weaker than the intra-ribbon exchange,
so ribbons can be regarded as isolated magnetic motifs. In amphiboles, they are four
octahedra wide, whereas in pyroxenes they are only two octahedra wide. The ferrous
900 J. M. D. Coey
50
σ(Am2kg–1)
00 1
Counts
2 25
1
I(T)/I(0)
2 1 1 2
μ0H (T)
0
0 10 20 30
T(K) –25
00 3 00 5 00 7
2 2 2
0 –50
0 10 20 30 40
q(deg)
Fig. 24 (a) Magnetic neutron diffraction pattern of minnesotaite showing the l/2 c-axis reflections
from the planar antiferromagnetic order. (b) A magnetic hysteresis loop measured at 4.2 K
exhibiting a spin flip in about 0.5 T [3]
amphibole grunerite has iron in all four sites. θp is positive, 67 K, but grunerite
nevertheless orders antiferromagnetically below the Néel temperature of 47 K with
a collinear structure where the ferromagnetic moments of each of the ribbons that
are magnetically aligned along the b axis order antiparallel to the moments of the
four neighboring ribbons. Crocidolite (blue asbestos) is a fibrous alkali amphibole
having Na in the outer M1 sites of the ribbon, charge compensated by Fe3+ in M2
sites. It orders antiferromagnetically at 30 K in a similar way to grunerite.
The ribbons in pyroxenes are two octahedra wide. Both sites are occupied
by ferrous iron in orthorhombic orthoferrosilite {Fe2+ 2 }[Si2 ]O6 . The exchange is
predominantly ferromagnetic with θp = 27 K, but the magnetic structure below the
17 Magnetic Oxides and Other Compounds 901
Fig. 26 Metal site occupancy in silicates: (a) trioctahedral sheet and (b) ordered and (c)
disordered dioctahedral sheets, (d) amphibole, (e) pyroxene, and (f) ilvaite
normally to be expected (Fig. 2a). A common feature of the iron-rich phases is that
nonmagnetic cations are generally present on some of the sites, leading to broadened
magnetic ordering transitions. The forsterite-fayalaite (Mg1-x Fex )2 SiO4 series is a
good example. There is no magnetic order below the percolation threshold xp , but
with increasing x, the Néel temperature increases linearly up to the fayalite value of
65 K. (Tables 30 and 31).
17 Magnetic Oxides and Other Compounds 903
Carbonates, Phosphates
Carbonates, like silicates, may order magnetically at low temperature. Two exam-
ples, each with the calcite structure, are siderite FeCO3 and rhodochrosite MnCO3
with Néel temperatures of 38 and 24 K, respectively. The manganese carbonate
was one of the first antiferromagnets where spin canting due to the Dzyaloshinskii-
Moriya interaction was identified, and there is a very sharp susceptibility peak at
the Néel temperature [40, 73]. The ferrous carbonate, vivianite Fe3 (PO4 )2 .8H2 O,
orders in a noncollinear antiferromagnetic structure at 9 K. The different signatures
of the three minerals in their low-temperature susceptibility may allow them to be
quantified in small concentrations in sedimentary mixtures [43].
The ability to deposit large-area oxide and metal thin films that are smooth to
within atomic dimensions has transformed research in magnetism and made spin
electronics possible [113]. Here we discuss magnetism of oxide thin films, bilayers,
multilayers, and superlattices, especially surface and interface effects. Nonmagnetic
oxide films play essential roles as tunnel barriers, cap, and buffer layers. Figure 28
illustrates these different structures.
Epitaxial magnetic oxide thin films are best grown on nonmagnetic oxide crystal
substrates with similar lattice parameters. The crystal surface frequently presents
Fig. 28 Oxide thin film structures on a substrate. (a) Capped film, (b) pinned tunnel junction,
(c) bilayer, (d) multilayer
904 J. M. D. Coey
square, cubic, or hexagonal oxygen packing, and epitaxial growth usually requires
a lattice mismatch of less than 2%. Strain is relaxed over a length scale of order
100 nm in the film thickness. Certain properties of magnetic thin films, such as
their crystal and electronic structure, magnetic structure, and magnetocrystalline
anisotropy, may be very sensitive to substrate-induced strain, which opens many
possibilities for strain engineering. For example, a film of cubic ferromagnet may
become tetragonal and acquire perpendicular magnetic anisotropy when deposited
on a mismatched substrate where it is subject to biaxial strain. There is a wide
choice of oxide substrates, including functional ones – conducting, ferroelectric, or
piezoelectric – which can be used to tune the magnetism of the thin film. A list of
substrates and their magnetic susceptibility is given in Table 32.
Since the thickness of the substrate, usually 0.3–1.0 mm, is much greater than
the thickness of the oxide film grown on it, which is typically tens or hundreds of
nm, it is particularly important to be aware of the influence of magnetic impurities
in the substrate, as well as interface defects. MgO, for example, often includes
Fe2+ impurities that produce a strong Curie-law upturn in the susceptibility at low
temperature. Small magnetic moments of order 10−8 Am2 that saturate in an applied
field of approximately 100 kAm−1 frequently appear in 5 × 5 mm2 oxide substrates
at room temperature [60]; they may be due to ferromagnetic impurities introduced
in the polishing process or else somehow associated with oxygen vacancies at the
surface [31].
Epitaxy is less important for oxide cap layers that serve to protect a thin film layer
or heterostructure. Buffer layers can be used to improve the lattice match between
a substrate and the thin film to be grown on it. Since silicon wafers are available in
much larger diameters than single-crystal oxides such as SrTiO3 , it is interesting for
oxide electronics to find buffer layers that will enable large-area oxide thin films to
be grown on silicon. CeO2 is a suitable candidate. Buffer layers may also serve as
diffusion barriers.
The technology to fabricate device-quality oxide thin films advanced rapidly after
the discovery of the cuprate high-temperature superconductors in 1986. The boom
in high Tsc research was facilitated by the development of the pulsed laser deposition
(PLD) method to prepare laboratory-scale samples of oxide thin films by ablating an
oxide target with repeated femtosecond pulses of UV laser radiation [37]. A further
spur to develop wafer-scale oxide thin films with sub-nanometer scale surface
roughness was the need for reliable and reproducible tunnel barriers in sensors and
memory elements based on tunnel magnetoresistance (Fig. 28b). A brief account of
the main methods for making oxide thin films follows.
Oxide thin films can be prepared by physical or chemical methods. Physical
deposition methods involve a source of material separated by a distance d from the
substrate, which is often heated in the range 400–1000 ◦ C to facilitate film growth
[98]. Several variants are indicated in Fig. 29. At low pressure, the atomic species
Table 32 Single-crystal substrates for oxide thin films
OxideAbbreviation Plane Space group Lattice parameter (pm) Susceptibility10−6 Comments
MgO 100 Fm3m 421 −18 Includes paramagnetic Fe2+
110 impurities
111
NaCl 100 Fm3m 564 −14 Soluble in water
Al2 O3 001 R3c 476: 1300 −18
Sapphire 100
SrTiO3 STO 100 Pm3m 391 −7 ε = 300
SrTiO3 :Nb 100 Electrical conductor
LaAlO3 LAO 100 Pm3m 379 −18
(La,Sr)(Al,ta)O3 100 Pm3m 387 −17 Stable
17 Magnetic Oxides and Other Compounds
LSAT 111
MgAl2 O4 MAO 100 Fd3m 808 −15
BaTiO3 BTO 100 P4mm 399, 404 Ferroelectric; P = 0.26 cm−2
Y3 Al5 O12 YAG 100 Ia3d 1200
Gd3 Ga5 O12 GGG 100 Ia3d 1238
TiO2 001 P42 /mnm 459; 296 4
100
ZrO2 :Y YSZ 100 Fm3m 512 Piezoelectric
ZnO 001 P63 mc 325;521 −24
SiO2 100 P33 21 491;541 −18
Si 100 Fd3m 542 −4 Large wafers available; buffered
111 with CeO2
GaAs 001 F43m 565
905
906 J. M. D. Coey
Fig. 29 Methods for preparing thin films by a vapor or plasma condensing on a substrate:
(a) thermal evaporation, (b) e-beam evaporation, (c) pulsed-laser deposition, and (d) sputtering
from the source arrive at the substrate without collision, but at higher pressure
they are thermalized by collision with the gas atoms in the chamber. The room-
temperature mean free path of the atom λ is approximately 6/P, where λ is measured
in millimeters and P is the chamber pressure in pascals. In situ measurement of the
thicknesses of the thin films may be achieved by optical reflectometry or with a
quartz crystal monitor.
Thermal Evaporation
Resistive evaporation is a commonly used vacuum deposition process in which
electrical energy is used to heat a boat containing the charge or a filament which
heats the material to be deposited to the point of evaporation [55]. The vapor
condenses in the form of thin film on the cold substrate surface, at a rate that
depends on the inverse square of the source-target distance. The method is restricted
to materials with moderately low melting points to avoid contamination by the
boat, which is usually made of graphite, molybdenum, or tungsten. Electron beam
(e-beam) evaporation is a variant that is used both in research and on an industrial
scale for thin film coatings. Here a target of the material to be evaporated is
bombarded with a beam of high-energy electrons. The target is placed directly in
a water-cooled crucible or else in a crucible liner made from a material such as
graphite or tungsten with a high melting point that does not alloy with it. The melting
is localized, and the evaporated target material is transported to a substrate. E-beam
evaporation can also be used in a reactive environment to make oxide films by
evaporating a metal target in the presence of oxygen that is either released directly
into the evaporation chamber or else introduced via a low-energy divergent-beam
plasma ion source directed at the substrate. This technique, known as ion-beam-
assisted deposition (IBAD), produces high-quality stoichiometric films. Very high
17 Magnetic Oxides and Other Compounds 907
Sputtering
Sputtering, the preferred thin film vacuum deposition technique in industry, is
widely used in research laboratories as well. Sputtered films exhibit excellent,
reproducibility, uniformity, density, purity, and adhesion. It is possible to make
oxides, nitrites, and other compounds of precise composition by reactive sputtering
from metal targets [98]. In dc sputtering, the substrates are placed in a high vacuum
chamber that is pumped down before a low pressure (0.05–1 Pa) of the process gas,
usually argon, is introduced. Sputtering starts when a negative potential of a few
hundred volts is applied to a target of the material to be deposited, causing a plasma
or glow discharge. Positively charged Ar+ ions generated in the plasma collide with
the negatively biased target. The momentum transfer ejects atomic-scale particles
from the target, which traverse the chamber and are deposited as a thin film on the
surface of the substrate. A magnetic field is usually created near the target surface by
an array of permanent magnets, known as a magnetron, which serve to improve the
ionization efficiency. Oxygen can be mixed with the argon sputtering gas to prepare
oxides from metal targets. Alternatively, oxide or other insulating films can be made
directly by radiofrequency sputtering using an rf power supply that usually operates
at 13.56 MHz. For part of the cycle, Ar ions bombard the target; while for the rest of
the cycle, electrons neutralize the buildup of positive charge. Electrons also ionize
the argon to create the plasma. An argon pressure of 0.02 Pa is usually sufficient to
maintain the radiofrequency discharge.
Most sputtering systems have multiple targets and power supplies, which permits
fabrication of the complex thin film stacks used for spin electronic devices. Double
facing targets used for off-axis deposition are particularly suitable for making
uniform, high-quality oxide thin films.
908 J. M. D. Coey
conformal films to be deposited on very high aspect ratio structures. ALD deposits
films using pulses of gas that produce one atomic layer at a time. Within fairly
wide process windows, the deposited film thickness only depends on the number of
deposition cycles, providing extremely high uniformity and thickness control. ALD
reactions are typically carried out in the 200–400◦ C range. In particular, ALD is
used in the semiconductor industry for high-k gate dielectrics (HfO2 , ZrO2 ), but
with appropriate organometallic precursors, it has potential for ultrathin magnetic
oxide films.
Wet chemical methods to produce oxide thin films include dip coating and spray
pyrolysis.
An important question is, how do the properties of a magnetic thin film differ from
those of the bulk material? There are obvious differences. Usually, the surfaces
of bulk material are neglected, and it is regarded as an infinite three-dimensional
continuum. The thin film is different. It is quasi two-dimensional with two quite
different surfaces – a lower one of effective thickness al in contact with the substrate
or buffer and an upper one of thickness au in contact with vacuum, the cap layer or
ambient air; al and au may be of order a nanometer, so if the total film thickness
is t, the bulk-like fraction, (t − al − au )/t, is a number that may be substantially
less than 1 or even zero for very thin films. The problem is aggravated by our
limited understanding of the real structure of the upper or lower oxide film surfaces,
especially the upper one in ambient conditions, where the classical physical methods
of surface characterization in UHV are not relevant. A monolayer of an adsorbed gas
forms in a matter of minutes, even in a vacuum of 10−5 Pa.
Surfaces of the principal iron oxides magnetite, hematite, maghemite, and
wüstite have been intensively investigated by surface scientists, and there is a
comprehensive review of their work by Parkinson [83]. They are of interest not only
for magnetism but also for catalysis, photoelectrochemistry, and nanomedicine. The
clean surfaces tend to reflect the defect chemistry of the bulk, with a close-packed
oxygen lattice maintained up to the edge and subsurface cation vacancies. Best
studied is the (100) surface of magnetite, which can readily be prepared in UHV
with a B-site iron/oxygen termination. The reconstructed surface is accompanied
by two subsurface octahedral cation vacancies and a tetrahedral interstitial, giving
a composition Fe11 O16 in the first unit cell. While bulk magnetite is half-metallic,
with only minority-spin t2g electrons at the Fermi level, there is little evidence for
complete spin polarization at the surfaces of magnetite based thin film structures.
The problems are less acute for metal thin films, but even there effects of
reduced bandwidth for the surface atoms with fewer nearest neighbours than the
bulk, reduced symmetry which can lead to strong perpendicular surface magnetic
anisotropy that scales with surface area and magnetic excitations with a two-
dimensional character may all strongly modify the magnetic ordering temperature,
and even alter the nature of the magnetic order. The nonmagnetic metals vanadium,
910 J. M. D. Coey
Dead Layers
By measuring the magnetization Ms of an oxide film as a function of film thickness
t, and plotting Ms t as a function of t, an extrapolated dead layer t* thickness can
be deduced. Some data for (001) (La0.7 Sr0.3 )MnO3 films on different substrates
are shown in Fig. 30 [88]. This procedure does not distinguish between al and au .
Furthermore, the analysis should take account of any weak ferromagnetic signal
persisting at high temperatures that arises from the surface of the substrate. It
can be separated by measurements above the Curie temperature of the manganite.
This d-zero magnetism arising at the oxide surface has been studied in different
SrTiO3 substrates [31], but the explanation is an open question [20]. The dead layer
thicknesses on LSAT, STO, and LAO are 0.8 nm, 1.5 nm, and 3.0 nm, respectively.
It remains to be established whether the dead layer is at the manganite surface or
interface (or both) and what is the relative importance of substrate polarity and
epitaxial strain.
17 Magnetic Oxides and Other Compounds 911
(Mx N1−x ) Oη ,
with x 0.1. From the discussion of percolation in Fig. 2, and the distribution of
magnetic ordering temperatures in Fig. 10, we would not anticipate any long-range
magnetic order in such a material when x is below the percolation threshold xp ,
which is approximately 2/Zc , where Zc is the cation-cation coordination number;
for example Zc is 12 for ZnO and 10 for TiO2 (rutile). Instead, we anticipate a
paramagnetic response reflecting the distribution of isolated ions, nearest-neighbor
pairs, and a few larger clusters, as illustrated in Fig. 2b). The dimers and clusters
are expected to couple antiferromagnetically, with a net moment for odd-membered
clusters. The paramagnetic response can be modeled approximately as a sum of
Curie and Curie-Weiss terms:
χ = C1 /T + C2 / (T–θ ) (9)
where C1 and C2 are Curie constants and θ is negative with magnitude <100 K,
representing the strength of a single antiferromagnetic exchange bond. This pre-
dicted paramagnetic behavior is found in well-crystallized bulk samples such as in
Co-doped ZnO crystals where the Co2+ substitutes for Zn on tetrahedral sites. The
Co-O-Co superexchange is antiferromagnetic.
It turns out that thin films of these oxides behave differently [21]. Following
a 2001 paper by Matsumoto et al. [70] on thin films of Co-doped anatase TiO2
produced by PLD, numerous reports appeared of ferromagnetic-like behavior in thin
films and nanocrystalline samples of dilute magnetic oxides. Some representative
results are shown in Fig. 31. Remarkably, the ferromagnetic-like behaviour was
observed at room temperature, and the corresponding Curie temperature should
912 J. M. D. Coey
Fig. 31 Some representative magnetization curves of thin film of dilute magnetic oxides [29]
be >400 K. Table 32 collects some of the early results [22]. The films may be
semiconducting (ZnO), insulating (TiO2 ), or metallic ((La,Sr)TiO3 ), and the effect
is seen for a variety of 3d cations – and even with nonmagnetic dopants such as
Sc3+ in ZnO.
At first these materials were believed to be dilute magnetic semiconductors
(DMS), where the 3d ions order ferromagnetically under the influence of long-range
exchange interactions. The thin films were thought to resemble (Ga1-x Mnx )As,
where homogeneous ferromagnetic ordering of Mn2+ ions, which occupy a level
just below the top of the As 4p valence band, occurs with a value of TC as high as
170 K for doping at the solubility limit x = 0.07 [59].
The possibility of high-temperature ferromagnetism in ZnO doped with 5% of
manganese due to a mechanism similar to that in (Ga,Mn)As was suggested by
Dietl in 2000 [36]. The ferromagnetism was mediated by spin-polarized holes in the
oxygen p band. However, ZnO, the most studied matrix [80], is exceptional insofar
as all the cations are in tetrahedral coordination and the bonding has significant
covalent character with mobile 2p holes Otherwise, oxides do not usually make good
semiconductors because the carriers tend to be trapped and form small polarons
because of their Coulomb interaction with the oxygen anions. This is the reasdon
why many off-stoichiometric oxides remain insulating.
The emerging consensus is that these dilute magnetic oxides are not dilute
magnetic semiconductors [21]. They are magnetically inhomogeneous, and only
a small fraction (of order 1% in thin films and 10 ppm in nanoparticles) of the
volume could be ferromagnetically ordered. The magnetic moment scales with
the film area rather than its volume, with values of order 10–20 μB per square
nm. The practice of relating the moment to the dopant content leads occasionally
17 Magnetic Oxides and Other Compounds 913
Table 33 Some reports of ferromagnetic oxide thin films with TC above room temperature [22]
Material Eg (eV) Substitutions Moment (μB ) per 3d ion TC (K)
TiO2 3.2 V – 5% 4.2 >400
Co – 7% 0.3 >300
Co – 1–2% 1.4 >650
Fe – 2% 2.4 300
SnO2 3.5 Fe – 5% 1.8 610
Co – 5% 7.5 650
ZnO 3.3 V – 15% 0.5 >350
Mn– 2.2% 0.16 >300
Fe5%,Cu1% 0.75 550
Co – 10% 2.0 280–300
Ni – 0.9% 0.06 >300
CeO2 2.0 Co – 3% 5.8 >750
In2 O3 3.7 Fe – 5% 1.4 >600
Cr – 2% 1.5 900
ITO 3.5 Mn – 5% 0.8 >400
(La,Sr)TiO3 – Co – 1.5% 2.5 550
to unreasonable moments per 3d ion (Table 33). The magnetism [62] (when it
is not attributable to experimental artifacts or impurity phases such as embedded
nanoclusters of metallic cobalt) is closely associated with lattice defects in the
material. Furthermore, atomic-scale probes such as XMCD [102] and Mössbauer
spectroscopy [28] failed to reveal any magnetic order of the 3d dopants at room
temperature. In dilute Co-doped ZnO films, for example, no evidence could be found
for ferromagnetic interactions among the dopants [76], and even in concentrated
films with x = 0.6, the antiferromagnetic ordering temperature does not exceed
20 K [77].
What is remarkable about the magnetization curves is that they are essentially
anhysteretic and exhibit little or no temperature dependence between 4 K and 400 K.
Curves obtained at different temperatures often superpose after correcting the data
for a diamagnetic or paramagnetic slope arising from the substrate or from the
oxide film itself. The lack of temperature dependence excludes any possibility of
superparamagnetism, for which the magnetization curves should superpose when
M/Ms is plotted versus (H/T).
The absence of hysteresis is a further argument against uniform magnetization, as
would be expected for a DMS. The small net magnetization values Ms ≈ 10 kA m−1
inferred for thin films should lead to an appreciable anisotropy field, with a uniaxial
anisotropy constant due to intrinsic crystal field or substrate-induced strain, and
therefore produce coercivity at low temperature. Another serious problem is the high
value of the Curie temperature. Relatively few insulating oxides are ferromagnetic
(Fig. 10); they usually order antiferromagnetically or ferrimagnetically on account
of the antiferromagnetic superexchange. Almost none order magnetically above
1000 K. It is unreasonable to expect oxide films with just 5% of magnetic ions to
have a Curie temperature exceeding 100 K. The magnetic energy density varies as x
914 J. M. D. Coey
√
or x, so high Curie temperatures could not be achieved with uniformly magnetized
material.
A defect-related origin rather than a magnetic dopant-related origin of the fer-
romagnetism is supported by its observation in some samples of undoped material,
including films of HfO2 , ZnO, TiO2 , and In2 O3 . This phenomenon is known as
d0 magnetism [20], and it reinforces the idea that while defects are necessary, 3d
dopants are not essential. It is a challenge to associate the magnetism, which is often
not quantitatively reproducible, with a specific surface, interface, or grain-boundary
defects. Extended defects may be a more likely source of percolating magnetism
than point defects. As regards the origin of d-zero magnetism two quite different
ideas are in contention.
One is to model the defects, probably oxygen vacancies, in terms of a narrow,
spin-split defect-related impurity band. This can lead to a high Curie temperature
since spin-wave excitations are suppressed in the half-metallic band. It is a Stoner
model of the magnetism, involving a small fraction of the sample volume. The
transition-metal dopants may nonetheless play a role when they exist in different
charge states, providing a reservoir of charge for the impurity band to ensure filling
to the point where the Stoner criterion is satisfied. This model is known as charge-
transfer ferromagnetism [28].
An alternative view is that there is actually no spin ferromagnetism in these
oxide films. The reversible nonlinear response to the magnetic field is really an
unusual form of giant orbital paramagnetism, which has been related to the coherent
response of quasi-two-dimensional electron systems to fluctuations of the vacuum
electromagnetic field [32]. The definitive explanation remains an open question [20].
Ultrathin nonmagnetic oxide barriers play an important role in spin electronics [7],
which has become the most innovative area of applied magnetism in the twenty-
first century [113]. Early tunnel barriers were made of amorphous aluminum oxide,
but the discovery that crystalline (100) MgO layers act as directional spin filters
when grown on a (100) film of αFe, or a body-centered cubic Fe-Co alloy [82, 115],
led to magnetic tunnel junctions (Fig. 28b) with a magnetoresistance in excess of
200%, which made them attractive both as magnetic sensors and memory or logic
elements. Other nonmagnetic oxide tunnel barriers, such as spinel MgAl2 O4 , have
been developed, but none rivals the efficiency of MgO.
Thin films of magnetic oxides and sulfides such as ferromagnetic EuO or EuS
and ferrimagnetic CoFe2 O4 or NiFe2 O4 can serve as tunnel spin filters with a
nonmagnetic metal electrode, since the bandgap is different for minority- and
majority-spin electrons [41].
Spin electronics [113] has progressed from its initial emphasis on magnetore-
sistive sensors for magnetic recording [119] to the development of a competitive
nonvolatile magnetic memory and logic technology based on switching magnetic
17 Magnetic Oxides and Other Compounds 915
Oxide Interfaces
At interfaces between oxides, the three-dimensional symmetry of each oxide is
broken, and proximity effects may emerge [30]. Interfacial exchange can modify
the magnetic structure at the interface, if one or both of the oxides is magnetically
ordered. Exchange bias, for example, may be a consequence. When the electronic
structure of the two oxides differs, charge transfer may result in an interface with a
different magnetic structure or different transport properties [30, 106].
The interfaces between polar and nonpolar oxides are especially interesting.
Charged two-dimensional surfaces are unstable in nature unless there is nearby
916 J. M. D. Coey
compensating charge, because of the energy density ½ε0 E2 associated with the
uniform perpendicular electric field created in the surrounding space – an instability
known as the polar catastrophe. Inevitably some electronic or ionic reconstruction
must occur to resolve the problem.
A celebrated and much-studied example is the (100) interface between formally
nonpolar SrTiO3 and polar LaAlO3 [79]. Both are insulators, yet a conducting
two-dimensional electron gas (2DEG) forms just below the interface in the SrTiO3
provided the thickness of the LaAlO3 overlayer exceeds four unit cells. The electron
density and orbital character in the Ti dxy or dyz/zx bands can be modified by gating,
and there is evidence of inhomogeneous ferromagnetic order in the 2DEG at liquid
helium temperatures. Spin diffusion lengths can be on the order of a micron [106].
Spin Pumping
The technique of spin pumping has been developed to create spin currents perpen-
dicular to the interface between ferro- or ferrimagnetic and nonmagnetic layers. It is
related to the spin Hall effect, whereby a spin current is created perpendicular to a
thin film of a heavy metal such as Ta, W, or Pt by passing an electric current through
it. The spin current can modify the magnetic state of an adjacent ferromagnetic
layer. In spin pumping, Larmor precession in the magnetic layer is excited by
a radiofrequency magnetic field at a frequency determined by the ferromagnetic
resonance that depends on an applied field or the anisotropy field of the layer. In that
case, a rectified spin current is injected into the adjacent nonmagnetic layer, which
may be detected by the inverse spin Hall effect. For this to work well, a magnetic
material with very low damping is required, which makes yttrium-iron garnet the
preferred option. The quality of the interface and the oxygen stoichiometry of the
YIG are critical for efficient spin injection [114].
Magnonics
Magnonics is the magnetic transport, storage, and processing of information using
spin waves. See Chap. 6, “Spin Waves”. The rich physics of the linear and
nonlinear dynamics of multimode spin wave systems has been extensively inves-
tigated using yttrium-iron garnet strip lines [93]. The uniquely low damping in YIG
allows spin wave propagation to be observed over distances of up to a centimeter,
a thousand times longer than in a metal such as permalloy and far greater than
the spin diffusion lengths encountered in spin electronics. Magnons, like diffusive
spin currents, involve the transport of angular momentum, which in the case of
magnons is correlated precession of the localized spin moments on neighboring
sites. The key functions of propagation, storage, amplification, echo, and logic
have all been demonstrated. Magnonics has the advantage of low power dissipation
and may be combined with spin transfer torque to enable controlled generation
of magnons along well-defined propagation directions [57]. Disadvantages are the
large footprint of the devices (square microns) and the low charge ↔ magnon
conversion efficiency at the input and output.
17 Magnetic Oxides and Other Compounds 917
Conclusion
Acknowledgments The author is grateful to Science Foundation Ireland for continued support,
including contracts 10/IN.1/I3006, 13/ERC/I2561 and 16/IA/4534.
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922 J. M. D. Coey
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 926
Dilute Magnetic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 928
Dilute Magnetic Metals (DMMs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 928
p-Type Dilute Ferromagnetic Semiconductors (DFSs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 928
Other Dilute Ferromagnetic Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929
Dilute Magnetic Semiconductors (DMSs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929
Dilute Magnetic Topological Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 930
Heterogenous Magnetic Semiconductors and Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 930
Energy States of Magnetic Dopants in Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 931
Exchange Interactions Between Band and Localized Spins . . . . . . . . . . . . . . . . . . . . . . . . . . . 936
A. Bonanni
Institut für Halbleiter- und Festkörperphysik, Johannes Kepler University, Linz, Austria
e-mail: [email protected]
T. Dietl
International Research Centre MagTop, Institute of Physics, Polish Academy of Sciences,
Warsaw, Poland
WPI Advanced Institute for Materials Research, Tohoku University, Sendai, Japan
e-mail: [email protected]
H. Ohno ()
WPI Advanced Institute for Materials Research, Tohoku University, Sendai, Japan
Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication,
Tohoku University, Sendai, Japan
Center for Spintronics Integrated System, Tohoku University, Sendai, Japan
Center for Innovative Integrated Electronic Systems, Tohoku University, Sendai, Japan
Center for Science and Innovation in Spintronics (Core Research Cluster), Tohoku University,
Sendai, Japan
Center for Spintronics Research Network, Tohoku University, Sendai, Japan
e-mail: [email protected]
Abstract
List of Symbols
N0 Cation density
p Hole carrier concentration
P Spin polarization
P Probability distribution
Tf Spin-glass freezing temperature
u Periodic part of the Bloch function
Vkd Hybridization energy
V Matrix element of conduction band offset
W Matrix element of valence band offset
x Magnetic cation fractional content
α s-d exchange integral
β p-d exchange integral
ηq Fourier transform of magnetization
φ(z), ψ(r) Envelope functions
List of Abbreviations
RKKY Ruderman-Kittel-Kasuya-Yosida
SQUID Superconducting quantum interference device
TEM Transmission electron microscopy
TM Transition metal
TMR Tunneling magnetoresistance
VCA Virtual-crystal approximation
wz Wurtzite
XANES x-ray absorption near-edge structure
XAS x-ray absorption spectroscopy
XES x-ray emission spectroscopy
XRD x-ray diffraction
ZFC Zero-field cooled
zb Zinc-blende
Introduction
Dilute localized magnetic moments are usually associated with open d or f shells
of magnetic dopants but sometimes originate from nonmagnetic impurities and/or
lattice defects. The dilute systems attract considerable attention for a number of
reasons.
Firstly, even a minute concentration of uncoupled magnetic impurities can
change dramatically the transport and the optical characteristics. A relevant example
is the Kondo effect in metals ( Chap. 2, “Magnetic Exchange Interactions”)
used for the fabrication of efficient thermocouples at low temperatures. Another
is represented by intra-impurity optical excitations in semiconductors and oxides,
which dominate the optical properties in the spectral region below the fundamental
gap ( Chap. 3, “Anisotropy and Crystal Field”), a property exploited successfully
in stained glasses and broadband lasers [1].
Secondly, dilute systems bridge the physics and functionalities of semiconduc-
tors and magnetic materials. The existence of strong spin-dependent interactions
between bands and open magnetic shells, coexisting with spin-orbit interactions,
leads to giant magnetotransport and magnetooptical phenomena and opens the door
for spintronic functionalities, the control of magnetization and spin current by
light, strain, electric fields, and currents in both topologically trivial and nontrivial
systems.
Thirdly, the randomness in the distribution of interacting localized spins accounts
for novel magnetic properties, not encountered in chemically ordered crystals. More
specifically, dilute magnetic materials have gained the status of model systems for
assessing the nature of thermodynamic phase transformations in the presence of
spatial disorder, competing interactions, and frustration. Another appealing question
concerns quantum phase transformations in disordered systems and how localized
magnetism evolves into an itinerant or nonmagnetic ground state as a function of
the magnetic ion concentration.
Fourthly, materials science of dilute magnetic systems is surprisingly rich. It has
been increasingly clear that information about the nominal chemical composition is
rarely sufficient to account for the effective characteristics of these media. Actually,
to a large extent, their properties, including the nature of the magnetic ground
18 Dilute Magnetic Materials 927
state, depend on the way a given sample has been obtained. In particular, the
distribution of magnetic ions over the specimen volume (random vs nonuniform),
their incorporation into the lattice sites (substitutional vs interstitial), the resulting
spin configuration, and spin-spin interactions depend on the substrate employed,
growth conditions, co-doping, post-growth processing, surface reactions, and con-
tamination.
In this context the extensive use of nanocharacterization tools, such as syn-
chrotron radiation, microscopy, particle beam, and scanning probe methods, is
essential [2], as elaborated in Chaps. 25, “Magnetic Scattering,” and 24,
“Magnetic Imaging and Microscopy.” Together with more traditional techniques
of magnetic resonance ( Chap. 26, “Electron Paramagnetic and Ferromagnetic
Resonance”) and optical magnetospectroscopy ( Chap. 10, “Magneto-optics and
Laser-Induced Dynamics of Metallic Thin Films”), these tools not only visualize
the micromagnetic characteristics but also reveal the distribution of magnetization
and magnetic constituents at the nanoscale as well as determine properties of energy
states relevant to magnetism with ever-improving spatial, chemical, spin, spectral,
and more and more often time resolution. Results of such combined structural
and spectroscopic investigations are now broadly employed to substantiate the
interpretation of experimental findings and to benchmark theoretical modeling,
particularly in newly developed systems [3].
Another specific feature of dilute magnetic materials is the small magnitude
of the magnetization, which makes these systems sensitive to both contamination
by ferromagnetic (FM) nanoparticles [4, 5, 6, 7] and experimental artifacts in
SQUID measurements [8]. A related timely question concerns the origin of a
temperature-independent anhysteretic magnetic signal often observed in nominally
diamagnetic solids. The search for new physics, such as contribution from orbital
currents, is now accompanied by an extensive use of spatially resolved analytic
tools, examination of samples from a range of suppliers and processed in various
ways [9].
Considering different hosts and magnetic ordering, dilute magnetic materials can
be grouped into six classes, as outlined in section “Dilute Magnetic Materials”.
A more detailed discussion of various aspects of dilute systems, together with
examples of experimental and theoretical findings, is presented in sections “Energy
States of Magnetic Dopants in Solids”, “Exchange Interactions Between Band
and Localized Spins”, “Effects of sp-d(f ) Exchange Interactions”, “Dominant
Spin-Spin Interactions”, and “Magnetic Properties of Dilute Magnetic Materials”.
The key parameter characterizing dilute magnetic systems is the concentration
of magnetic ions x. We warn the readers that various conventions exist in literature.
Here, by x we understand the fractional cation content. For instance, x in the
case of Mn-doped cadmium arsenide is defined by (Cd1−x Mnx )3 As2 . Within this
√ dopants per√unit volume is xN0 , where the
definition, the concentration of magnetic
cation concentration N0 = 4/a03 , 4/( 3a 2 c), 12/( 3a 2 c), and 8/a03 for the zinc-
blende and rock-salt, wurtzite, tetradymite, and elemental diamond-structure dilute
magnetic semiconductors, respectively.
Another convention of interest concerns the description of exchange coupling.
Here, the exchange interaction between a pair of localized spins is expressed in the
928 A. Bonanni et al.
form Hij = −2Jij S i · S j , whereas the exchange interaction between a band carrier
and a localized spin is expressed as Hi = −Jsp−d(f ) s · S i .
freezing at Tf < 1 K for x < 0.1 (section “Spin-Glass Systems”). The use of magne-
tooptical and quantum transport techniques has revealed and quantified the influence
of sp–d coupling upon the exciton and Landau-level spectra, quantum Hall effect,
quantum localization, universal conductance fluctuations, and spin dynamics in
DMS systems of various dimensionality [43] (section “Effects of sp-d(f ) Exchange
Interactions”) as well as made it possible to demonstrate electrical spin injection
[44]. Conversely, the spin subsystem has been probed by the Faraday effect [45]
or quantum noise [46] (section “Spin-Glass Systems”). The physics of bound
magnetic polarons, a single electron interacting with spins localized within the
confining potential of impurities or quantum dots, has been advanced in DMSs
[47] (section “Bound Magnetic Polarons”). Most of the end-member compounds,
for instance, MnSe and EuTe, are antiferromagnets, which together with related
materials, like CuMnAs, constitute the building blocks for the emerging field of AF
spintronics [48]. Another ultimate limit of DMSs is represented by qubit systems
consisting of single magnetic ions in single quantum dots [49].
A good starting point for the description of dilute magnetic materials is the
Vonsovskii model, according to which the electron states can be divided into two
categories: (i) localized magnetic states, typically originating from open d or f
atomic shells, and (ii) extended band states built up of s, p, and also d atomic
orbitals. The understanding of how particular hosts perturb open shells of magnetic
impurities or defects is built on two pillars:
nism) [60] and (ii) the disappearance of localized magnetic moments for Vkd >
U, the case of many combinations of magnetic impurities and metallic hosts.
However, as long as localized magnetic moments survive in a given host, so that
the corresponding d states do not contribute to the Fermi volume, the presence of
hybridization does not invalidate the expectations of the crystal-field theory but
only modifies the magnitudes and microscopic origins of particular crystal-field
parameters.
ZnTe
ZnS
ZnSe
A(0/-)
CdTe
CdS
ZnO
CdSe
HgTe
2
Energy (eV)
D(0/+)
Sc Ti V Cr Mn Fe Co Ni Cu
0 1 2 3 4 5 6 7 8 9
d d d d d d d d d
-2
AlN
AlSb
AlAs
AlP
GaP
Ti V Cr Mn Fe Co
GaSb
GaAs
1 2 3 4 5 6
d d d d d d
GaN
2
InP
InSb
A(0/-)
Energy (eV)
InAs
InN
0 D(0/+)
-2
E (a) E (b)
HF HF
DOS DOS
E (c) E (d)
HF
HF
DOS DOS
Fig. 2 Schematic forms of density of states (DOS) if magnetic impurities introduce states
overlapping with a continuum of band states; (a) resonant state; (b) Abrikosov-Shul resonance
at the Fermi level εF appearing below the Kondo temperature; (c) Efros-Shklovskii Coulomb gap
at εF in the impurity DOS appearing if inhomogeneous broadening of the impurity band is larger
than lifetime broadening; (d) hybridization gap for Kondo insulators
18 Dilute Magnetic Materials 935
fragile coherence leading to the hybridization gap and in some cases to topological
states remains largely an open question.
Beyond the solubility limit: The stability of a particular alloy A1−x Bx against the
decomposition is described by the mixing energy, i.e., the alloy energy in respect to
the weighted energies of the end compounds:
E(x) = EAB − (1 − x)EA − xEB . (1)
The key feature of dilute magnetic materials is the existence of strong spin-
dependent coupling between magnetic ions and band carriers, which accounts for
the unique low-energy properties – transport, optical, and thermodynamic char-
acteristics of these systems. Neglecting non-scalar corrections that can appear for
magnetic ions with nonzero orbital momentum, L = 0, a one-electron Hamiltonian
that perturbs dynamics of the Bloch electrons assumes the Kondo form, HK =
i Hi , where
K
HiK = [V (r − R i ) − J (r − R i )s · S i ]. (2)
2 CdS
CdSe ZnSe GaN
ZnTe ZnS
1 CdTe GaAs
InAs
0
ZnO
-1 solid symbols: photoemission, XAS GaN
open symbols: magnetooptics
-2
0 10 20 30 40 50
Fig. 3 Compilation of experimentally determined energies of the p-d exchange interaction −N0 β
for various Mn-based DMSs as a function of the cation concentration N0 . Solid symbols denote
the values evaluated from photoemission and x-ray absorption spectra. The values shown by
open symbols were determined within the virtual-crystal and mean-field approximations (i.e.,
neglecting effects of strong coupling) from excitonic or band splittings in a magnetic field. Solid
line corresponds to a constant value of β across the DMS series. (The data collected by Dietl and
Ohno [23])
positive [the case of Zn1−x Crx Se [78]]. These findings are supported by theoretical
considerations [73, 74].
It should be emphasized that the role of hybridization depends crucially on the
symmetry of band states and the parity of the localized state. The description of
carrier-impurity interactions had to be reconsidered entirely in rock-salt DMSs, such
as (Pb,Mn)Te [72], as well as when rare-earth atoms are involved, as in (Pb,Eu)Se
[72].
Finally, we note that appropriately far away from the band extremum, the kp
method [79] ceases to work and, additionally, the term exp(ikr) in the carrier wave
function generates additional hybridization with the open magnetic shells.
Hav = x[Vs (r − R j ) − J (r − R j )s · S], (3)
j
where now j runs over all atoms in the sublattice containing magnetic ions (typically
the cation sublattice) and S is a thermodynamic average value of spin operators
Si . In terms of S, macroscopic spin magnetization M o (T , H ) = −g0 μB xN0 S,
where g0 = 2.0. In the case of impurities with nonzero orbital momentum L (e.g.,
the rare-earth case [80]), M o (T , H ) = −gJ μB xN0 J , and S = (gJ − 1)J
( Chap. 3, “Anisotropy and Crystal Field”).
The above approach is suitable for describing the influence of magnetic impu-
rities onto the spin-resolved band structure under two conditions: (i) there is no
correlation in the distribution of magnetic ions, as the presence of any superstructure
would lower point symmetry; (ii) the total potential introduced by a single impurity
is too weak to give rise to bound states, so that the effect of HK on extended states
can be treated perturbatively (weak coupling limit).
Within a first-order perturbation theory and in the spirit of the multiband
effective mass approximation [79, 41], the effect of Hav is described by matrix
elements ui |Vs |ui and ui |J |ui , where ui are periodic Kohn-Luttinger amplitudes
corresponding to bands at the relevant band extremum. In the case of substitutional
magnetic impurities in zinc-blende DMSs, for which typically bands with Γ6 , Γ7 ,
and Γ8 symmetries at k = 0 should be taken into account, there are four relevant
matrix elements: V = uc |Vs |uc and α = uc |J |uc ; W = uv |Vs |uv and
β = uv |J |uv involve s-type (uc ) and p-type (uv ) periodic parts of the Bloch
wave functions at k = 0, respectively. This formalism can be extended into low-
dimensional nanostructures and topological materials, particularly by mapping the
multiband effective mass approach onto a multiorbital tight-binding approximation
[81, 82].
In general, due to kp coupling between bands and the spin-orbit interaction, the
impurity-induced shift and spin-splitting of bands depend in a complex way on k,
M 0 , and the angle between them. However, at k = 0 this shift is xN0 V and xN0 W
for the Γ6 and Γ8 band, respectively, whereas the corresponding splitting is h̄ωs =
αMo /gμB for the Γ6 band and h̄ωs(h) = βMo /gμB for the heavy-hole Γ8 band at
k = 0. For x = 0.05, N0 β = −1 eV (see Fig. 3), and saturated spins S = 5/2,
(h)
|h̄ωs | = 0.125 eV.
A combination of the MFA and the effective mass formalism has been success-
fully applied to describe spin-splittings of bands and excitonic spectra in bulk,
films, and various dimensionality quantum structures of DMSs as well as spin-
splittings of Landau levels in these systems as a function of temperature and a
magnetic field [41, 42, 43, 83]. Such studies have provided quantitative information
on the magnitudes of sp–d(f ) exchange integrals in various families of DMSs;
some examples are collected in Fig. 3. The VCA and MFA formalism can readily
be employed to assess spin-splittings of boundary states specific to topological
materials [84, 51].
When the relevant physics involves length scales greater than an average distance
between magnetic ions (see Chap. 7, “Micromagnetism”), it is convenient to work
940 A. Bonanni et al.
If the local perturbation of the crystal potential introduced by a single impurity HiK
is strong enough to bind a carrier even in the absence of a Coulomb potential, VCA
and MFA do not describe adequately the influence of magnetic doping on the band
states. This is particularly the case for nitrides and oxides, where a relatively short
bond length results in a sizable p–d hybridization. In this strong coupling case, the
spectral density of states Asz (ω) was determined by a non-perturbative generalized
alloy theory for noninteracting Heisenberg spins. A maximum of Asz (ω) provides
the position of the valence band top (if holes can be trapped) for particular spin
orientations in respect to magnetization Mz (T , H ) of localized spins at given values
of the integrals W and β as well as of the width of the potential well, which
controls the binding ability of the neutral magnetic impurity [86]. This approach
demonstrates that both the band shift and splitting can even assume an opposite sign
to that expected within the VCA and MFA, as extended states are pushed away from
the impurity, if the spectrum contains a bound state for a given spin orientation. As
shown in Fig. 3, the values of β determined from excitonic splittings neglecting this
effect appear as anomalous and do not follow chemical trends in the case of nitrides
and oxides.
18 Dilute Magnetic Materials 941
enter the formulae for τsi via the fluctuation-dissipation theorem. The term in
square brackets in Eq. 6 describes the effect of chemical disorder (inhomogeneous
broadening). For spherical bands and in the 3D case, the density of states (DOS)
ρ(ε) = m∗ k(ε)/π 2 h̄2 ; for a single electric subband in 2D systems, k(ε) should be
replaced by π/L̃W , where the participation length
L̃W = 1/ dz|φ(z)|4 . (8)
Here, φ(z) is the envelope function describing the carrier confinement, and the
integration extends over the region where the magnetic ions reside.
In the vicinity of the critical temperature for magnetic ordering, where χ tends
to diverge, several additional effects have to be considered in evaluating τsi (T ),
including the q dependence of χ , screening of magnetization fluctuations by carrier
redistribution, and finite quantum coherence length [92]. A careful description of
the pertinent effects will be essential in order to explain the behavior of resistance
and its temperature derivative at criticality [93].
Since the exchange part of Hsc breaks spin rotation symmetry, spin-disorder
scattering, together with spin-orbit effects (section “Interplay of sp–d(f ) Exchange
Interactions and Spin-Orbit Coupling”), accounts for carrier spin relaxation in
magnetic systems as well as controls the magnitude of quantum interference
effects underlying Anderson-Mott localization and mesoscopic transport phe-
nomena (section “Quantum Localization and Mesoscopic Phenomena: Colossal
Magnetoresistance”).
α
s−d = | drM(r)|ψ(r)|2 |, (9)
g0 μB
where α is the s–d exchange integral and ψ(r) is the electron envelope function.
Hence, in the presence of a collinear magnetic field B and an average magnetization
M 0 of bath spins S in the absence of donor electrons, assumes the form
α
= g ∗ μB B + (M 0 + bq ηq ). (10)
g0 μB q
Here g ∗ is the electron effective Landé factor; bq and ηq are Fourier components
of |ψ(r)|2 and of bath magnetization fluctuations M(r) − M 0 , respectively. If the
electron localization length is much longer than an average distance between the
bath spins, the summation over q can be extended to infinity, but otherwise an
appropriate cutoff qmax should be implemented.
Except in the immediate vicinity of the spin ordering temperature, the probability
distribution of ηq is, to a good approximation, Gaussian for any mixed state that
can be described by spin temperature with variance, according to the fluctuation-
dissipation theorem, determined by an appropriate integral over ω of the imaginary
part of χq (ω). Since is linear in ηq , the central limit theorem implies that the
probability distribution of in the absence of the electron, PS (), is also Gaussian:
α
0 = g ∗ μB B + Mo , (12)
g0 μB
2
α
2
σ(⊥) = kB T χ̄(⊥)q |bq |2 /μ0 . (13)
g0 μB q
944 A. Bonanni et al.
If energies of bath magnetic excitations are smaller than the thermal energy kB T
and their q-dependencies are irrelevant, then χ̄(⊥)q (T , H ) are given in Eq. 7. Far
from magnetization saturation, χ⊥ = χ = χ .
By adding the free energy of the electron, so that
P() = Z −1 2 cosh(
/2kB T )PS (), (14)
the BMP effects in thermal equilibrium are taken into account with the partition
function Z being determined by the probability normalization condition. Accord-
ingly, the BMP free energy becomes F = −kB T ln(Z/ZS ), from which the
BMP contribution to magnetization and specific heat is obtained. Furthermore, by
minimizing F in respect to the BMP localization radius, self-trapping effects can
be assessed [95]. Integrating P() over directions, one obtains the probability
distribution of the electron spin-splitting
that can be directly probed by a
variety of optical and magnetic resonance experiments. In particular, theoretically
determined P(
) describes quantitatively the shape, width, and position of the
spin-flip Raman scattering line in a number of n-type DMSs [96]. Additional
inhomogeneous spin-splitting broadening caused by statistical fluctuations of com-
position x (chemical disorder), leading to different
0 values in particular BMPs,
can also be incorporated into the theory [42].
In a paramagnetic phase and in the absence of an external magnetic field, P(
)
attains a maximum at
= 2εp and (8kB T εp )1/2 for εp kB T and εp
kB T ,
respectively, where the polaron energy
α 2 χ (T )
εp (T ) = , (15)
32πg02 μ2B aB3
where aB is an effective Bohr radius of the relevant carrier localized state. As seen,
spontaneous spin-splitting appears even in the paramagnetic phase. It is dominated
by the polaron effect, i.e., by bath spin polarization produced by the carrier spin
at low temperatures, whereas thermodynamic magnetization fluctuations lead to
a molecular field whose contribution to
takes over in the high-temperature
regime.
Since non-scalar spin-spin interactions, such as Dzyaloshinskii-Moriya coupling,
break spin momentum conservation, the BMP formation time is of the order of T2(S)
of the bath spins. Hence, up to a time scale of T1(S) , adiabatic rather than isothermal
magnetic susceptibilities describe energetics of the system [97]. Furthermore, by
solving the quantum Liouville equation with the Hamiltonian Hs = ŝ · and
averaging the resulting spin-density matrix with P(), one obtains information on
dephasing of the electron spin for t < T2 at arbitrary values of M0 (T , H ) and
magnetic field B [47].
18 Dilute Magnetic Materials 945
to predict the anomalous quantum Hall effect in topological materials [84, 51]
(sections “p–d Zener Model” and “Dilute Ferromagnetic Insulators and Topological
Insulators”). The incorporation of spin-orbit effects into theories of spin-disorder
scattering, magnetic polarons, strong coupling, and quantum localization, particu-
larly in the case of overlapping p-type subbands, is technically more demanding.
Dipole-Dipole Interactions
Dipolar interactions are ubiquitous in nature and due to their long-range may domi-
nate other types of interactions in the limit of low magnetic impurity concentrations,
particularly in magnetic insulators with rare earth impurities, where competing
exchange coupling decays rapidly with spin-spin distance. Due to randomness, the
resulting ground state is a spin glass, as discussed in section “Spin-Glass Systems”.
100
ZnS
ZnTe ZnSe
Exchange energy - JNN (K)
CdSe
10 CdTe
CdS Mn2 ZnO
HgSe
HgTe
PbSe
triangles: Co
1
squares: Mn
PbTe circles: Eu
PbS
0.1
10 20 30 40
Cation concentration N0 (nm )
-3
Superexchange
This indirect coupling between localized spins exists in virtually all compounds
with localized spins and typically dominates in nonmetallic materials containing
transition metals (TMs). The superexchange ( Chap, 2, “Magnetic Exchange
Interactions”) proceeds via hybridization of magnetic levels with orbitals of atoms
located between the spins in question, usually, but not always, p orbitals of relevant
anions. For this indirect interaction, within the lowest-order perturbation theory
in the hybridization, the interaction Hamiltonian is bilinear, Hij = −2S i Jˆij S j .
Components of the exchange tensor Jˆij are proportional to |Vkd(f ) |4 and decay fast
with the distance rij corresponding to NN, NNN, NNNN, ... spin pairs, typically
on average exponentially, though not necessarily monotonically, as the direction of
r ij in respect to the orientation of molecular orbitals is relevant, too. The scalar
(isotropic) part of Jˆij [i.e., Jij I , where I is the identity (unit) matrix] usually
dominates though the remaining components brought about by spin-orbit coupling,
particularly the Dzyaloshinskii-Moriya antisymmetric term, Hij DM = −2D DM ·(S ×
i
S j ), play often an important role in media with inversion asymmetry, also associated
948 A. Bonanni et al.
with proximity to an interface. In general, group theory determines the form, if not
the magnitude, of Jˆij for particular spin pairs and hosts.
RKKY Interaction
As shown by Ruderman, Kittel, Kasuya, and Yosida, under the presence of a sp–
d(f ) exchange interaction, a localized spin S i generates a spin polarization of the
carrier sea that affects another localized spin S j ( Chap, 2, “Magnetic Exchange
Interactions”). Since spin polarization shows Friedel oscillations (associated with
the Kohn anomaly due to the Fermi energy cutoff), the sign of resulting bilinear
coupling energy Jij , as given by the lowest-order perturbation theory in Jsp−d(f ) ,
changes between FM and AF as a function of rij with period λF /2, where λF is the
de Broglie wavelength of carriers at εF ; the period is short in metals but substantially
longer than an average distance between spins in doped semiconductors, where
carrier density typically n < xN0 . The interaction amplitude is proportional to
(Jsp−d(f ) /N0 )2 and the density of carrier states at εF and decays as rij−d , where d
is the DOS dimensionality. Similarly to superexchange, spin-orbit interactions give
rise to the presence of non-scalar terms in spin-spin coupling.
Bloembergen-Rowland Mechanism
This mechanism takes into account the presence of spin polarization of occupied
bands generated by localized spins. Since here the perturbation theory involves
interband matrix elements, this coupling is expected to be particularly strong in the
inverted band structure cases of topological materials, such as (Hg,Mn)Te [114] and
(Bi,Cr)2 Se3 [51]. In the case of (Hg,Mn)Te and related alloys and to the lowest order
in perturbation theory that leads to bilinear coupling, Jij is ferromagnetic for the NN
γ
and antiferromagnetic for more distant pairs for which it decays as 1/rij , where γ
varies between 4 and 5 in the HgTe type of systems [114], a much slower decrease
with rij compared to superexchange. Furthermore, this mechanism is relevant for p-
type tetrahedrally coordinated DMSs, in which quantum hopping between various
valence subbands is allowed [55].
M
FS [M](T , H ) = dM o · h(M o ) − M · H . (16)
0
By expanding BS (M) for small M and introducing the spin susceptibility of the
magnetic ions in the absence of carriers, χ̃S = χ /(gμB )2 , one arrives at the mean-
field formula allowing to determine TC :
18 Dilute Magnetic Materials 951
where β should be replaced by the s–d exchange integral α in the case of electrons
(section “Exchange Interactions Between Band and Localized Spins”) and q denotes
the Fourier component of the magnetization texture, for which TC attains the
highest value. It is convenient to parametrize experimental values of χ̃S by χ̃S =
xeff N0 /S(S + 1)/(T − Θp ), where xeff = x and Θp = 0 take into account coexisting
superexchange interactions. For the spatially uniform magnetization (q → 0), one
then obtains
TC = TF + Θp , (19)
where TF is given by
The magnitude of χ̃c appearing in Eq. 18 can be determined from the linear
response theory. Assuming that Jsp−d /N0 ≡ β in Eq. 4, so that only anion p bands
are relevant [55]:
where the term i = j describes the intraband (RKKY-like) coupling, whereas the
interband (Bloembergen-Rowland-like) interactions correspond to i = j terms; sM
is the component of the spin operator along the direction of magnetization; ui,k is the
periodic part of the Bloch wave function; and fi (k) is the Fermi-Dirac distribution
function for the i-th band.
In thin films, heterostructures, and superlattices, owing to the formation of inter-
facial space charge layers, the hole density and corresponding Curie temperatures
TC [p(z)] are nonuniform even for a uniform distribution of acceptors and donors.
The role of nonuniformity in the carrier distribution grows on reducing the thickness
t of magnetic layers and is particularly relevant in those structures where p(z) can
be tuned electrostatically, for instance, by the gate voltage. When t is larger than the
phase coherence length Lφ , the region with the highest TC value determines TC of
the whole structure. If, however, t < Lφ , the value of local magnetization M(z) and
TC are determined by the distribution p(z) across the whole channel thickness. In
this regime two situations are relevant.
If disorder is strong < t, the scattering broadening makes dimensional
quantization irrelevant though quantum mechanical non-locality remains important.
Under these conditions the magnitude of a layer’s TF can be expressed as [115]
TF = dzTF [p(z)] dzp(z)2 /[ dzp(z)]2 , (22)
952 A. Bonanni et al.
Here m∗ denotes the in-plane effective mass, and L̃W is an effective width of the
region occupied by carriers and spins relevant to ferromagnetism given in Eq. 8 [22,
117]. As seen, owing to a steplike form of DOS in the 2D case, TF does not depend
on the hole density in this case. The expression for TF was generalized further to the
case of arbitrary degeneracy of the hole liquid and by including effects of disorder
via scattering broadening of DOS [118].
Theoretical approaches were developed to allow evaluation of the Curie temper-
ature for ferromagnetic ordering of magnetic impurities mediated by Dirac carriers
at the surface of 3D topological insulators [119, 120]. The Ising type of exchange
was assumed, Hex = −N0 Jz sz Sz , leading to a gapped dispersion given by
where vf is the Fermi velocity. For such a case [119], in our notation,
TF = N0 xeff S(S + 1)AF rJz2 (Ec − |εF |)/(24π h̄2 kB vf2 L̃W ), (25)
Spin-Glass Systems
where the bar denotes the configuration average with respect to random spin
positions and the brackets denote the thermal or dynamical average. The existence
of a phase transition at nonzero temperatures is supported by a careful experimental
examination of static [124] and dynamic [125, 45] critical scaling behavior of
magnetization as function of T , H , and f in the immediate vicinity of Tf for AgMn,
Fe0.5 Mn0 .5 TiO3 , and (Cd,Mn)Te, respectively.
Another relevant question is whether the lower critical dimensionality for
Heisenberg spins is dl < 3, so that the observed phase transition in 3D cases is
driven by magnetic anisotropy that effectively makes the spins Ising-like. Figure 6
shows Tf of CuMnPt and AgMnAu as a function of a magnetic anisotropy parameter
A that increases with the concentration of Pt and Au impurities bringing a sizable
spin-orbit interaction to this Heisenberg spin system [126]. As seen, the data point
to nonzero values of Tf in the limit A → 0. A similar conclusion emerges from
Fig. 7 showing comparable magnitudes of Tf in Mn-doped II-VI selenides and
tellurides, despite the strength of the Dzyaloshinskii-Moriya interaction differing
18 Dilute Magnetic Materials 955
35
25
20
15
0.0 0.1 0.2 0.3 0.4
Magnetic anisotropy parameter A0.8
by a factor of about two for these two families of Heisenberg DMSs [127].
Altogether these findings suggest that the spin-glass phase transition occurs also
for the Heisenberg case. However, somewhat surprisingly critical exponents appear
similar for Heisenberg [45] and Ising [125] spins.
A great deal of information on spin glasses comes from Monte Carlo numerical
simulations [11, 12]. Within the Edwards-Anderson model, classical spins residing
in a cubic lattice are coupled by NN exchange interactions Jij , whose magnitudes
are randomly selected from a Gaussian distribution with a zero mean value. There is
a converging view that for such a model Tf > 0 for both Ising and Heisenberg spins
in the 3D case [12, 128]. There is also a growing amount of evidence that spin-glass
freezing of Heisenberg spins is accompanied by a chiral order, i.e., by a nonzero
value of the chiral order parameter:
(μ)
qchiral = S i−μ̂ · (S i × S i+μ̂ ), (27)
where μ̂ is the unit lattice vector along x, y, or z [12, 128]. The presence of chiral
ordering is thought to account for the lack of proportionality between the anomalous
Hall resistivity and magnetization observed in spin glasses, such as AuMn [129].
Since a number of optimization problems can be mapped onto the determination
(z)
of thermal equilibrium spin orientations {Si } for a given set of interaction
magnitudes {Jij }, progress in spin-glass computation tools has had a significant
impact on other fields [13]. A particularly timely question concerns the effectiveness
956 A. Bonanni et al.
x
1.0 0.064 0.0156
Zn1-xMnxSe
Zn1-xMnxTe
Cd1-xMnxTe
10 Cd1-xMnxSe
Hg1-xMnxTe
Tf(K)
Hg1-xMnxSe
(Cd1-xMnx)3As2
1
0.1
1.0 1.5 2.0 2.5 3.0 3.5 4.0
x-1/3
Fig. 7 Spin-glass freezing temperature Tf in various bulk II1−x Mnx -VI DMSs and
(Cd1−x Mnx )3 As2 as a function of x −1/3 (points), as implied by the percolation theory for
spin-spin couplings decaying exponentially with the pair distance [34]. Straight line is a guide for
the eye. Relatively high values of Tf for inverted band structure semiconductors Hg1−x Mnx Te(Se)
at x 0.1 and (Cd1−x Mnx )3 As2 point to the presence of an additional exchange interaction,
presumably ferromagnetic interband Bloembergen-Rowland (Van Vleck) contribution (sections
“Bloembergen-Rowland Mechanism” and “p–d Zener Model”). (The data points collected by
Gała̧zka et al. [54])
(z)
of quantum annealing procedures [14] that aims at accelerating the search for Si
by adding a transverse field Hx , which means that i S (z) zi ceases to be a constant
of motion and, thus, the ground state {Si(z) } for Hx → 0 can be achieved by quantum
tunneling.
On the theoretical side, two approaches have generated a considerable interest.
One is the Sherrington-Kirkpatrick model, in which the probability distribution
P(Jij ) is Gaussian but the range of interactions between classical Ising spins is
infinite, so that a mean-field approach should be valid. Its implementation proceeds
by employing a replica trick allowing, in the configurational averaging of the free
energy over P(Jij ), the replacement of ln Z[Jij Si(z) Sj(z) ] by (Z[Jij Si(z) Sj(z) ])n ,
i.e., by n replicas of the system. In the time-honored and exact solution proposed
by Parisi, order parameters involving different pairs of replicas (actually their
overlap) are not identical (replica symmetry breaking – RSB). Within the RSB
model, wandering of the coupled spin system between closely lying local free
energy minima accounts for glass-like dynamics (hierarchical dynamics) [15]. An
18 Dilute Magnetic Materials 957
In virtually all semiconductor families, the coexistence of hole carriers with dilute
Mn2+ ions results in ferromagnetic ordering at sufficiently low temperatures.
This ferromagnetism is mediated by itinerant or weakly localized holes that are
strongly coupled to Mn spins via p–d hybridization. In DFSs of III-V [(Ga,Mn)As,
(In,Mn)As [20]] and V-VI [(Bi,Mn)2 Te3 [133]] compounds and also of elemental
semiconductors [(Ge,Mn) [134]], the holes are provided by Mn ions themselves,
which act as acceptors. Deviation from stoichiometry, such as cation vacancies, is
another source of holes, the case of IV-VI DFSs [(Ge,Mn)Te [28,29], (Pb,Sn,Mn)Te
958 A. Bonanni et al.
1.5
1.0
0.5
Log second spectral density (Hz-1)
Cd0.8 Mn0.2Te
-0.5
10-3 10-2 10-1
2.0
Cu0.9 Mn0.1
Cd0.8 Mn0.2 Te
1.5
1.0
0.5
0.0
10-3 10-2 10-1
Frequency f (Hz)
(2,φ)
Fig. 8 Upper panel: Second noise spectra in the phase domain sf of (Cd,Mn)Te quantum wires
at 50 mK in the bandwidth from 0.1 to 0.6 Hz [46] (points) are compared to expectations for
(2)
the Gaussian 1/f noise (solid line). Lower panel: Frequency dependence of sf (normalizing to
and subtracting the Gaussian expectation) for Cd0.8 Mn0.2 Te at 50 mK [46] and Cu0.91 Mn0.09 at
11 K [132] (points). Lines, except for the Gaussian background, are guides for the eye. (From
Jaroszyński et al. [46])
[21]] and also of I-II-V systems [Li(Zn,Mn)As [135]]. In certain compounds holes
can be introduced by co-doping with anion- or cation-substitutional acceptors [e.g.,
(Cd,Mn)Te/(Cd,Mg,Zn)Te:N [22] and (K,Ba)(Zn,Mn)2 As2 [30], respectively]. In
the case of (Ge,Mn)Te, ferromagnetism coexists with ferroelectricity [136].
These systems share a number of common features affecting their magnetic
properties.
First, the hole-mediated interaction competes with a short-range antiferromag-
netic superexchange, so that there is an optimum Mn content for achieving the
highest TC (so far reaching ∼200 K in (Ga,Mn)As, (Ge,Mn)Te [28, 29], and
(K,Ba)(Zn,Mn)2 As2 [30]) which according to magnetization saturation corresponds
to xeff 0.1.
18 Dilute Magnetic Materials 959
Second, these materials show a strong tendency to phase separation (see sec-
tion “Heterogenous Magnetic Semiconductors and Oxides”) – dilute Mn spins can
coexist with nanocrystals of, for instance, ferromagnetic Mn-rich (Mn,Ga)As in
(Ga,Mn)As [137] or antiferromagnetic MnTe in (Ga,Mn)Te [29].
Third, in addition to the solubility limit of Mn ions, there exists a self-
compensation mechanism with generation of donor defects (e.g., Mn interstitials
or As antisites) that limit the achievable hole density (section “Heterogenous Mag-
netic Semiconductors and Oxides”). These and other defects may alter magnetic
properties.
Fourth, as in any doped semiconductor, carriers in DFSs undergo the Anderson-
Mott metal-to-insulator transition (MIT) at pc ≈ (0.26/aB )3 , where the effective
Bohr radius aB is diminished by coupling to localized spins, rather substantially
in the strong coupling limit (section “Spin-Splitting of Extended States: Strong
Coupling”). Nanoscale critical fluctuations in the carrier density on approaching
and crossing the MIT result in the appearance of spin-glass (section “Spin-Glass
Systems”) and superparamagnetic regions [31].
However, despite these materials issues, films of (Ga,Mn)As and related com-
pounds, optimized by appropriate epitaxy and annealing procedures, show excellent
micromagnetic properties, which has opened the door to demonstrating novel func-
tionalities and to verifying the understanding of carrier-mediated ferromagnetism
and spintronic phenomena in DFS-based devices [23, 24]. In particular, it has
been found (by employing the independently determined exchange energy N0 β
as well as kp or tight-binding parameters) that the p–d Zener model (sections
“p–d Zener Model” and “p-Type Dilute Ferromagnetic Semiconductors”) even
within MFA and neglecting disorder allows one to describe semiquantitatively and
often quantitatively pertinent phenomena as a function of temperature, magnetic
field, pressure, strain, and dimensionality [23, 24]. The studied properties include
(i) thermodynamic characteristics such as Curie temperature, spin magnetization,
specific heat, carrier spin polarization, and orbital magnetization; (ii) micromagnetic
parameters including magnetic anisotropy, exchange stiffness, spin wave dispersion,
domain-wall width and intrinsic resistance; and (iii) spintronic functionalities,
e.g., electric-field control of magnetization, spin-transfer and spin-orbit torques,
intrinsic component of the anomalous Hall effect, interlayer coupling, spin injection
efficiency, current-induced domain-wall velocity and intrinsic pinning, MCD, TMR,
and TAMR. The progress in semiconductor spintronics of p-type DFSs has triggered
search for similar effects in metals that by supporting ferromagnetic ordering above
room temperature are more suitable for applications.
As an example, Fig. 9 presents the predicted and observed values of TC in p-type
(III,Mn)V compounds. As seen, there is a good agreement in TC values and chemical
trends. An analysis of theoretical results indicates that a contribution of interband
terms involving valence band subbands (the Bloembergen-Rowland mechanism) to
the magnitudes of TC is about 30%.
For verification of how TC varies with the hole concentration p, particularly
useful are studies of TC (p) in a single sample, as such a dependence is virtually
independent of poorly known values of Θp in Eq. 19 and background concentrations
of compensating donors. According to numerical results for the p–d Zener model
960 A. Bonanni et al.
In the course of the years, Ga1−x Mnx N has gained the status of a model dilute
magnetic insulator, in which strong p–d coupling leads to tight binding of the hole at
a Mn acceptor (the Zhang-Rice polaron) precluding the insulator-to-metal transition,
18 Dilute Magnetic Materials 961
p(z) (10 cm )
86 1.5 -7 MV/cm
-3
84
20
1.0
82
0.5
TC (K)
3D p-d Zener
80 +7 MV/cm (uniform distribution)
0.0
78 2 nm z
p-d Zener +
76 Experiment non-uniform hole
(Device B2) distribution
74 0.23
TC v p
0.21
TC v p
72
0.5 1 1.5 2 2.5
20 -3
pS / t (10 cm )
Fig. 10 Curie temperature TC in a metal-oxide-semiconductor structure, in which the gate electric
field EG changes the hole distribution (inset) and density (the areal hole concentration ps
normalized to the thickness t of the (Ga,Mn)As channel). The solid line represents the generalized
p-d Zener model for thin layers (Eq. 23), whereas the dotted line shows the dependence predicted
by the p–d Zener model for the 3D case (Eq. 20). (From Nishitani et al. [141])
Ga1-xMnxN
10
0.1
1 2 3 4 5
x-1/3
Fig. 11 Experimental Curie temperatures TC as a function of x −1/3 in Ga1 − xMnx N (symbols)
as collected by [33] compared to theory within the tight-binding approximation and Monte Carlo
simulations, serving to determine TC (stars [33]). The slope of the straight solid line agrees
quantitatively with the percolation theory [34] for the magnitude of the exponential decay of spin-
spin coupling with the pair distance evaluated within the tight-binding approximation
J0 exp(−rij /b), one obtains [34] TC (x) = T0 exp[−0.87(N0 x)−1/3 /b], where b =
0.11 nm in Ga1−x Mnx N, the expectations corroborated by experimental and Monte
Carlo data (Fig. 11). This model implies also that all spins join the percolation
cluster only in the limit T → 0, whereas ferromagnetic and superparamagnetic
regions coexist at T > 0 in dilute ferromagnets with a finite range of spin-spin
interactions, | drJ (r)| < ∞.
An additional mechanism of FM coupling operates in topological materials. One
of the consequences of the inverted band structure specific to these systems is a
large contribution of anion p-type wave functions to Kohn-Luttinger amplitudes uik
of both the valence and conduction bands. Accordingly, appreciable magnitudes
of TF , described in Eqs. 20 and 21, can be expected from interband polarization
(the Bloembergen-Rowland mechanism) even if the Fermi energy resides in the
bandgap [51].
This FM interaction competes with AF superexchange in the case of Mn2+
ions and, as shown in Fig. 7, enhances the spin-glass freezing temperature of
Hg1−x Mnx Te, Hg1−x Mnx Se, and (Cd1−x Mnx )3 As2 in the topologically nontrivial
regime. Without strain, Hg1−x Mnx Te and Hg1−x Mnx Se are topological semimetals
for x 0.06, whereas under tensile and compressive strain, they become topolog-
ical insulators [142] and Weyl semimetals [53], respectively, in this low x limit.
18 Dilute Magnetic Materials 963
[Cr0.11(BixSb1-x)0.89]2Te3
The magnetic properties discussed above have concerned systems with a random
distribution of cation-substitutional magnetic impurities, except for possible Jahn-
Teller distortion for ions with a nonzero value of the orbital momentum, like the case
of Mn3+ in GaN. A challenge but also a resource of dilute magnetic materials is a
crucial dependence of their properties on the spatial distribution of magnetic ions
and their position in the crystal lattice. These nanoscale structural characteristics
depend, in turn, on the growth and processing protocols, as in the extensively studied
field of magnetic metallic alloys and nanocomposites [146] ( Chap. 15, “Metallic
Magnetic Materials”). By employing a range of photon, electron, and particle beam
methods, with structural, chemical, and spin resolution down to the nanoscale, it
has become possible to correlate surprising magnetic properties with the spatial
arrangement and the electronic configuration of the magnetic constituent [3].
A number of striking properties of nonmetallic dilute magnetic materials dis-
cussed in this section stem from a contribution of the p–d hybridization to the
binding energy, which results in attractive chemical forces between TM impurities.
Numerous ab initio studies of TM-doped semiconductors and oxides, by determin-
ing the pairing energy of TM cation dimers [147, 3], have revealed that such forces
exist in virtually all studied combinations of TM ions and nonmetallic hosts, except
for Mn in II-VI chalcogenides in which Mn-induced states lie far from the Fermi
level (see Fig. 1). These attractive forces can be overcompensated by Coulomb
repulsion if co-doping with electrically active dopants changes the charge state
of the magnetic impurities [148] though, in general, the effect of co-doping can
be more intricate leading, for instance, to the formation of impurity complexes or
affecting TM diffusion coefficients.
Fig. 13 Temperature dependence of remanent magnetization and resistivity (inset) for three
Ga0.76 Al0.24 As/Ga1−x Mnx As/Ga0.76 Al0.24 As quantum well (QW) structures. The width of the
QW is 5.6 nm, x = 0.06. Beryllium acceptors were introduced either into the first barrier (grown
before the ferromagnetic QW, I-MDH) or into the second barrier (N-MDH), or the sample was
undoped, as marked. The presence of holes originating from Be either enhances TC (N-MDH) or
reduces it by generation of Mn interstitials during the epitaxy (I-MDH). (From Wojtowicz et al.
[150])
wz-GaN:TM
temperature, opening the door for laser applications in spectral windows relevant
for telecommunication [158].
Surface aggregation: Epitaxial growth proceeds under conditions allowing for
surface migration, which leads to aggregation of TM cations if the dimer pairing
energy Ed is negative at the growth surface rather than in the bulk. According to ab
initio data collected in Fig. 14, the values of Ed for Cr, Mn, and Fe cations in the bulk
GaN are negative, and |Ed | is much larger than kB T under conditions of epitaxial
growth of GaN. However, Ed becomes positive for Mn surface cation dimers. This
may explain why the solubility limit of Mn compared to that of Fe is about one order
of magnitude greater under the same growth conditions [159].
Formation of nanocolumns: There is a steady progress in controlling spinodal
nanodecomposition in DMSs, particularly the nanocrystal size distribution as well
as lateral and vertical ordering [47]. Remarkably, under specific growth conditions,
the surface aggregation and associated mismatch strain lead in some systems to the
self-organized growth of TM-rich nanocolumns embedded in the TM-poor host, an
effect observed in (Al,Cr)N [161], (Ge,Mn), and (Zn,Cr)Te [3]. The resulting TM
distribution is illustrated in Fig. 15 for the case of (Ge,Mn). These nanocolumns are
typically metallic and thus can serve as nanocontacts (in, e.g., energy harvesting
systems) or as active devices [3]. For instance, by interrupting the TM flow for a
certain time during the epitaxy, tunnel barriers can be formed resulting in a dense
array of nanoscale TMR junctions or single-electron transistors [162].
968 A. Bonanni et al.
33x33x10 nm3
28x28x50 nm3
Fig. 15 Visualization of Mn-rich nanocolumns in a Ge0.94 Mn0.06 film by 3D atomic probe. In the
nanocolumns, Ge1−x Mnx with x 0.5 is formed. (Reproduced from Mouton et al. [160], with
the permission of AIP Publishing)
Acknowledgments The work of A. B. was supported by the Austrian Science Foundation, FWF
(P31423 and P26830), and by the Austrian Exchange Service (ÖAD) project PL-01/2017. T. D.
acknowledges a support by the Foundation for Polish Science through the IRA Programme
financed by EU within SG OP Programme.
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Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 980
Spin Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 982
Single Ion Spin Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 982
Multi-spin Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 987
Giant Spin Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 988
Quantum Tunneling of Magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 988
Landau–Zener–Stückelberg (LZS) Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 989
Spin Parity and Quantum Phase Interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991
Quantum Coherence in Molecular Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
Resonant Photon Absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
Rabi Oscillations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
Molecular Quantum Spintronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 995
Direct Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 996
Indirect Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 999
Quantum Algorithms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002
Abstract
Introduction
Fig. 1 Size scale spanning atomic to nanoscale dimensions. On the far right is shown a high-
resolution transmission electron micrography of a typical 3 nm diameter cobalt nanoparticle
containing about 1000 Co atoms. The Mn84 molecule is a 4.2 nm diameter particle. Also shown for
comparison are the indicated smaller Mn nanomagnets which are drawn to scale. An alternative
means of comparison is the Néel vector (N) which is the scale shown. The arrows indicate the
magnitude of the Néel vectors for the indicated SMMs which are 7.5, 22, 61, and 168 for Mn4 ,
Mn12 , Mn30 , and Mn84 , respectively. (Reprinted from [10])
Fig. 2 Left: Structure of the Mn12 SMM with the formula [Mn12 O12 (CH3 COO)16 (H2 O)4 ] ·
2CH3 COOH·4H2 O. Middle: Structure of the Fe8 SMM with the formula [Fe8 O2 (OH)12 (tacn)6 ]8+
where tacn is a macrocyclic ligand. Right: Mononuclear terbium complex TbPc2 . The upper Pc
ligand is a mirror image of the lower Pc ligand but rotated by 45◦
SMMs lead to breakthrough observations and to this day remain among the most
investigated systems [7].
SMMs are constituted by an inner core of magnetic ions which is surrounded
by a shell of organic ligands. They come in a variety of shapes and sizes and
permit selective substitution of the ligands in order to alter the coupling to the
environment. It is also possible to replace the magnetic ions, thus changing the
magnetic properties without greatly modifying the structure and the interaction with
its surroundings.
982 G. Taran et al.
The technological interest in the field of SMMs is fueled by the desire to use
molecular structures as memory units and quantum bits (qubits). There are currently
two different approaches that try to satisfy the observed miniaturization tendencies
in the current state-of-the-art technology. The first one is a top-down approach in
which the nanometer-sized objects are obtained by reducing the dimensions of a
bulk material (a common way for obtaining magnetic nanoparticles). The second
method is a bottom-up approach [8], which for the field of SMMs means enhancing
the magnetic moment of the molecule by ion substitution or through adding
new magnetic centers to the molecule. Figure 1 shows a dimensional comparison
between the above presented methods.
One big advantage of SMMs over magnetic nanoparticles is their monodisperse
properties, as chemical synthesis yields a large number of molecules with identical
characteristics. In many cases, the SMMs can be made to form insulating monocrys-
tals; thus, the environment of each molecule is very similar. This gives access to the
properties of a single molecule from the measurements performed on the ensemble.
The found alignment between the magnetic principal axis of the molecule and the
crystallographic axes [9] is especially important when determining the intrinsic
characteristics of the magnetic centers.
SMMs belong to the mesoscopic realm (we refer to the vector space associated
with the spin degree of freedom) where properties from both the quantum and the
classical worlds transpire. The interest of working in this dimensional range comes
from the desire of using quantum properties characterizing microscopic systems
while addressing and manipulating them with simple means.
We start by presenting the spin Hamiltonian formalism, alongside introducing the
concepts essential for understanding the magnetism of molecular magnets. Then,
we show how SMMs were used as a vehicle to explore quantum phenomenologies
like quantum tunneling of magnetization (Sect. “Quantum Tunneling of Magneti-
zation”), spin parity effect and the Berry phase interference (Sect. “Spin Parity and
Quantum Phase Interference”), and quantum coherence (Sect. “Quantum Coherence
in Molecular Magnets”). The last section is devoted to recent achievements in the
field of molecular spintronics.
Spin Hamiltonian
The first step in describing the static and dynamic properties of SMMs is writing the
characteristic Hamiltonian. The application of the general formalism to mononu-
clear and polynuclear complexes will allow us to highlight both the strengths and
the range of validity of the different spin models.
The coupling between J and the external magnetic field (H ) is modeled through
the Zeeman term:
HZ = μB μ0 H ĝJ
where ĝ is a tensor that links the total angular momentum to the magnetic moment
and μB is the Bohr magneton.
The effect of the ligand field can be accounted for through the use of the
equivalent Stevens operators [11, 12]. Thus, the total Hamiltonian is:
2S
q
H= Bqk Oqk + HZ (1)
q=2 k=0
where Oqk are equivalent Stevens operators and Bqk are parameters related to the
ligand field and electronic structure of the ion. The Stevens operators are functions
of Jz , J− , J+ and are listed in [11, 12]. The index q represents the order of the
operators. The sum includes only even terms as only even terms generate nonzero
matrix elements. The subscript k denotes the operator’s rotational symmetry.
where D and E are commonly used notations that stand for the Stevens coefficients
3B20 and B22 , respectively. D is negative when z-axis is chosen to coincide with the
easy axis of the molecule, which will be assumed in the following, and |E| |D|
in most cases.
Considering only the first term in the above Hamiltonian, we see that the states
pertaining to the S multiplet and labeled by the quantum number m = −S...S,
are only doubly degenerate: E(±m) = −|D|m2 . For this reason, the magnetic
anisotropy constant D is often denoted as zero-field splitting (ZFS).
The discrete energy levels follow a parabola, illustrated in Fig. 3. U = |D|S 2
is called the anisotropy barrier. The two sides of the barrier correspond to opposite
orientations of the magnetic moment; thus, the ZFS term gives the approximate
energy barrier the spin has to overcome to flip its orientation.
984 G. Taran et al.
Fig. 3 Left: Energy levels of a spin S = 10 subject to the ZFS term. Right: A zoom of the energy
level diagram near an avoided level crossing where m and m are the quantum numbers of the
energy levels. PLZ is the Landau–Zener tunnel probability when sweeping the applied field from
the left to the right over the anticrossing. The greater the gap Δm,m and the slower the sweeping
rate, the higher is the tunnel probability PLZ (equation (9))
The height of the barrier and the characteristic time of the experiment lead to
the definition of the blocking temperature (TB ), as the temperature under which
the phonons do not have sufficient energy to promote reversal processes (e.g., for
Mn12 -ac, TB ∼ 4 K for a characteristic time of the experiment of 1 s). Increasing the
blocking temperature remains a central research goal in the field of SMMs [13, 14,
15] with the current record anisotropy barrier being 1760 K and TB ∼ 60 K [16,17].
The last term in (2) breaks the axial symmetry of the system and strongly affects
the low-temperature relaxation of the magnetization (Sect. “Quantum Tunneling of
Magnetization”).
Lanthanide(III) Ions
As a second example, let’s look at the lanthanide (III) ion complexes whose
magnetic properties are mainly determined by the strongly anisotropic and partially
filled 4f orbitals. Opposite to the case of transition metal ions, the angular orbital
momentum of the rare earth atoms is not quenched by the ligand field, and the spin–
orbit coupling is much stronger due to their larger nuclear charge. Thence, neither
L or S are good quantum numbers, the magnetic moment being described by a total
angular momentum, J = |L − S| . . . (L + S), where L + S is the ground state for
more than half-shell filling (Hund’s rule).
For instance, the Tb3+ ion exhibits the [Xe]4f 8 electronic structure, which leads
to a spin S = 3 and an orbital angular momentum L = 3. The ground state of the
Tb3+ ion is thus J = L+S = 6. The strong spin–orbit coupling leads to a separation
of about 2900 K between the ground state and the excited state (J = 5). We can
therefore restrict the following discussion to the ground state multiplet, J = 6,
comprised of 2J + 1 (degenerate) substates |J, mJ .
The Tb3+ ion can be embedded between two parallel phthalocyaninato (Pc)
ligand planes. The crystal field interaction generates a quantization axis oriented
perpendicular to the Pc planes. The Tb3+ ion is coordinated by four nitrogen atoms
from each ligand plane, and the upper Pc ligand (blue in Fig. 2) is a mirror reflection
of the lower one (with respect to the x-y plane) rotated by 45◦ around the z-axis. The
19 Single-Molecule Magnets and Molecular Quantum Spintronics 985
Tb3+ is therefore exposed to an antiprismatic ligand field that was modeled by the
following Hamiltonian [18]:
Hlf = B20 O20 + B40 O40 + B44 O44 + B60 O60 + B64 O64 (3)
where Ahyp = 26.7 mK is the hyperfine constant and P̂quad is the quadrupole tensor.
The hyperfine interaction, Ahyp I · J , splits the electronic states from the ground
state doublet mJ = ±6 into (2I + 1) hyperfine states, labeled by the additional
nuclear quantum number mI = −3/2 . . . 3/2.
Fig. 4 Left: Ligand field splitting of the ground state multiplet in different mononuclear lanthanide
complexes LnPc2 . (Modified from [18]). Right: Calculated Zeeman diagram for the ground state
multiplet, J = 6, in a TbPc2 SMM. (Extracted from [19])
986 G. Taran et al.
Because I > 1/2, the 159 Tb nucleus has a quadrupolar moment that couples to
the electric field gradient through IP̂quad I with the dominant term being the axial
component with magnitude Pquad = 17 mK. The tensorial nature of P̂quad reflects
the non-axial character (with respect to the easy axis of the ligand field) of the
quadrupolar interaction which together with transverse terms in Hlf was shown to be
responsible for the observed tunneling dynamics of TbPc2 in diluted single crystals
[20] (Fig. 5).
1
a)
0.5
Δ
M/M s
0
M/M s
-0.5
-1
b)
0.6
Energy (K)
0.3
-0.3
Fig. 5 (a) Zoom on the magnetic hysteresis loop of an assembly of TbPc2 SMMs in a diluted
single crystal (1% TbPc2 in an YPc2 matrix) measured with the microSQUID setup at T =
40 mK. The insets show: (left) a zoom of a level anticrossing between two hyperfine states and
(right) the entire hysteresis loop. The red markers (right inset) indicate the continuous change
of magnetization at high fields attributed to phonon-assisted relaxation. (b) Zeeman diagram of a
TbPc2 SMM. The characteristic steps in the magnetization curve around zero field correspond to
QTM events in the single crystal and are highlighted by dashed lines. (Changed from [21])
19 Single-Molecule Magnets and Molecular Quantum Spintronics 987
Multi-spin Hamiltonian
Although a number of molecules having a single magnetic ion have been synthe-
sized [22], most SMMs contain multiple magnetic centers within their organic shell,
and their description thus requires a multi-spin Hamiltonian. For a pair of spins
coupled through exchange interaction, the Hamiltonian can be written as [23]:
In general, the interaction tensor Jˆ12 is not symmetric, so it’s customary to put the
above equation in a form that highlights an isotropic term (J12 S1 · S2 ) that favors
a parallel alignment of the spins, an anisotropic, symmetric component (S1 Dˆ12 S2 )
that tends to align the spins along a certain direction in space, and Dzyaloshinskii–
Moriya term (d12 · (S1 × S2 )) that works toward orienting the spins perpendicular
to each other. Usually, the isotropic term is significantly larger than the others, and
its sign will dictate the ferromagnetic or antiferromagnetic character of the ground
state.
The generalization to a system containing an arbitrary number of spins is done by
putting together the single ion anisotropies with the pairwise exchange interactions,
leading to the following multi-spin Hamiltonian:
H= Si D̂i Si + ˆ Sj
Si Ji,j (6)
i ij
where we considered only the quadratic term in the ligand field Hamiltonian. Even
with this simplification, the number of parameters involved can be quite large,
especially for clusters with high nuclearity. This difficulty cannot be completely
eliminated, even when one considers a very symmetric molecule. As an example,
let’s consider the archetypal Mn12 -ac molecule (Fig. 2). It contains an inner ring
of four Mn(IV) ions (S4 = 3/2) and an outer ring of eight Mn(III) (S3 = 2)
coupled together through superexchange interactions involving oxygen bridges. The
number of states that characterizes the system is (2S4 + 1)4 (2S3 + 1)8 , which yields
an overwhelming 108 eigenstates. Because the Mn12 -ac molecules crystallize in a
body-centered tetragonal crystal, the unit cell contains two equivalent Mn ions so
one independent zero-field splitting tensor is needed. When choosing a coupling
scheme with only isotropic interactions [2], another four exchange parameters are
required. Adjusting this model to experimental results, such as electron paramag-
netic resonance (EPR) measurements, is far from trivial. Nevertheless, this model is
valuable for low nuclearity systems [24]. A common way to shrink the dimension
of the Hilbert space in which we have to study the system is done by replacing pairs
of strongly interacting spins with a single equivalent spin.
988 G. Taran et al.
Applying the above procedure recursively to all spin pairs leads to the giant spin
approximation, which describes in an effective way the ground state multiplet. This
simplification works especially well when the temperature is low enough so that the
dominant energy in the system is the exchange interaction. In this case, the system
is always found in its spin ground state (e.g., S = 10 for Fe8 and Mn12 -ac), allowing
the use of the single ion model presented at the beginning of this section. Therefore,
we write the giant spin model:
where D and g are now effective parameters and HT describes non-axial interac-
tions and can be written as a function of rising and lowering spin operators (S+ ,
S− ). In order to relate the effective parameters of the giant spin model and the
parameters characterizing each individual magnetic center, one can use projection
techniques [25], where single ion anisotropies are projected onto the vector space
corresponding to the molecular ground state. This method is less accurate when the
Hilbert space is very large, like in the case of Mn12 -ac, but the model retains its use
because of its simplicity and intuitive form.
The energy range in which the giant spin model is valid can be found in the
multi-spin Hamiltonian. Indeed, the weakest exchange link gives with a good
approximation the upper temperature limit to which the predictions are expected to
be accurate. Experimentally one can observe the crossover to higher spin subspace
by determining the magnetic moment associated with the molecular cluster [26,27].
For a ligand field Hamiltonian described only by the ZFS term, the magnetic field
lifts the twofold degeneracy of the ±m energy levels. However, two different levels
(denoted by m and m ), align for specific field values Hrm,m , applied along the
magnetic principal axis:
|D|(m + m )
Hrm,m = (8)
gμB μ0
Due to transverse terms of the spin Hamiltonian, the degeneracy can be trans-
formed into an avoided level crossing; see Fig. 3. The energy separation is called
the tunnel splitting, Δm,m , and is a central parameter that characterizes the quantum
tunneling dynamics of spins.
There are several theoretical tools that can be used to determine the tunnel
splitting, including path integral formalism [28, 29], perturbation theory [30, 31],
and numerical methods. The latter allows the possibility to consider arbitrarily
19 Single-Molecule Magnets and Molecular Quantum Spintronics 989
complex spin Hamiltonians but leaves little intuition on the system’s behavior. Thus,
a combination of the above techniques is to be preferred when performing both
quantitative and qualitative analyses of the magnetic properties of SMMs.
At an avoided level crossing, the eigenvectors of the Hamiltonian are a linear
combination of the base vectors that correspond to negative and positive spin
projections. This means that in these states, the magnetization of the spin has a
nonzero probability to be found on either side of the barrier. This behavior is
called spin tunneling, that is, the spin is in quantum resonance between the opposite
orientation states.
At a constant field tuned at an avoided level crossing, a spin initially situated
on one side of the well will oscillate coherently between the mixed states with a
characteristic angular frequency, ωTm,m , related to the tunnel splitting through the
relation: Δm,m = 2h̄ωTm,m . The field interval where this behavior is predicted to
Δ
happen is given by [23]: δH0 = gμB μ0m,m
|m−m | . This quantity is called the bare tunnel
−9
width and can be as small as 10 T. However, environmental interactions broaden
the observed width of the resonance and hinder coherent oscillations [32,33,34,35].
The nonadiabatic transition between the states of a two-level system was first
discussed by Landau, Zener, and Stückelberg [36, 37, 38]. The original work by
Zener concentrates on the electronic states of a bi-atomic molecule, while Landau
and Stückelberg considered two atoms that undergo a scattering process. Their
solution to the time-dependent Schrödinger equation of a two-level system driven
through resonance has been applied to many physical systems, and it became an
important tool for studying tunneling transitions. The LZS model was used to
analyze spin tunneling in nanoparticles and clusters [39, 40, 41, 42]. The tunneling
probability, PLZ , between the states m and m , after sweeping the applied field at a
constant rate, α, through the resonance (Fig. 3), is given by:
δH0
PLZ = 1 − exp −π ωT (9)
α
With the LZS model in mind, we can now start to understand qualitatively the
hysteresis loops of SMMs (Fig. 6), which exhibit steps of fast relaxation separated
by regions where the magnetization is almost constant. The steps happen at specific
fields where the levels from both sides of the well are mixed by transverse terms in
the spin Hamiltonian, as discussed in the previous section.
Let us start at a large negative magnetic field Hz . At very low temperatures,
all molecules are in the m = 10 ground state (Fig. 6). As the applied field Hz is
ramped down to zero, all molecules will stay in the m = 10 ground state. When
ramping the field over the Δ10,−10 region, at Hz ≈ 0, there is a Landau–Zener
probability, P10,−10 , for the spins to tunnel from the m = 10 to the m = −10
990 G. Taran et al.
state. P10,−10 depends on the sweeping rate (9); the slower the sweeping rate, the
larger is the tunneling probability. This is clearly demonstrated in the hysteresis loop
measurements showing larger steps for slower sweeping rates [43,6]. When the field
Hz is now further increased, there is a remaining fraction of molecules in the now
metastable m = 10 state. The next chance to escape from this state is when the field
reaches the Δ10,−9 region. There is a Landau–Zener tunnel probability P10,−9 to
tunnel from the m = 10 to the m = −9 state. As m = −9 is an excited state, the
molecules in this state relax quickly to the m = −10 state by emitting a phonon. An
analogous procedure happens when the applied field reaches the Δ10,−10+n regions
(n = 2, 3, . . . ) until all molecules are in the m = −10 ground state, that is, the
magnetic moment of all molecules is reversed. As phonon emission can only change
the molecule state by Δm = ±1 or ±2, there is a phonon cascade for higher applied
fields.
Figure 5 shows the magnetic hysteresis loop, measured by microSQUID tech-
nique [44], of a crystal containing TbPc2 SMMs randomly distributed in a
diamagnetic, isostructural matrix formed by YPc2 molecules, with [TbPc2 ]/[YPc2 ]
ratio of 1%. Upon sweeping the magnetic field from −1 T up to positive fields as
small as 0.05 T, approximately 75% of the TbPc2 SMMs undergo quantum tunneling
19 Single-Molecule Magnets and Molecular Quantum Spintronics 991
transitions, resulting in sharp steps in the magnetization curve. The QTM transitions
take place between mixed states of nuclear and electronic origin; thus, both spin
projections can change [20]. The remaining SMM reverse their magnetic moment
at larger magnetic fields by a direct relaxation process [45].
When using the above formalism for a quantitative analysis, one should keep in
mind that the LZS model is exact only for an isolated spin. Deviations from the ideal
coherent dynamics are due to environmental interactions of both elastic (dephasing)
and inelastic (relaxation and excitation) nature [21]. Thus, in order to try to search an
agreement with LZS theory, one should use large sweeping rates, so that in the time
the resonance is swept, the local environmental field does not change significantly.
The model also doesn’t include relaxation through phonons so one should work at
very low temperatures and focus on ground state tunneling.
LZS theory was successfully used to determine the tunnel splitting in molecular
systems such as Fe8 [6] and Mn4 [43]. As mentioned, the agreement with the
experiment must be searched in the fast sweeping rate regime, which has the
drawback of a small sensitivity. To overcome this difficulty, the resonance can be
swept repeatedly. This way, the probability for the spin to remain in the original
state, for small variations of the magnetization, after n back-and-forth sweeps, is
proportional to (1 − 2nPLZ ), with PLZ given by (9).
Spin Parity
The general form of a transverse term of order n is Bn S±n ; thus, a transition between
n
the levels m and m is made possible by applying S± operator an integer number of
times. Consequently, the degeneracy is removed only when the change in the spin
projection is a multiple of the perturbation’s order: n|(m − m ).
The above quantum tunneling selection rule is called spin parity effect and has
its origin in the symmetry of the non-axial Hamiltonian term. For example, in the
case of the Mn3 cluster [48], with a C3 rotational symmetry, level splitting should
occur only if the selection rule m − m = 3k is satisfied.
Another interesting example is the observation of Kramer’s degeneracy in half-
integer spin molecular clusters [49], which tells us that in zero applied magnetic
field, the ground state is at least doubly degenerate. This degeneracy can be lifted
992 G. Taran et al.
Fig. 7 Unit sphere showing degenerate minima A and B which are joined by two tunnel paths
(heavy lines). The hard, medium, and easy axes are taken in the x-, y-, and z-direction, respectively.
The constant transverse field Htrans for tunnel splitting measurements is applied in the xy-plane
at an azimuth angle ϕ. At zero applied field H = 0, the giant spin reversal results from the
interference of two quantum spin paths of opposite directions in the easy anisotropy yz-plane.
For transverse fields along an axis perpendicular to the easy axis, by using Stokes’ theorem, it has
been shown that the path integrals can be converted in an area integral, yielding that destructive
interference – that is, a quench of the tunneling rate – occurs whenever the area enclosed by the
two paths is kπ/S, where k is an odd integer. (Reprinted from [6])
19 Single-Molecule Magnets and Molecular Quantum Spintronics 993
Fig. 8 Measured tunnel splitting Δ as a function of transverse field for (a) several azimuth angles
ϕ at m = ±10 and (b) ϕ ≈ 0◦ , as well as for quantum transition between m = −10 and (10 − n).
Note the parity effect that is analogous to the suppression of tunneling predicted for half-integer
spins. It should also be mentioned that internal dipolar and hyperfine fields hinder a complete
quench of Δ which is predicted for an isolated spin. (Reprinted from [6])
acquired by moving in the parametric space along a closed path containing these
two points.
The magnetic field has the ability to modulate the phase by modifying the paths,
so an interference pattern is observed as the transverse field is increased.
Figure 8 depicts tunnel splitting oscillations of a Fe8 complex showing equally
spaced minima as a function of the transverse field. The difference between the
maxima and the minima of the tunnel splitting can be as large as one order of
magnitude.
The anisotropy of the Fe8 molecule, similar to many low symmetry molecules, is
modeled by adding a biaxial crystal field (HT = E(Sx2 − Sy2 )) to the uniaxial term.
Therefore, when the tunnel splitting between the levels S and S − n is measured,
the spin parity effect is observed (the second-order transverse anisotropy term
forbids odd resonances at zero field). Also, a monotonic increase of Δ with n is
observed: the lower is the energy barrier, the higher are the tunneling rates.
The predicted field separation between two consecutive minima of the tunnel
splitting, when we consider only the biaxial term, is given by:
2
ΔH = 2E(E + D) (10)
gμB
Using the anisotropy parameters determined in [55], one obtains a field separa-
tion of 0.26 T, which is smaller than the experimental value of 0.4 T. In order to
account for this difference, higher order terms must be considered. This is easily
done in the numerical approach that involves the diagonalization of the system’s
Hamiltonian.
Other systems in which it was possible to observe the Berry phase interference
include Mn12 complexes [56,57,58], Mn4 [59], and dimer molecular magnets [60].
994 G. Taran et al.
The study of coherence in molecular magnets is very important for the potential
applications in the field of quantum information processing. Here we briefly account
on the quest for the observation of coherent time evolution of molecular spins under
electromagnetic (EM) radiation.
In EPR experiments involving molecular magnets [55, 61, 62], transitions between
the m and m states of the S multiplet happen when the energy of the incoming
photons is equal to the energy difference between the states: hν = |E(m) − E(m )|,
obeying the selection rule Δm = ±1. An important question that had to be answered
concerns the effect of the photon-induced excitations on tunneling.
The first important results [63] were obtained when a Fe8 complex was
investigated using micro-Hall bars in a dilution refrigerator. The study proved that
the lifetime of the excited states is large enough (relative to the tunneling time)
for an enhanced relaxation to be observed. In order to clearly show the photon-
assisted quantum tunneling regime, circular polarized microwave radiation was used
because it allows to select the Δm = +1 or Δm = −1 transitions. Thus, an
asymmetric hysteresis loop is observed. From the dependence of the transition rates
on the power of the microwave source used, it was shown that the effective spin
temperature (the parameter which describes the occupation number of the excited
states) depends linearly on the power of the EM field. Subsequent experimental
work further proved the photon-assisted tunneling regime [64,65,66] leading toward
eventual observation of Rabi oscillations [62].
Rabi Oscillations
The coherent evolution of the system between two eigenstates coupled by the EM
field is described by the Rabi model [68,69]. If the system’s initial state is |m, then
the probability to find it in the state |m , at time t, is proportional to sin2 (ΩR t).
The Rabi frequency, ΩR , is proportional to the amplitude of the perturbative field.
This property is used in the spin-echo measurement protocols [70] to determine the
characteristic relaxation times of the system.
The longitudinal relaxation time (T1 ) is obtained from the recovery of the
equilibrium magnetization after an inversion pulse, π − T − π2 − τ − π − τ − echo,
is applied, where the variable is T and τ is being kept constant. T1 is directly
connected to the coupling of the spins to the phonon bath and thus can be
significantly long at mK temperatures.
The second important characteristic time is the phase coherence time (T2 ) and is
determined by spin–spin interactions. As the name suggests, it tells us the time over
which the memory of the quantum phase is preserved, so the quantum properties of
the spin can be exploited. Employing a similar Hahn-echo sequence, π2 − τ − π −
19 Single-Molecule Magnets and Molecular Quantum Spintronics 995
Fig. 9 Comparison of
state-of-the-art T2 values of
notable molecular and
solid-state electronic spin
qubits. (Extracted from [67])
τ − echo, with τ variable, T2 is obtained from the echo signals that are fitted to a
stretched exponential, I (τ ) = I (0) exp(−(2τ/T2 )x ).
The interaction with environmental spins of nuclear and electronic origin,
phonons, and photons represents the main sources of decoherence [71] in SMMs
[72, 73] and thus limits T2 . In order to reduce the dipolar interactions, one usually
chooses a system with a small collective spin [65, 74, 62] because the magnitude
of the interactions scales as the square of the spin magnitude. Then, SMMs can be
diluted without greatly effecting their individual properties [74, 62, 75]. Also, the
initial choice of a molecular complex with S = 1/2 [74] avoided the problems
associated with the distribution of the anisotropy axis.
The above measurements led to the first observations of a long phase coherence
time in Cr7 Ni (S = 1/2) and Cr7 Mn (S = 1) clusters [74]. Afterward, Rabi
oscillations were observed in V15 [62, 76], and T2 on μs scale was measured in
Fe8 [77] through the application of a high transverse magnetic field.
Recent developments showed that a strict control over lattice rigidity and
hyperfine interactions can lead to significantly large phase coherence times, even
when compared to other qubit candidates ( [75] and Fig. 9). The coherence also
has been shown to be preserved at room temperature [78, 79]. These are valuable
observations that encourage possible spintronics applications.
ion compounds, tunable environmental interactions that can lead to a long coher-
ence time (Sect. “Quantum Coherence in Molecular Magnets”), and chemically
controlled functionalities like switchability with light or electric field [83]. The
coupling to external structures can be facilitated by choosing an appropriate ligand.
Delocalized bonds, which mediate the interaction between the magnetic ions, often
imply great conduction properties.
The above-outlined properties allowed the realization of some essential circuit
elements, like [81] molecular spin transistors [84, 85], molecular spin valves [86]
and spin filters, and molecular double-dot devices.
Direct Coupling
Fig. 10 Schematic
representation of different
device geometries for
molecular spintronics
devices. (a) Three-terminal
spin-dot device. This is a
direct coupling scheme, in
which the current flows
through the spin dot (SD). (b)
Three-terminal double-dot
device. This is an indirect
coupling scheme, in which
the current flows through a
second nonmagnetic quantum
dot, the read-out dot (RD),
which is coupled with the
spin dot (SD) via exchange
interaction (J). (c)
Supramolecular spin valve
device, with two SD’s
coupled to the RD. The
current in the RD is therefore
sensitive to relative spin
orientation in the two SD’s.
(d) Multiterminal multi-dot
device. (Reprinted from [45])
19 Single-Molecule Magnets and Molecular Quantum Spintronics 997
current control over the spin state [88]. The spin-polarized STM allows direct space
resolved observations of spin-split orbitals [89].
Another configuration is represented by a three terminal device where a molecu-
lar magnet bridges the gap of a break junction. A gate electrode is used to tune the
transport properties of the conduction electrons [90]. First implementation of this
design involved a Mn12 compound bound covalently to gold electrodes. To explore
different conduction regimes, weak binding ligands were also used. In both cases
the peripheral group acted as a tunnel barrier, helping to conserve the magnetic
properties of the cluster.
By knowing the magnetic properties of the redox species that are formed
when the electrons pass through the molecule, one can compare the information
obtained from spectroscopic transport measurements and established experimen-
tal methods like: magnetization measurements, EPR or neutron scattering. First
studies involving Mn12 in a magnetic field showed that it exhibits transistor like
properties [90, 91]. Both degeneracy in zero field and non-linear behavior of the
excitations as a function of field are typical of tunneling via a magnetic molecule.
However, follow up experiments indicated an alteration of the Mn12 magnetic
properties during the deposition on gold electrodes [92]. In contrast to Mn12 , both
Fe4 [93] and TbPc2 [94] are known to preserve their magnetic properties upon
deposition.
In the following we show how such a three terminal device, containing TbPc2
deposited on electromigrated gold electrodes, was used to read-out not only the
electronic spin state but also the nuclear spin state of Tb3+ [94].
Fig. 11 Artist view of (left) a nuclear spin qubit transistor based on a single TbPc2 molecular
magnet, coupled to source, drain, and gate (not shown) electrodes, and (right) a three-spin-dot
device. (Reprinted from [85])
The lifetime of the nuclear states can be determined by doing subsequent mea-
surements separated by a waiting time [85]. A T1 of order of tens of seconds was
observed, which shows that this is a non-invasive method.
The hyperfine Stark effect was used to manipulate the nuclear spin within a
single molecule with an individual relaxation time (T1 ) exceeding 20 s [85]. Rabi,
Ramsey and Hahn echo experiments (Fig. 13), performed on the 159 Tb nuclear
spin [95], compare well with similar experiments involving P or Bi defects in
Si. Ramsey T2 -times are 300 microseconds with π/2 pulse-lengths of 100 ns, i.e.,
about 1000 spin manipulations are possible before decoherence sets in. This allowed
the implementation of Grover’s algorithm using the four states of the nuclear
spin [96].
Indirect Coupling
In order to avoid the strong back action characterizing the above presented devices,
the molecule can be coupled to the electrodes by indirect means, that is, by establish-
ing a link between the SMM (a spin dot) and a non-magnetic molecular conductor
(read-out dot) connected to the electrodes (Fig. 10). The coupling between the spin
dot and read-out dot is usually realized through an exchange interaction and can be
modulated by a gate voltage.
Among possible candidates for read-out dots (e.g., nanowires, carbon nanotubes,
nano-SQUIDs and ligands), carbon nanotubes are special due to their outstanding
structural, mechanical and electrical properties. Because a carbon nanotube is
essentially a 1D molecular conductor, with a diameter of the same order as a
molecular magnet, a good coupling is easily achieved. At low temperature, it
presents electronic properties like Coulomb blockade [97] and Kondo effect [98].
Thus, carbon nanotube conductance is sensitive to any charge fluctuations including
the spin reversal processes.
A number of devices with a carbon nanotube as the detector and TbPc2 as the
spin dot showed that the indirect coupling mechanism allows the determination of
both the electronic and nuclear spin of Tb3+ ion. Urdampilleta et al. [86] showed
that a carbon nanotube functionalized with two SMMs has a supramolecular valve
behavior (Fig. 14). Indeed, the two TbPc2 molecules behave as a spin polarizer-
analyzer system exhibiting a strong magnetoresistive effect.
Mediated by exchange interaction, the magnetic moment of each molecule
induces a localized spin-polarized dot in the carbon nanotube quantum dot that can
be controlled by a magnetic field (Fig. 14). Depending on the relative orientation of
the molecular spins, a high- or low-conductance regime can be observed. A butterfly
hysteresis loop, characteristic of spin valve devices, with a magnetoresistance up to
300% has been measured for temperatures smaller than 1 K. For a more detailed
description, the reader may refer to Urdampilleta et al. [86].
Increasing the number of SMMs coupled to the carbon nanotube (Fig. 10)
and addressing each individual molecule through a local gate may allow the
implementation of complex quantum computation protocols.
1000
Fig. 13 Qubit coherent manipulations. Each color is a transition between consecutive levels: red being the transition between the ground state and the first
excited level, and the next two in green and blue. (a) Rabi oscillations, the frequency of these oscillations can be tuned from 1.5 to 9 MHz. The maximum
visibility is respectively 0.6, 0.9 and 0.6. (b) By recording the maximum of the visibility of the Rabi oscillations as function of the detuning, the shape of the
three transitions can be measured. (c) Ramsey fringes give a coherence time of the order of 0.3 ms for the three transitions. (d) The Results of the Hahn-echo
measurement show that we are far from the limit T1 = 2T2 . This indicates that the decoherence mechanism is not due to the relaxation process. (Changed
from [96])
G. Taran et al.
19 Single-Molecule Magnets and Molecular Quantum Spintronics 1001
Fig. 14 Spin valve behavior in a supramolecular spintronics device based on a carbon nanotube
quantum dot functionalized with TbPc2 SMMs. Figures from [86,99]: (a) Butterfly hysteresis loop
at T = 40 mK. (b) Antiparallel spin configuration: the spin state in dot A is reversed with respect
to that of dot B. The energy mismatch between levels with different spins results in a current
blockade. (c) Parallel spin configuration for both molecules A and B. Energy levels with same spin
are aligned allowing electron transport through the carbon nanotube
Quantum Algorithms
The research aimed at using molecular magnets for qubit encoding started mainly
after the theoretical proposal of Leuenberger and Loss [100, 101], followed by
others [102,103,104,105,106,107]. We shall follow DiVincenzo [108] to summarize
the steps taken toward successful implementation of a quantum computer using
molecular magnets.
To use molecular magnets as qubits, external constrains (e.g., temperature,
electric or magnetic field) should be applied in order to confine the system to a
subset of two levels (|0 and |1). The scalability of the system is facilitated by
the synthetic bottom-up fabrication process that guarantees cheap production of
identical molecular units.
The implementation of proposed quantum algorithms [109, 110, 111, 112]
involves the use of one-qubit and two-qubit gates. The former represents a rotation
on the Bloch sphere. The output of the gate, after realizing an electric or magnetic
coupling to the spin and applying an EM pulse sequence (Sect. “Quantum Coher-
ence in Molecular Magnets”), is the state: α|0 + β|1. A strong-coupling regime, at
high temperatures, between a molecular spin ensemble and microwave resonators,
has been achieved. The possibility of coupling strongly with single molecules has
been put forward, and experiments are in progress. This opens a way to develop
scalable architectures using molecular spins coupled to quantum circuits [113, 114,
115, 116, 117]. Moreover, by molecular engineering of the crystal field, molecular
spins can also be manipulated by electric fields [118, 119, 120, 84, 121].
A two-qubit gate can be implemented by controlling the exchange interaction
between the spins. Schemes and compounds for switchable effective qubit–qubit
interactions in the presence of permanent exchange couplings are now available
1002 G. Taran et al.
[122, 123]. Spin entanglement between and within molecules was shown by
different techniques. Molecular spin clusters/arrays offer an incredible variety of
spin topologies to test entanglement at the molecular scale [119].
It is necessary that the system remains in a coherent state (preserve α and
β), for a time considerably larger than the computational clock time. This is an
important requirement for the system to be amenable to quantum error corrections.
As noted in Sect. “Quantum Coherence in Molecular Magnets”, long coherence time
(T2 ) at low temperature has been reported for many ensembles of molecular spin
systems with T2 approaching 1 ms in nuclear spin-free environments [74, 124, 72].
Recent reports have shown microsecond coherence times and Rabi oscillations at
room temperature [78, 125, 75, 126, 127, 79]. Strategies to protect spin states from
decoherence (e.g., via atomic clock transitions) have been experimentally tested by
fine engineering of molecular states and levels [128]. The development of theoretical
schemes to implement quantum error correction codes in molecules with multiple
spin degrees of freedom has also been started [129, 130, 131, 132, 133].
Another important requirement is the possibility to initialize and read out the
qubit state. As seen in previous sections, the read-out of a single molecular
spin located at a tunnel junction or on a CNT/graphene quantum dot has been
demonstrated [134, 86, 135].
All these achievements are important milestones in molecular magnetism. They
bring this research field closer to being able to provide the future basic components
of quantum devices [136].
Conclusion
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19 Single-Molecule Magnets and Molecular Quantum Spintronics 1009
Contents
Ideal Single-Domain Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1012
How Real Magnetic Nanoparticles Can Be Different . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1015
Magnetic Nanoparticle Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1017
General Nanoparticle Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1017
Liquid Phase Syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1018
Applications of Magnetic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1021
Important Magnetic Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1021
Magnetic Separation and Manipulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1023
Magnetic Hyperthermia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1024
Magnetic Particle Imaging (MPI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1026
Contrast Agents for Magnetic Resonance Imaging (MRI) . . . . . . . . . . . . . . . . . . . . . . . . . 1026
Ferrofluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1028
Magnetic Recording Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1029
Nonbiomedical Topics of Recent Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1030
L10 FePt Nanoparticles for Magnetic Recording Media . . . . . . . . . . . . . . . . . . . . . . . . . . . 1030
Core-Shell NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1032
Surface Effects and Spin Canting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1033
Frontiers and Future Directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1035
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1037
Abstract
S. A. Majetich ()
Physics Department, Carnegie Mellon University, Pittsburgh, PA, USA
e-mail: [email protected]
In 1930 Frenkel and Dorfman first suggested the existence of ferromagnetic domains
[6]. Bitter confirmed them by dusting fine magnetic particles over the surface of a
ferromagnetic material [7]. We now know that in bulk ferromagnetic materials, the
spins are parallel due to short-range quantum mechanical exchange interactions.
There are also long-range magnetostatic interactions, and the combination of
exchange and magnetostatic interactions leads to the spontaneous formation of
magnetic domains, where locally the spins are parallel but over the sample the
domain magnetization directions form magnetic flux closure paths to minimize the
overall energy.
Below a critical size, it is not energetically favorable to form a domain wall, and
the particle is said to be monodomain. An ellipsoidal particle of a ferromagnetic
or ferromagnetic material will be uniformly magnetized. The magnetic moment of
the particle μ = μ0 Ms V, where Ms is the saturation magnetization and V is the
particle volume. The maximum monodomain diameter can be estimated from the
parameters of the bulk ferromagnetic (FM) or ferromagnetic (FiM) material [8]:
20 Magnetic Nanoparticles 1013
Fig. 1 A monodomain
magnetic nanoparticle. Here Easy Axis
µ
the direction of the particle
moment μ depends on the
effective anisotropy, which H
determines the easy axis
direction, and the external
magnetic field H
72(Ak)1/2
dcr = (1)
μ0 Ms2
Here A is the exchange stiffness and K is the anisotropy. A and Ms depend on the
material, while the anisotropy has contributions from the crystallographic structure
and direction and particle shape. Figure 1 shows the case for spherical particle of a
uniaxial material, where the energy is minimized when the magnetization lies along
an easy axis. For more complex cases with biaxial and cubic anisotropy, see Ref. [1].
Maximum single-domain sizes for different materials based on bulk parameters
have been tabulated elsewhere [9]. While Eq. 1 is useful as a guide, there are many
reasons it can be inaccurate. Surface spins have fewer near neighbors for exchange
coupling. Symmetry breaking at the surface leads to an additional anisotropy
contribution that can distort the NP spin configuration [10]. If the oxidation state
of surface atoms differs from that of the interior, as with metal NPs, the effective
Ms will be reduced compared with that for the bulk metal, even if the spins
are not canted. For materials with very large magnetocrystalline anisotropy, the
theoretical dcr could be hundreds of nanometers, but structural defects such as grain
boundaries or antiphase boundaries limit the experimentally observed domain size.
At the opposite extreme, with very low magnetocrystalline anisotropy, there is little
energetic cost if they are not perfectly collinear. Here the domain wall width is a
better estimate of the single-domain threshold.
In bulk ferromagnets magnetization reversal occurs through domain wall motion,
but in single-domain particles, the exchange-coupled spins remain parallel to one
another as they rotate coherently, as a macrospin [11, 12]. The switching field or
coercivity, Hc , is a maximum for particles at the largest monodomain size [13] and
can be predicted from an energy barrier model [14], where the barrier to reversal is
given by
Ms H 2
E = KV 1 − . (2)
2K
1/3
6kT B
dSP = , (3)
π K ln (τmeas /τ0 )
where τ 0 is the inverse of the Larmor precession frequency, ∼10−9 s, and τ meas is
the measurement time. The threshold temperature for superparamagnetism is called
the blocking temperature, TB , defined as
but it too will depend on the measurement time. For a superconducting quantum
interference effect device (SQUID) magnetometer, the time is ∼100 s, but Möss-
bauer spectroscopy and neutron scattering have measurement times of ∼10−7 s or
shorter. In magnetic hyperthermia, the frequency ranges from 100 kHz to 1 MHz,
and particles that look superparamagnetic based on SQUID magnetometry may be
blocked over the shorter time scales [2].
By definition, superparamagnetic particles do not interact with each other, and
the magnetization of an ensemble of superparamagnets, relative to its value at zero
temperature, is a Langevin function:
M 1
= L(x) = coth(x) − , (5)
M(0) x
Fig. 2 Langevin function fit of a dilute sample of 8.5 nm Fe3 O4 nanoparticles. Below the blocking
temperature of ∼65 K, the two branches of the loop have been averaged. (unpublished results)
20 Magnetic Nanoparticles 1015
This is a reasonable approximation if the particle spends the majority of its time
in the local or global ground state, rather than in a transition state. To understand
dynamics on shorter time scales (100 ns or less), the Landau-Lifshitz-Gilbert
equation provides a more accurate picture of precessional switching [16].
The view of magnetic NPs as macrospins is a helpful starting point, but real particles
can be more complex in many ways. Here we describe a few of the most common
differences.
The nanoparticles need not be chemically uniform. Most nanoparticles have a
surfactant or polymer coating that forms a diffusion barrier to oxygen, but does not
prevent oxidation of sensitive materials. Sudden exposure to air can cause magnetic
metal NPs of Fe or Co to catch fire, but gradual exposure leads to a core-shell
structure. Metals oxidize by O2 adsorption and dissociation on the surface, followed
by metal ion migration to react and nucleate the metal oxide. The oxide shells
surrounding magnetic metal cores are usually polycrystalline, with ∼1–2 nm grains
having different crystallographic orientations, relative to the interior. In extreme
cases, the Kirkendall effect is observed, in which the particles become hollow, and
all that remains is a porous metal oxide shell [17]. Since Fe and Co oxides can be
magnetically ordered. Bulk Fe3 O4 and γ-Fe2 O3 are ferromagnetic, while FeO is
antiferromagnetic. Bulk CoO and Co3 O4 are antiferromagnetic. When these phases
form a thin shell around a metallic core, there can be exchange bias between metal
core and oxide shell spins [18], just as in bilayer thin films [19, 20]. However, the
behavior is much more complex due to the polycrystalline nature of the shell, which
leads to a wide variety of superexchange interactions within a single particle.
Many NPs show reduced Ms compared with that of the bulk material. In some
cases thin magnetic films and NPs are said to have a “dead layer” without ascribing
an origin, but there are many hypotheses about the underlying reasons. Some are
inherent in the symmetry breaking at the surface. This introduces a new contribution
to the anisotropy that can distort the spins from the completely parallel configuration
of the ideal monodomain particle. Negative surface anisotropy favors spins that lie
in the plane of the surface [10, 21]. Positive surface anisotropy favors perpendicular
orientation [10]; at moderate values this leads to surface distortion akin to a
point dipole pattern. If the NP cores are amorphous, the surface anisotropy will
dominate [22]. Many groups have assumed that the surface anisotropy contribution
1016 S. A. Majetich
Nonaqueous Syntheses
For studies of fundamental physics where monodispersity and high crystallinity are
important, hydrophobic syntheses have been most promising. Here a high boiling
point organic solvent is used to control the thermal decomposition of organometallic
precursors and therefore the nucleation threshold. This is done in a dilute dispersion
in the presence of surfactant molecules to prevent coalescence. The most commonly
used surfactant for magnetic nanoparticles is oleic acid, which has a carboxylic acid
group that binds to magnetic metal atoms at the NP surface. With Au and CdSe
NPs, surfactants with thiol groups are used because they form strong bonds to Au
or Cd. With magnetic nanoparticles there are no surfactants that form such strong
20 Magnetic Nanoparticles 1019
Fig. 3 Transmission electron microscopy images of different types of Fe3 O4 nanoparticles. (a)
Spherical NPs with a size of 13 nm prepared by high-temperature decomposition in nonaqueous
solvent, (b) cube-shaped NPs, (c) NPs made by aqueous coprecipitation, and (d) magnetic beads
containing NPs. (Note: distortion of the beads is due to particle melting of the polystyrene matrix
by the electron beam)
bonds, and there will be an equilibrium between adsorbed and desorbed surfactant
on the NP surface. For this reason care should be taken when diluting a dispersion of
magnetic NPs with a pure solvent. The NP size can be controlled to some extent by
temperature, reaction time, and the precursor to surfactant ratio [50–52]. However,
most of these syntheses have a sweet spot, and it is difficult to find a single synthesis
that can be tuned over a wider size range. The upper limit is often set by the density
of the compound or alloy. Using the same surfactant molecules, it is more difficult to
sterically stabilize dense materials (e.g., Au or FePt) than lighter ones (e.g., Fe3 O4
or γ-Fe2 O3 ). Another problem is the occurrence of antiphase boundaries. Some of
the iron oxide syntheses proceed through a FeO (wustite) NP precursor that is then
transformed into Fe3 O4 . In larger FeO NPs, there can be multiple nucleation sites,
which can lead to antiphase boundaries when the grains meet [25]. The Fe-O-Fe
superexchange across the antiphase boundary is antiferromagnetic and can make
the NPs multi-domain even when they are very small. This can lead to greatly
1020 S. A. Majetich
Aqueous Syntheses
Most magnetic NPs for biomedicine are spinel oxide NPs such as Fe3 O4 or
γ-Fe2 O3 made in aqueous solution [53–56]. In this coprecipitation method, metal
salts are dissolved, and a base such as ammonium hydroxide is used to generate
a metal oxyhydroxide phase that loses water to form a spinel ferrite. The reaction
temperature limits the crystallinity of the NPs, though improvements are achieved
by calcining, heating near the boiling point of water, or through hydrothermal
synthesis where the particles are heated under pressure in an autoclave. Once the
NPs are formed, a surfactant is usually added in order to aid in stabilization. Since
iron oxide is amphoteric, collisions between uncoated particles can neutralize the
surface charge. Without surfactant coating a typical charge-stabilized dispersion
will show noticeable settling within a day. Compared with nonaqueous solution
syntheses , the coprecipitation and hydrothermal methods yield particles with
greater polydispersity and lower crystallinity. Depending on the method and particle
size, the specific saturation magnetization of these particles can be significantly
lower than that of the bulk iron oxide.
Most applications of magnetic nanoparticles rely on their small size, which enables
them to be dispersed in liquids and moved with a magnetic field. These applications
depend on several magnetic properties, but the most central is the magnetic moment
| −
→
μ |= Ms V . The magnitude of μ depends on the material the particle is made
1022 S. A. Majetich
−
→ 2μ cos θ μ cos θ
H = 3
r̂ + θ̂ , (7)
r r3
where θ is the angle between the moment μ and the point of interest. This local field
shifts the resonance frequency of nearby water molecules and enables the removal
of the background signal from water molecules so that the response of protons (1H)
in tissue can be seen more clearly.
In magnetic separation, a spatially varying external magnetic field is used to
apply a force on the magnetic moment:
F = (μ · ∇) H (8)
chemotherapy drugs [78]. Cancerous tumors often develop hypoxic regions where
chemotherapy drugs do not penetrate as effectively. A novel suggestion has been
to utilize magnetotactic bacteria for targeting [79]. Normally these bacteria use the
earth’s magnetic field to swim to the aerobic-anaerobic boundary in the sediment of
a pond. When magnetotactic bacteria are bound to drug-containing liposomes, 55%
were able to penetrate the hypoxic regions [79].
Finally, there is a mechanical stimulation-based approach to cancer treatment
involving magnetic nanoparticles [80]. Here micron-sized magnetic disks are
introduced into cultures of tumor cells and then exposed to magnetic fields to apply
an AC magnetic torque . In vitro studies show that this increases cell death. This
work is in the early stages and many questions remain about how to extend it to
in vivo application, but clearly there are multiple ways that magnetic particles can
influence cells.
Magnetic Hyperthermia
Magnetic hyperthermia has become the most popular area for research on biomedi-
cal applications of magnetic NPs. Local magnetic hyperthermia was first used over
60 years ago [81], and in recent years there have been ongoing clinical trials,
but most work is in the preclinical stage. When cancerous tissue is exposed to
temperatures of 42–45 ◦ C, chemotherapy and radiation become more effective.
Temperatures above 50 ◦ C can kill cells directly. The challenge is to kill cancerous
cells but not healthy ones, so localized heating is important. Magnetic NPs bound
to a tumor offer a mechanism to achieve localized heating. The area of a hysteresis
loop corresponds to an energy dissipated as heat. When the loop is cycled by an
AC magnetic field, this leads to power dissipation. The NPs used in hyperthermia
are often referred to a superparamagnetic, but as shown in Eq. 3, this classification
depends on the measurement time. NP sizes that are superparamagnetic at nearly
DC frequencies used for magnetometry (τmeas −1 ∼ 0.01 Hz) may be blocked if
measured at AC frequencies typical of hyperthermia (100 kHz–1 MHz). Viewed
in terms of Eq. 6, there will be a blocking frequency that depends on size and
effective anisotropy. The usable frequency range is determined by the requirement
that H0 f ≤ 4.85 × 108 Am−1 s−1 [82], where H0 is the amplitude of the AC
magnetic field. Above this threshold the AC field causes nerve stimulation. When
NPs are dispersed in a liquid, Brownian rotation, where the whole particle rotates,
can also change the magnetic moment direction, so both Néel and Brownian rotation
must be considered. The rotational diffusion relaxation time τ B is given by.
clinically meaningful parameter. SAR values of nearly 2.5 kWg−1s at 520 kHz with
a field amplitude of 29 kAm−1 have been reported [83].
The Intrinsic loss power (ILP) defined as SAR/fH0 2 is convenient for comparing
results from measurements with different frequencies and field amplitudes, and it
is meaningful for comparing the intrinsic effects of the NPs. The SAR is measured
by calorimetry, but there are numerous pitfalls that can make it difficult to compare
results from different laboratories [84]. Optical thermometers must be used to avoid
eddy current heating that would arise in a thermocouple sensor. Because the thermal
insulation is imperfect, the heating is measured under nonadiabatic conditions, and
the initial slope of the temperature versus time graph should be used. Data should
be collected as a function of NP concentration. While dense assemblies heat faster,
high concentrations of Fe are toxic [85]. Concentrations of a few mg/mL are most
relevant for clinical application.
There have been numerous simulations of magnetic heating based on combi-
nations of Brownian rotation and Néel-Brown or Stoner-Wohlfarth behavior, all
aiming to maximize the SAR. More sophisticated models have considered the roles
of the size distribution, NP concentration, and magnetic field amplitude [86–88].
Ex vivo experiments have been providing new insights about how magnetic
hyperthermia works. In multicore NPs, the strong coupling between nearby cores
impacts the heating [89, 90]. When NPs are internalized by cells, the SAR is reduced
[91, 92], presumably due to increased viscosity within the cell that would reduce
the Brownian contribution to heating. However, another study reported no change
in the AC susceptibility when NPs were inside cells and after cell lysis [93]. It is
possible that after incorporation into magnetosomes within the cell, the NPs cannot
be redispersed even when the cell walls are ruptured. This would be possible if much
of the NP coating were removed.
According to classical models of heat diffusion, the temperature change should
scale with the size of the heat source, and the temperature increase from a single
nanoparticle should be on the order of 10−8 K [94]. Temperature is an equilibrium
property, but magnetic heating is intrinsically nonequilibrium. A single particle may
be ineffective for hyperthermia, but together a concentration of NPs can raise the
local temperature [95]. One of the most intriguing experimental results has been
the observation of increased cell death after exposure to an AC magnetic field even
when no temperature rise is detected [96]. It is the local power deposition, on the
cellular scale, that leads to cell death. The mechanism by which the local heating
triggers biochemical response that leads to cell death is still unknown, but could
be associated with heat shock proteins. Hyperthermia has been shown to control
ion channel and neurons in microorganisms [97]. The mechanism involved remains
unclear, since ion channels can also be controlled by magnetic forces on attached
magnetic beads, without heating [98].
There have been clinical studies of hyperthermia for 15 years [99], but there are
still many challenges. It is far easier to generate a high amplitude magnetic field in a
laboratory rat than deep inside a person. The wavelength of the AC electromagnetic
field radiation is much larger than the size of a person, so it is difficult to focus
1026 S. A. Majetich
the energy on the tumor target. Most of the initial studies have aimed at tumors of
the breast, prostate, neck, and esophagus, where it is possible with the help of a
probe to achieve therapeutic levels of the AC field. The electrical permittivity and
magnetic permeability of fat and muscle tissue are different [100], and the tissue
structure of the patient must be imaged and modeled [101, 102] to optimize the
hyperthermia dosing treatment. The location of the tumor is also important, because
blood perfusion counteracts the effect of local heating. Magnetic hyperthermia has
the potential to transform certain cancers from life-threatening to chronic diseases
requiring periodic treatment. However, there is still a fair way to go before such
treatment becomes routine.
Magnetic particle imaging can detect moving particles in vivo and so can be used
to monitor biological function in real time. Consider the S-shaped magnetization
curve of a superparamagnet. The magnetization M will oscillate in time in response
to a sinusoidally varying magnetic field. When the field amplitude is high, the
magnetization approaches saturation, so M(t) is not sinusoidal, and a Fourier
transform of the wave would have multiple harmonics. If this process is repeated
with a large DC magnetic field together with the AC field, the AC amplitude can
be much lower and still generate higher harmonics. One of these harmonics is used
to detect the signal from the magnetic particles. Here the particles are micron-sized
polymer beads containing superparamagnetic particles. Frame rates of 50 Hz have
been used to image particles passing through a live mouse heart [103].
While MPI is not a commonly used technique, it has great potential. An
intriguing possibility is to combine it with hyperthermia [104]. Here the MPI field
gradients saturate magnetic NPs everywhere except in a small volume. An AC
magnetic field is then applied for hyperthermia, but only NPs that are not already
saturated can respond , thereby localizing the heating. NPs with an SAR of 150 W/g
were able to selectively heat regions spaced by 3 mm, with a concentration of 5 mg
NP per g of tumor.
The nuclear spins of hydrogen atoms act like paramagnets that have a very high
saturation field. Because of this there is only a slight imbalance between spin-up
and spin-down populations even in large magnetic fields. However magnetization
dynamics are sensitive to the imbalance and can be used to distinguish different
chemical and magnetic environments. Magnetic resonance imaging (MRI) is spatial
mapping of nuclear magnetic resonance (NMR). Ferromagnetic resonance of
electron magnetic moments in a ferromagnet typically occurs at GHz frequencies,
but NMR is commonly in the MHz range, with DC magnetic fields of 1.5–3.0 T.
In micromagnetics the Landau-Lifshitz-Gilbert equations is used to describe
20 Magnetic Nanoparticles 1027
∂Mz −
→ − → M s − Mz
= −γ M × B = (10)
∂t z T1
and
∂Mx,y −
→ − → Ms − Mx,y
= −γ M × B = . (11)
∂t x,y T2
Here the static magnetic field B0 is applied in the z-direction, and an rf magnetic
field pulse is applied to rotate the magnetic moments by 90◦ . They precess about the
field as they relax back toward B0 . The rate of relaxation is quantified by the longi-
tudinal relaxation time T1 and the transverse relaxation time T2 . The total magnetic
field B is the sum of B0 and the rf field, which are the same everywhere, plus an
effective magnetic field due to moving electrons, which varies spatially depending
on the local H atom environments. Contrast agents are frequently used to enhance
these differences. T1 contrast agents such as Gd diethylaminetriamine pentaacetate
(Gd DTPA) cause a large decrease in the T1 of protons in water molecules due
to the large Gd3+ magnetic moment. Water is abundant, but the signal from water
molecules provides little information about tissue damage. Magnetic NPs containing
Mn2+ , such as Mn ferrite [105, 106] have also demonstrated potential as T1 contrast
agents, as have Fe3 O4 coated with zwitterion Gd3+ complexes [107], but most NP
contrast agents are iron oxide and have greater effect on T2 of water molecular
protons [106]. T2 is associated with dephasing, whereby different moments precess
at slightly different rates. Here the NP increases dephasing because it generates
an additional magnetic field nearby. The figure of merit for contrast agents is the
relaxivity, which is the change in T1 or T2 per concentration of contrast agent.
Gd DTPA is still the dominant contrast agent, but some people, such as dialysis
patients, cannot tolerate it, and here NP contrast agents are a good alternative. The
NPs used as MRI contrast agents are generally small and not part of magnetic beads
so that they can modify the relaxation of many nearby water molecules. The spatial
resolution of MRI depends on the magnetic field strength and is typically ∼50 μm
for a 3 T field.
The body has natural Fe-containing nanoparticles, mainly in the form of ferritin,
an 8 nm antiferromagnetic iron oxyhydroxide core coated with a protein shell [108].
Uncompensated spins and/or spin canting enables magnetic detection. Because of
this, MRI can be used to diagnose diseases such as thalassemia or iron overload
disease [109], thereby avoiding the need for liver biopsies. The MRI scan is not only
noninvasive but also more accurate because the Fe is not distributed homogeneously
within the liver. Magnetite and maghemite nanoparticles have been found in the
brains of Alzheimer’s patients, but the mechanism of their formation is not yet
understood [110]. Though the abundance is not high enough for MRI detection, the
correlation of magnetic nanoparticle formation and a range of neurodegenerative
1028 S. A. Majetich
Ferrofluids
Fig. 4 Ferrofluid spikes (a) top view; (b) side view. Here a commercial ferrofluid of iron oxide
nanoparticles in organic solvent is placed in a glass container that is placed on top of a neodymium
iron boron magnet. The density of spikes and their direction roughly follow the magnetic field lines
from the permanent magnet. (Photos courtesy of A. Abdelgawad)
20 Magnetic Nanoparticles 1029
ferrofluid, which gives rise to the collective response, but also the lack of resistance
to a shear force. The particle diameters range from 5 to 20 nm and are most
commonly iron oxide [114]. The NPs are superparamagnetic, so that the moments
will quickly randomize after the removal of an applied field. Typical ferrofluids
have ∼5 volume percent particles, based on the average core size. With much lower
concentrations, the particles are too far away from each other to induce collective
movement of the fluid droplet. At much higher concentrations, the dispersion
becomes unstable.
The earliest application of ferrofluids in 1938 used the Bitter method [7], but with
colloidal dispersions of Co particles [115] instead of a powder, for the observation
of domain walls by depositing ferrofluid on a ferromagnet surface. Here the fringe
field gradient above the domain walls attracts the particles of the ferrofluid. Today
ferrofluids find frequent use in rotary vacuum seals. An external magnet holds
the ferrofluids in place around a rotating shaft, which can then apply torque
without breaking vacuum. Ferrofluids for this application require low vapor pressure
solvents. Because a ferrofluid has a higher overall density than most liquids, it is a
good heat conductor [116]. At high power there is considerable heat generation
in audio speakers due to resistive heating of the voice coils. When the coils are
immersed in a ferrofluid, which is held in place by permanent magnets, the heat can
be carried away more efficiently than by air cooling alone. The density of the fluid
also helps to damp lower frequencies and unwanted resonances.
A new but promising application of ferrofluids is in magnetic cooling through
the magnetocaloric effect, where temperature changes of up to 28 ◦ C have been
achieved [117]. Here the ferrofluid is made of manganese zinc ferrite NPs that have
a Curie temperature slightly above room temperature. An aqueous dispersion of the
particles flows through a closed coil with a heat sink in one region and a magnetic
field gradient in the other. At 300 K the NPs are ferromagnetic, and due to their
size, superparamagnetic, the ferrofluid is attracted by an external permanent magnet.
When heated above Tc , the particles are only paramagnetic and are able to diffuse
away from the magnet. This leads to self-pumping behavior that reduces the energy
required to cycle the ferrofluid coolant between the heat source and heat exchanger.
Given the environmental concerns about fluorinated and chlorinated hydrocarbon
coolants, magnetic cooling could become the major application of ferrofluids in the
future.
Modern hard disk drive media are not made of chemically synthesized nanopar-
ticles, but the concept of a monodomain magnet is still relevant. The media
consist of a monolayer of monodomain magnetic grains embedded in a dielectric
matrix. The media are deposited by co-sputtering onto a seed layer chosen to favor
crystallographic orientation that leads to an easy axis perpendicular to the substrate.
The matrix prevents exchange coupling between grains, and the anisotropy is large
enough that magnetostatic interactions have minimal effect on Hc . A bit contains
multiple grains that are ideally magnetized in the same direction. Variations in grain
size and crystallographic or magnetic orientation lead to variations in the magnetic
fringe field generated by the bit that is detected by the read head. The signal-to-noise
ratio is proportional to the square root of the number of grains per bit. In order to
shrink the bit size without compromising performance, the grain size was reduced.
In the 1990s there was concern about reaching the superparamagnetic limit
with further reduction in grain size, which would be at ∼10 nm for hexagonal Co
[118]. The ability to store information for 10 years is estimated using an energy
barrier model based on monodomain NPs [14]. The thermal stability parameter
= KV/ kB T is a figure of merit and will ideally be ∼60–80. The problem of the
superparamagnetic limit was overcome by shifting to higher anisotropy alloys such
as CoCrPt, used today with an average grain size of 6.5–8 nm, and L10 FePt, which
is used for heat assisted magnetic recording (HAMR). The high magnetocrystalline
anisotropy of L10 FePt could enable grains as small as 4 nm to be used [119].
Exchange bias has been proposed as a method to enhance stability [120], and
exchange-coupled composite media [121], where the grains are coupled to an
underlayer, has been put into practice. Heat-assisted magnetic recording (HAMR)
media [122] are based on sub-10 nm grains of L10 FePt, where chemical and
structural order are important for uniformity in both the switching field and the
Curie temperature.
The energy barrier model of magnetization reversal assumes an attempt fre-
quency related to the Larmor precession rate. There have been proposals for faster
switching [123], and there has been a demonstration of precessional switching
without thermal activation using ps pulses from a synchrotron, which generate large
magnetic fields ∼20 T [124]. However, extending this to use in hard disk drives is
still a long way off.
paper, the nanoparticles were annealed in order to transform the as-made face-
centered cubic (fcc) or A1 phase into the face-centered tetragonal (fct) or L10 phase,
since the surfactant coating decomposes at temperatures below that of the phase
transformation [125]. A coercivity of 480 kAm−1 was achieved, but at the expense
of sintering the 4 nm particles into an irregular assembly. Many researchers have
since investigated FePt nanoparticles, due to the potential technological significance
for magnetic recording. While this potential has not yet been realized, the results of
these studies provide insight about magnetic alloy nanoparticles.
There were two main synthetic approaches. The first sought to reduce the
temperature required to transform the particles into the L10 phase. The addition
of third elements (Cu, Ag, W) to the FePt during synthesis lowered the minimum
temperature needed to observe the L10 phase. However, the particles were irregular
in shape afterwards. The rate of A1 to L10 transformation was increased because
self-segregation of the third element created vacancies within the FePt. The second
approach was to embed the A1 phase NPs in a matrix that was immiscible to Fe
and Pt, such as MgO [126], NaCl [127], or alumina [128], and then heat to the
temperature needed to obtain the L10 phase. Later work applied this idea to prepare
particles that could be redispersed in liquids after electrocatalysis in acid [129].
However, while the coercivity is large these particles are not monodisperse enough
to self-assemble.
It is more challenging to prepare the phase in nanoparticles than in thin films.
The high coercivity L10 phase has a balance of ferromagnetic and antiferromagnetic
interactions [130], and site occupancy disorder disrupts this balance. The surfaces
of the chemically prepared nanoparticles are often Pt-rich [29, 131]. Recent work
using tilt series images from scanning transmission electron microscopy (STEM)
together with 3D reconstruction was able to locate Fe and Pt atomic positions within
a single 8.4 nm Fe0.28 Pt0.72 nanoparticle [132]. The sample had been annealed under
conditions expected to lead to partial transformation from the A1 phase into either
the L10 phase or the chemical ordered Fe3 Pt or FePt3 L12 phases. The analysis
revealed five distinct L12 grains, three L10 grains, and one Pt-rich A1 grain.
The current outlook for magnetic recording media based on self-assembled
arrays of FePt nanoparticles is not promising. In order to self-assemble, the
magnetic interactions along particles must be weak and isotropic, which would
make it difficult to use self-assembly after phase transformation. The A1 to L10
phase transformation problem is solvable. Crystallographic orientation, which is
critical to uniformity in the magnetic media, will not be easy to achieve starting
from surfactant-coated nanoparticles. That said, FePt continues to be a fascinating
system, and FePt nanoparticles may find applications elsewhere, either in catalysis
or in ex vivo biomedical applications.
One of the most important lessons of the extensive research on FePt NPs is
that even a binary alloy can be hard to synthesize with high homogeneity and
monodispersity. Materials that are nontrivial to prepare in bulk or as thin films,
such as Heusler compounds or Nd2 Fe14 B, are going to be much more challenging
to make in nanoparticle form, if milligram quantities are desired.
1032 S. A. Majetich
Core-Shell NPs
By core-shell NPs we refer to structures where both the core and shell are magnetic
phases. When both the core and shell are magnetic and in direct contact, exchange
interactions dominate, which leads to strong coupling. For a more extended
discussion, readers are encouraged to consult a focused review on this topic [133].
Here we will summarize the main ideas of exchange bias in NPs and highlight some
recent results.
The first core-shell NPs studied had Co cores and CoO shells [134]. Air oxidation
nucleates CoO formation at different locations on the surface, so the shell is
polycrystalline, and there is a range of crystallographic relationships between the
core and shell phases. Since metal atoms migrate to the surface to react with
adsorbed oxygen due to the Kirkendall effect, in extreme cases this can lead to
partly hollow particles [17]. Theoretically a hollow shell could have a vortex rather
than single-domain structure [135], but this has not yet been observed, presumably
because of roughness of structural inhomogeneity in the shell that creates pinning
sites. FePt/MnO dumbbells start out as core-shell NPs, but upon heating phase
segregate into two NPs with a shared interface [136, 137]. Due to exchange bias
effects, they share many of the properties of core-shell NPs.
Most core-shell NPs have a ferro- or ferri-magnetic core and an antiferromag-
netic shell, where the anisotropy of the AF phase is greater than that of the FM
or ferrimagnetic (FiM) phase. In this case an exchange bias effect can be seen in
hysteresis loops, whereby there is a loop shift after cooling in a large magnetic
field, together with a higher coercivity than in the FM core alone. Because of
these features, core-shell NPs have been proposed for use in magnetic recording
media [120]. However, several factors are limiting, including the orientation issue
described for FePt. Specific to exchange-bias systems is the requirement for some
sort of training of the system. This could involve field cooling through the Néel
temperature TN of the AF or exposure of the system to a large magnetic field for
a long time. This is theoretically possible but would require a core-shell NP with a
very high anisotropy AF that has a high TN . However, thermal fluctuations will tend
to relax the ordering faster in a NP than in a thin film. In real particles interfacial
roughness would lead to a broad range of exchange bias fields [138].
Since there are multiple magnetic oxide phases, it is possible to prepare core-
shell NPs with two oxide phases. Of particular interest are Fe3 O4 /γ-Fe2 O3 , which
are both ferrimagnetic, and MnO/Mn3 O4 , where the core is AF below TN = 118 K
and the shell is ferrimagnetic below 43 K [139–141]. In both cases the two phases
have the same structure and differ only in the vacancy concentration. It is therefore
feasible to have a single crystal core-shell particle with epitaxial interfaces. While
small regions with epitaxy have been seen for MnO/Mn3 O4 [141], these do not
extend throughout the NPs. The MnO lattice can be transformed into Mn3 O4 by
cation migration, and this will introduce defects. Low-temperature small angle
neutron scattering (SANS) measurements on ordered assemblies of such NPs do
not show evidence of a uniformly magnetized shell or NP, unlike similar Co/CoO
NPs. It is believed that defects such as antiphase boundaries [25] limit the size and
20 Magnetic Nanoparticles 1033
uniformity of the regions that have exchange bias coupling. With γ-Fe2 O3 , evidence
of gradual transformation of Fe3 O4 to γ-Fe2 O3 is observed by a color change
from black to reddish brown. NPs tailored for biomedical applications, which are
dispersed in water, degrade more rapidly. However, there is no abrupt boundary
between the Fe3 O4 and γ-Fe2 O3 phases, suggesting a gradation of the vacancy
concentration. Most “magnetite-like” NPs have an average vacancy concentration
on the order of 5%. In contrast, there are significant exchange bias effects in NPs
with antiferromagnetic FeO cores and ferromagnetic Fe3 O4 shells [142].
While there have been hundreds of papers about core-shell NPs with exchange
bias between ferro- (or ferri) and antiferromagnetic phases, there are relatively few
on exchange spring NPs with coupling between two ferromagnetic phases with
large and small anisotropy. This is complicated for several reasons. First, many hard
magnetic materials such as Nd2 Fe14 B and Sm2 Co17 have complex crystal structures
that are difficult to achieve by chemical synthesis. From this point of view, L10 FePt
is by far the simplest of the hard magnetic materials, and we have seen that it is
nontrivial to make in NP form. Second, the high oxidation sensitivity of rare earth
materials makes it difficult to find soluble reducing agents. Third, strong exchange
coupling requires lattice matching. Core-shell NPs with Co grown around L10 FePt
have been reported [143]. However, the high coercivity FePt requires coating with
MgO prior to annealing, followed by removal of the MgO, and deposition of the
Co shell. This work builds on earlier research where nanocomposites were prepared
by sintering mixtures of FePt and Fe3 O4 NPs [144]. Until methods are developed
so that large quantities of these NPs could be prepared quickly and economically, it
remains a challenge to apply this approach on a large scale.
Even if the NP were made in vacuum and had no chemically distinct coating, the
exchange stiffness and anisotropy would differ from the bulk values because of the
surface. Eq. 1 defines the maximum monodomain size for an ellipsoidal particle
in terms of the saturation magnetization Ms , the effective anisotropy K and the
exchange stiffness A, of the bulk ferromagnetic material. The magnetic moment
per atom has been measured for small Fe, Co, and Ni clusters as a function of size
and shows deviations from the bulk value that oscillate with the cluster size up to
about 500 atoms [47]. These clusters were prepared in a mass-selected cluster beam
and have no surface ligands. However, it is unclear that surface atoms on a larger NP
behave like atoms in a small cluster. Symmetry breaking at the surface contributes
to changes in K in complex ways, depending on whether energy minimization
favors spins perpendicular or parallel to the surface. Since it is impossible for all
spins to be parallel to the surface, the latter condition leads to vortices near the
north and south poles of the NP. In both cases the spin configuration is nonuniform
within the particles unless magnetocrystalline or shape anisotropy dominate surface
contributions. The surface atoms will have fewer magnetic neighbors and therefore
reduced exchange energy per atom leading to lower magnetic exchange stiffness A,
1034 S. A. Majetich
which is proportional to the Curie temperature [8]. The symmetry breaking could
also give rise to Dzhaloshinskii-Moriya contributions to the exchange, so that the
spins need not be parallel. Deviations in Tc have been reported, but interpretation
of experimental results has been tricky. For bulk ferromagnets, Tc is found by
measuring the spontaneous magnetization as a function of temperature in small
magnetic fields and then extrapolating to H = 0, but the spontaneous magnetization
of an ensemble of NPs is zero above the blocking temperature. At TB , spins within
a NP are still coupled, but the moments of different NPs are randomly oriented. At
Tc the spins within a NP are random. Since purely dipolar ferromagnetism has been
observed for NP arrays even close to Tc [42], measurements of the exchange-based
Tc would require measurements on dilute assemblies. This is one possible origin of
the disagreement between reports of increased Tc for assemblies [145, 146] and
decreased Tc for single Ni NPs < 100 nm measured using interference electron
microscopy [147], a technique similar to electron holography. The other possible
artifact arises from deviations in site occupancy. In bulk spinel ferrites, equilibrium
site occupancy is reached after annealing at ∼1000 ◦ C, far higher than any solution
phase synthesis used to prepare NPs.
Most of the nanoparticles discussed here have surface coatings that could
potentially change the magnetic moment of the surface atoms. This effect is
usually small in the case of magnetic oxides such as spinel ferrite (e.g., Fe3 O4 )
NPs coated with organic surfactant molecules such as oleic acid (OA). Here the
carboxylic acid –COO− group of the OA molecule forms two bonds to a surface
Fe2+ or Fe3+ ion, whereas Fe ions in the interior are surrounded by a tetrahedral
or octahedral arrangement of O2− ions. Fe-O-Fe superexchange is responsible
for the ferrimagnetism of spinel ferrites, and there are both ferromagnetic and
antiferromagnetic contributions that depend on the Fe-O-Fe bond angle [148]. Since
OA molecules bind to single surface ions, no additional superexchange pathways are
formed, and the balance is unchanged.
Some of the first evidence for deviations from the macrospin model came
from Mössbauer spectroscopy of spinel ferrite nanoparticles [149, 150]. Mössbauer
spectroscopy is an extremely sensitive probe of the local Fe environment; it can
differentiate the ionic charge, the lattice site, and whether the spin is magnetically
stable (on a 100 ns time scale) or superparamagnetic. In the absence of a magnetic
field, the spectrum for Fe3 O4 nanoparticles can be described by sextet contributions
from Fe3+ ions in tetrahedral (A) sites and Fe2+ and Fe3+ ions in octahedral (B)
sites. For γ-Fe2 O3 nanoparticles, which have no Fe2+ ions, there are two subspectra.
However, in a 5 T field, the same sample has three sextet subspectra, suggesting
that some spins have canted in the high field [150]. The effect has since been
observed in high field Mössbauer spectroscopy for a wide range of spinel ferrite
nanoparticles [151–155]. Surface spins were presumed to be most likely to cant,
but direct evidence came from small-angle neutron scattering, which is sensitive
to the length scale of magnetic order [156]. Using polarization analysis of the
scattered neutrons, three-dimensional magnetic correlations can be differentiated
[157]. Fe3 O4 nanoparticles with a size of 9 nm were found to have uniform
magnetization in zero field, but at moderate fields of 1.4 T, the surface spins formed a
20 Magnetic Nanoparticles 1035
coherent shell that canted coherently. The effect is reversible, and the shell thickness
is temperature-dependent. Subsequent measurements have found minimal distinct
surface canting in CoFe2 O4 NPs that have high K and Tc [158] but strong surface
and core canting in NPs with low K and Tc [159]. A combination of high-resolution
electron energy loss spectrometry and density functional theory calculations has
shown differences in the density of states at the edges of NPs in a high magnetic
field associated with spin canting [160].
While there is ample evidence for spin canting in high fields, there is still debate
about the driving force. Studies of different materials will help to differentiate the
effects of disorder and symmetry breaking. To date spin canting in zero magnetic
field has not been demonstrated, but as characterization techniques improve in
sensitivity and spatial resolution, it may someday be possible to experimentally
verify the predictions of surface anisotropy models [10].
a NP in the right position. Conductive atomic force microscopy (CAFM) has been
used to measure 18 nm Fe3 O4 NPs deposited on a magnetic thin film that acts as the
reference layer [172]. Here superparamagnetic fluctuations in the magnetoresistance
varied depending on the applied magnetic field. However, there are still no reliable
methods to crystallographically orient the chemically prepared particles, which
would enable single particle measurements of anisotropy. Cube-shaped NPs would
be a natural choice, since they would lie preferentially along a (100) plane.
Magnetic force microscopy (MFM) has been a versatile tool for characterizing
domain structures in thin films, but it relies of the force on the tip magnetic moment
due to the vertical component of the fringe field generated by the sample, and that
has limited its use with NPs. While reduced lift heights can be used, with a spherical
NP, it can be difficult to distinguish topographic and magnetic contrast. To be
detectable by MFM, the NP must be magnetically stable. 715 nm × 148 nm × 50 nm
thick permalloy patterns with magnetic moments ∼10−16 Am2 have been measured
[173], along with 50 nm diameter dots patterned into perpendicular Co/Pd multilay-
ers [174].
Electron microscopy is a common technique for imaging NPs, and magnetic
electron microscopy has been applied to single NPs. Electron holography is sensitive
to the in-plane magnetization and can be used for quantitative measurements, but
it requires a specialized microscope with an electron biprism. Flux from individual
20 nm Co in rings NP has been imaged by electron holography [175], as have chains
of ∼45 nm magnetite NPs that form naturally in magnetotactic bacteria [176]. The
estimated moment of a chain of ∼20 NPs was 7 × 10−16 Am2 , but the features
of individual particles could be seen. Fresnel Lorentz microscopy [41] and electron
holography [42] have been applied to NP arrays and correlated with the conventional
transmission electron microscopy images of the same regions, but single NP features
were not observed. With improvements in instrumentation, together with modeling,
imaging of sub-10 nm NPs is feasible.
In the biomedical area, single magnetic beads have been detected by various
methods. Changes in magnetoresistance due to the attachment of a single magnetic
bead have been demonstrated [177]. While single NPs have been detected by
magnetoresistance [172], this is less likely to translate to biomedical use because
the viscous drag is inversely proportional to the particle diameter. It is easier to
guide a magnetic bead to the attachment site by the sensor. The performance of
magnetoresistive sensing systems is measured in terms of the concentration of
analyte they can detect, rather than the size of the sensor or the number of beads.
Here nonmagnetic factors such as the number of selective binding surface receptors
are likely to improve performance. For MRI contrast from a single bead has been
detected [178]. However, the volume spatial resolution of MRI is still lower than the
volume of a 5 micron bead. MRI can be used to track the location of a bead over
time, but smaller particles would not give better resolution.
In the Néel-Brown model , switching is thermally activated, and the switching
time is proportional to the Larmor precession time. Direct precessional switching
has been shown to be faster [142] but requires a short pulse of a very large magnetic
field. While the initial experiments were done with X-rays at a synchrotron, ultrafast
20 Magnetic Nanoparticles 1037
laser pulses can also lead to rapid switching [179]. Here the magnetization reversal
involves a new mechanism where the size of the magnetic moment changes linearly
over time, rather than remaining constant. Theoretical models predict that short
laser pulses could be used to switch L10 FePt nanoparticles [180], though the linear
reversal mechanism would only apply if there were heated to within a few degrees
of their Curie temperature [181].
In summary, research on magnetic nanoparticles covers many different areas,
both fundamental and applied. Magnetic nanoparticles are an intriguing model
system because they act in many ways like giant spins, though the detailed
spin configurations are more complex. In addition to their relevance to magnetic
recording media, they have found application in medical imaging, diagnostics, and
therapies. Research on magnetic nanoparticles is advancing in different, separate
directions: physics-oriented efforts that focus on the spin configuration, switching,
and magnetization dynamics and interdisciplinary work where the nanoparticles
are a tool that can be manipulated with magnetic fields to understand or control
biological systems.
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1046 S. A. Majetich
Contents
Nanocomposite materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1048
Thin-film structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049
Bilayers and multilayers with engineered properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049
2D electron gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056
Nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
Template-grown nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
Edge states in 2D topological insulators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
Lithographically-patterned 2D ferromagnetic arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
Hysteresis of nano/microdisc arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
Artificial spin-ice structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
Artificial atoms and the Coulomb blockade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
Coulomb blockade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
Single electron spintronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1065
Single atom manipulation and measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1068
Quantum corrals and wave function imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069
Magnetism at the atomic scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1070
Anisotropy of individual atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1070
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1071
Abstract
C. H. Marrows ()
School of Physics and Astronomy, University of Leeds, Leeds, United Kingdom
e-mail: [email protected]
methods. There is a tendency towards control of the material over a larger number
of dimensions as we progress through this list. These different metameterials
also represent increasingly fine levels of control over the atomic-scale structure
that is to be engineered to yield the desired properties. There is also a trend
from bottom-up to top-down assembly methods as we move through this
series of material form factors, indicating the increasing difficulty of imposing
structure on matter. Nevertheless, the emergent properties become more and
more remarkable, and less easy to achieve in other ways, making the mastery
of these difficulties very rewarding, both scientifically and technologically.
Nanocomposite materials
Composites are systems where distinct materials are intermixed, whilst maintaining
their own separate identities, in order to provide complementary desired properties.
Nanocomposites are those where this mixture of phases occurs at lengthscales that
are substantially below 1 μm. In the field of permanent magnetism, an example
is the exchange spring magnets (dealt with in Chapter PMM §2.6), where high-
moment and high-coercivity materials are mixed at the nanoscale in order to provide
superior permanent magnet performance. Another example from the field of soft
magnetism are the the FINEMET-type materials, which are nanocomposites of
crystallites of α-FeSi in an amorphous matrix [1].
A typical composition for this alloy is Fe73.5 Cu1 Nb3 Si13.5 B9 : the addition of
Cu provides nucleation centres whilst the role of the Nb is to prevent the growth
of large grains of FeSi. A transmission electron micrograph showing the type of
grain structure possessed by this material is shown in Fig. 1. The structure is
nanoscale grains of α-Fe(Si) in a matrix of amorphous residue. The precipitation
of these grains greatly improves the soft magnetic properties with respect to the
precursor. This is explained through the averaging out of any magnetocrystalline
anisotropy over many grains when the grains are smaller than the exchange length
lex = A/μ0 Ms2 [3], as is expected within random anisotropy models [4].
Comparison of mechanically-alloyed material, which lacks any amorphous content,
with melt-spun amorphous ribbon found poorer soft magnetic properties in the
mechanical alloys, underlining the importance the of the amorphous matrix for
exchange coupling the nanoscale grains [2]. FINEMET materials are discussed in
detail in Chapter SMM §6.3.
21 Artificially Engineered Magnetic Materials 1049
Thin-film structures
Exchange bias
A layer of ferromagnetic material placed in contact with an antiferromagnet will
be exchange coupled to it, the most remarkable manifestation of which is a shift
1050 C. H. Marrows
in the hysteresis loop along the field axis, breaking the usual M(H) = −M(−H)
symmetry. This effect is known as exchange bias, and was first discovered by
Meiklejohn and Bean six decades ago in partially oxidised Co nanoparticles [5].
The shifted hysteresis loop they observed is reproduced in Fig. 2. Notable reviews
of the exchange bias phenomenon over the intervening years include those by
Nogués and Schuller [6] and Stamps [7]. A review of theory was given by Kiwi
[8]. Whilst long considered a curiosity, the ability of exchange bias to provide a
pinned reference layer in a spin-valve structure [9] means that the effect is now of
enormous technological importance in magnetic recording and MRAM applications
(see Chapter MMY).
A notable feature of the data shown in Fig. 2 is that the loop shift is only
observed when the system is field-cooled. When cooled in zero field, the loop
remains symmetric but broadens. In this case, the cooling matters since CoO has a
Néel temperature TN that is just below room temperature, and so is not magnetically
ordered until it is cooled. This gives an important clue as to how exchange bias
comes about. At the heart of the phenomenon is the fact that the spins in the
ferromagnet are exchange-coupled to the spins in the antiferromagnet across the
interface. When a field is applied to the system, only the ferromagnet can respond
21 Artificially Engineered Magnetic Materials 1051
since the antiferromagnet lacks a net moment, but the ferromagnet will exert a
torque on the antiferromagnet. If its spins are held in place, by magnetocrystalline
anisotropy, for instance, then the ferromagnet will not so easily respond to the field.
The requirement for anisotropy in the antiferromagnet was demonstrated using an
artificial exchange bias system [10]. In order to reverse the ferromagnetic spins
whilst leaving those in the antiferromagnet unaffected, it is necessary to break the
exchange bonds at the interface, This energy cost increases the field required to
reverse the ferromagnet magnetisation. When the field is removed, the ferromagnet
returns to its original direction as this exchange energy is recovered. The effect
in low applied fields is unidirectional (as opposed to the more usual uniaxial)
anisotropy, with the ferromagnetic moment ‘pinned’ to point in a particular direction
in low fields. The offset along the field axis is known as theexchange field Hex , given
by the expression
Jex
Hex = , (1)
μ0 MtFM
where tFM is the ferromagnet thickness. This reveals the 1/tFM dependence that is the
signature of an interfacial effect. The field offset is thus a measure of the interfacial
exchange interaction density Jex . Typical values for μ0 Hex are tens of millitesla,
meaning that Jex is orders of magnitude smaller than the usual interatomic exchange
energies. The reason is that it is reduced to an effective value, either by winding an
in-plane domain wall in the antiferromagnet [11], or by averaging over a domain
structure in the antiferromagnet caused by the inevitable atomic scale imperfections
at the interface [12].
Field-cooling is necessary to set the direction in which the moment is pinned. As
the ferromagnet-antiferromagnet system is cooled through the Néel point TN , the
antiferromagnet spin structure orders onto the uniform spin structure of the saturated
ferromagnet, and pins it in place once the field is removed in the cooled state. If the
ferromagnet is not saturated then the local antiferromagnetic order is determined by
the local magnetisation in the domain state of the ferromagnet, leading to a broader,
but unshifted loop. On heating, Hex decreases and vanishes at a temperature that
is referred to as the blocking temperature TB , which is often lower than TN for
the antiferromagnet in question. The width of the hysteresis loop is usually large
at this point [13], and the coercivity remains enhanced up to TN . The blocking
temperature is the point above which the energy barriers in the antiferromagnet
are no longer large enough to prevent the reversal of the entire spin structure in
that layer, following the reversing ferromagnet. Making these irreversible transitions
with the antiferromagnet increases the hysteresis of the entire system.
Perfect antiferromagnetic order is not required for exchange bias to be observed.
Whilst some canonical systems such as CoO, NiO [14], or L10 PtMn [15] show
simple antiferromagnetic spin structures, solid solution Mn alloys such as FeMn
[16] or IrMn [17] are also widely studied, where the spin structure is non-collinear
and lacks spatial periodicity. Exchange bias has even been observed when a
ferromagnetic is coupled to a true spin glass [18].
1052 C. H. Marrows
−1
kF n
= − , (2)
π d
where n is an integer.
These ideas were first used to explain the interactions in rare earth/Y superlattices
by Yafet [27]. In 4f systems the spins are localised on the atomic sites and the
RKKY model is clearly valid. Bruno and Chappert attempted to use the RKKY
model to describe the situation in transition metal multilayers and found that whilst
the periods of the oscillations were correct, the phase and amplitude could not
be properly reproduced [28]. This is because the RKKY model assumes point-
like spins, and does not properly take account of the delocalised magnetism in 3d
materials.
21 Artificially Engineered Magnetic Materials 1053
Fig. 3 Indirect exchange coupling for various transition metal spacers between ferromagnetic Co
layers. The quantities given are the spacer thickness for the first antiferromagnetic coupling peak
A1 , the magnitude of the coupling at this peak J1 , the width of the first coupling peak ΔA1 , and
the period P of the oscillation, as well as the crystal structure and Wigner-Seitz radius rW−S for
each element, in units of Ångströms. An asterisk indicates that only one antiferromagnetically-
coupled spacer-layer thickness region was observed, so it was not possible to directly determine P.
Reprinted figure with permission from [S.S.P. Parkin, Phys. Rev. Lett. 67, 3598 (1991)] Copyright
(1991) by the American Physical Society. [22].
Density of States
spin-dependent reflection
coefficients (solid line), and
of free electrons in the bulk
(broken line).
Fermi
level
Energy
for the confined system, which zigzags above and below it as each quantised energy
level is passed through (see Fig. 4). These quantum well states have been observed
experimentally in inverse photoemission experiments [30].
Both the RKKY and quantum well pictures, as well as other related calculations,
share some common features: an s-d exchange mechanism, polarisation of the
electron gas in the spacer, and periods set by the extremal points of the spacer Fermi
surface. This commonality was made explicit by Bruno in his unified picture [31],
in which he treated the spacer as being analogous to a Fabry-Perot cavity, in which
electron waves reflect back and forth from the interfaces. Since the interfaces are
with ferromagnets, the reflection coefficients are spin-dependent and so the standing
waves set up in the spacer are spin-polarised. Different models then amount to
different ways of calculating these spin-dependent reflection coefficients. This might
be done ab initio, by treating 2D arrays of point spins (the RKKY model), within a
tight-binding model (the quantum well theory), or even just in a simple free electron
picture [32].
It is remarkable that these coupling oscillations are a quantum interference
phenomenon that is robust enough to be observed at room temperature in disordered,
polycrystalline material. Structures exploiting this effect have found applications as
the reference layers in magnetoresistive recording heads [33], and in the operation
of toggle-mode MRAM cells [34]. They also show promise for ultrafast racetrack
memories [35].
Dzyaloshinskii-Moriya interaction
Usually magnetic order can be described in terms only of the Heisenberg exchange
interaction between neighbouring spins S, which is usually written as − J(S1 ·S2 ).
This scalar product normally leads to collinear states. (The effects of frustration
can prevent this.) However, when structural inversion symmetry is broken, the
Dzyaloshinkii-Moriya interaction [41, 42] (DMI) can also be present, a form of
anisotropic exchange that has a chiral, vector product form: −D · (S1 ×S2 ). The
magnitude of the vector D expresses the strength of the interaction, whilst its
direction is determined by crystal symmetry rules [43].
Inversion symmetry is broken by an interface, and so it is expected to find an
interfacial DMI at the interfaces of a ferromagnetic layer [44, 45]. As shown in
Fig. 5, the DM vector D lies in-plane in this situation. The DMI is a manifestation
of spin-orbit coupling, which is generally weak in 3d ferromagnets, and so the other
metal at the interface needs to be a heavy one from the 5d series for large effects.
Since this is an interfacial effect, very thin films ( 1 nm) are needed in order for it
to play any appreciable role.
Chiral spin states have now been observed in several different systems. A
monolayer of Mn on a W substrate forming a spin spiral was one of the very first
examples [47]. The DMI creates an effective field at a domain wall [48], so that the
domain wall chirality is fixed by the sign of the DMI. Examples systems where this
has been observed include Fe nanowires on a W substrate [49], Co/Ni multilayers
on Pt or Ir substrates [50], and polycrystalline sputtered Pt/Co/AlOx stacks [51].
1056 C. H. Marrows
S2
S1 D12
Large SOC
Fig. 5 Sketch of a DMI at the interface between a ferromagnetic metal (grey) and a metal with a
strong SOC (blue). The DMI vector D related to the triangle composed of two magnetic sites and
an atom with a large SOC is perpendicular to the plane of the triangle. [46].
The DMI also plays a key role in stabilising topologically non-trivial (impossible
to deform smoothly into the ferromagnetic state) vortex-like spin textures with
quasiparticle properties known as skyrmions [52]. This interfacial form of the
DMI is able to stabilise these objects in ultrathin films [53], and the possibility to
construct complex mutilayers means that their properties can be tailored. As well as
examples where truly nanoscale skyrmions have been observed at low temperatures
[54], larger skyrmions [55, 56, 57], and bubble domains with skyrmion topology
[58] have been observed at room temperature. They have been shown to respond to
currents and so can be moved electrically within spintronic devices [59].
2D electron gases
a b
Fig. 6 Spin-momentum locked boundary states in topological insulators. (a) Schematic of the 1D
edge states in a 2D topological insulator. The red and blue curves represent the edge current with
opposite spin character. (b) Schematic of the 2D surface states in a 3D topological insulator. [80].
Bi2 Se3 crystal and measuring the induced voltage for different directions of current
flow in the crystal’s surface [79].
The ordinary Hall effect requires a magnetic field, whilst the anomalous Hall
effect, observed in ferromagnets, does not. Similarly, whilst 2-dimensional systems
can show a quantum Hall effect under field, a quantum anomalous Hall effect is
possible at zero field in the 2-dimensional surface state of a magnetically doped
topological insulator [81], as first observed in a Cr-doped (Bi,Sb)2 Te3 epilayer [82].
Nanowires
Magnetic nanowires are, broadly speaking, magnetic nanostructures that are much
longer in one dimension than the other two. One way to make such a structure
is to pattern it lithographically from a thin film. Nanowires made by this planar
processing approach are common in spintronic applications and can be fashioned
into networks and used to perform logic operations [83] or used as racetrack
memories [84]. These topics are dealt with in more detail in other chapters.
Template-grown nanowires
Co layer
Cu film
a single material are straightforward to grow by this method [88], it is also possible
to form multilayers by either using a pair of baths [89] or by using a single bath and
potentiostatic control toggling between two values of the overpotential [90], which
provides superior results.
The pore densities in anodic aluminium oxide are typically in the range 102 -103
μm−2 , leading to strong dipolar coupling between the nanowires. Arrays of Fe wires
are good examples of strongly coupled systems [91, 92]. Although the easy axis is
usually along the lengths of the wires as expected, the squareness ratio Mr /Ms is
smaller than unity unless the wire diameter is very small, indicating a non-uniform
reversal mode.
On the other hand, nanoporous polycarbonate membranes can have pore densities
as low as 10−2 μm−2 and hence permit the investigation the properties of practically
isolated magnetic nanowires. Enhanced coercivity and squareness can be achieved
in such arrays for suitably small wire diameters [93, 94]. Ni wires made by this
method reveal properties dominated by the shape anistropy of the wire, whilst the
large magnetocrystalline anisotropy of Co modifies their properties due to the local
easy directions that vary from grain to grain [94].
Multilayer nanowires can display a giant magnetoresistance (GMR), measured
in the current-perpendicular-to-plane geometry, with early examples being Cu/Co-
Ni-Cu alloy superlattices [90] and Co/Cu multilayers [95]. The fact that individual
layers can be very thick in structures prepared by this method allowed models of
the GMR in the limit of structures large compared to the spin diffusion length to be
tested [96]. The fact that superconducting contacts are not required due to the high
aspect ratio of the structure means that this is also a method suitable for studying
the temperature dependence of the GMR [97].
In GMR, magnetic configurations affect current flow across interfaces, whilst the
inverse effect where current flow across interfaces affects magnetic configurations
is the domain of spin-transfer torque. It is natural to expect these effects also
to be present in multilayer nanowires. This effect has been used to tailor the
shape of hysteresis loops using current pulses [98] and to effect current-driven
switching [99].
1060 C. H. Marrows
Special examples of nanowires are the 1-dimensional channels that form the edge
states in quantum Hall systems. In a conventional (integer) quantum Hall system,
all the carriers travel in the same direction around the edges and the edge states are
said to be chiral.
A two-dimensional topological insulator will have conducting edges that form
helical edge states, as shown in Fig. 6b. The spin-orbit interaction, which can be
thought of as a momentum-dependent magnetic field, spin-momentum locks the
carriers in the same way as in the 3-dimensional systems discussed above. This
means that carriers of opposite spin circulate around the edge states in opposite
directions, leading to the flow of dissipationless pure spin currents in these 1-
dimensional channels.
First introduced theoretically by Kane and Mele [100] and Bernevig and Zhang
[101], to observe the quantum spin Hall effect experimentally requires specially
engineered heterostructures. The first experimental example was a HgTe quantum
well system [102], and more recently InAs/GaSb coupled quantum wells have
emerged as candidate systems [103, 104].
The phase diagram of micro- or nanoscale magnetic discs as their thickness and
diameter is varied was determined by Cowburn et al. [105]. This was done by
measuring the shape of the hysteresis loops of an array of Permalloy discs by
the magneto-optical Kerr effect, with the results shown in Fig. 8. When the discs
are very thin and small they are superparamagnetic and show no coercivity. If the
thickness or diameter is increased a little then ferromagnetism is stabilised within a
single domain state, which has leads to a rather square hysteresis loop. Once the disc
is large enough it displays a wasp-waisted loop with a significantly higher saturation
field. This is due to the formation of a vortex state at remanence, which is only
possible when the disc is large enough that savings in magnetostatic energy in this
flux-closed state are sufficient to compensate for the high exchange energy costs
caused by the large magnetisation gradients around the vortex core.
Those results were obtained on discs spaced sufficiently far apart that they are
non-interacting, and hence reproduce the hysteresis properties of an individual disc.
When the spacing is reduced, magnetostatic coupling between the discs comes into
play. A dramatic consequence is that it can stabilise magnetic order in arrays of
21 Artificially Engineered Magnetic Materials 1061
discs that are too small to be thermally stable as individuals [106]. The interactions
between single-domain discs in a chain can also be exploited to perform logic
operations magnetically [107].
The flux-closed nature of the vortex state means that it creates very little lateral
stray field, so interdisc coupling is far weaker than in the case of the single domain
state. Nevertheless, just as non-polar molecules can interact via van der Waals
forces, dynamic displacements of the vortex core from the disc centre will produce
a net dipole moment and hence some stray field. This means that whilst the static
states are largely uncoupled, dynamically coupled states can emerge [108]. These
magnonic vortex crystal states have been confirmed experimentally [109].
Spin ices crystals with the pyrochlore structure, where rare earth ions with large
magnetic moments appear at the vertices of the corner-sharing tetrahedra [110].
They are an example of a geometrically frustrated magnetic system: the crystal
geometry means that it is not possible to satisfy all of the interactions in a given
1062 C. H. Marrows
tetrahedron simultaneously. The best that can be done is to find a state where two
of the moments point into the tetrahedron and two point outwards. This is a perfect
analog the proton displacements occuring according to the Bernal-Fowler ‘ice rules’
[111] of the Ice Ih phase of H2 O, leading to exactly the same statistical mechanics
and the prediction of the same residual Pauling entropy [112], hence the name
“spin ice”. Excitations of pyrochlore systems can be described as separated pairs
of magnetic monopole quasiparticles [113].
It is now possible to study geometrical frustration in a in a wide range of artificial
systems that make use of phenomena such as magnetism, superconductivity , and
colloids [114, 115, 116, 117, 118]. Since they are built using nanotechnology,
the structure of such systems, and the frustrated interactions they embody, can be
designed rather than discovered. In magnetic systems, single domain nanoislands
with a well-defined easy axis are used to create Ising-like macrospins that stand in
for the atomic scale magnetic moments in the pyrochlore systems. Such systems are
known as artificial spin ices [119], in which the details of the magnetic configuration
can be inspected macrospin-by-macrospin using advanced magnetic imaging tech-
niques to reveal the exact microstate of the artificial statistical mechanical system.
It is not possible to replicate the tetrahedral symmetry in a 2-dimensional system,
and so a projection into the plane of the substrate of some sort must be made.
Two different ways to do this lead to the square [115, 120, 121, 122] and kagomé
[114, 123, 124, 125] ice arrays that have been widely studied, illustrated in Fig. 9a
and b, respectively. The square ice array has a long-range ordered antiferromagnetic
ground state with the lowest possible twofold degeneracy that is easily accessible
through annealing [126, 127, 128]. By introducing an offset in height between the
two sublattices of the square ice array the equivalence between the interactions
between the four islands that meet at each vertex can be restored, recovering the
extensive degeneracy that is the hallmark of the spin ice state in the pyrochlores
[129]. Meanwhile the kagomé pattern has stronger frustration and a richer phase
diagram [130, 131]; its phase transitions have been probed by low energy muon
spectroscopy [132].
The first examples of these systems were athermal, since the blocking tempera-
tures of the nanoislands were ∼ 105 K, and so the magnetic microstate was entirely
frozen on any realistic laboratory timescale. In order to relax these systems into a
low energy state, various ac demagnetisation protocols were designed [134, 135].
Whilst reducing the system energy, the ground state was never obtained [120, 121].
Although true thermalisation was not possible, an effective thermodynamics was
possible, with analysis of the microstates allowing the effective temperature [136,
137] and entropy [138] to be obtained.
The discovery that it is possible to perform a one-shot anneal into a well-
thermalised state during sample fabrication [126] was quickly followed up by a
demonstration that it is possible to “melt” that macrospin system at temperatures
below the Curie point of the underlying magnetic material in systems where
the blocking temperature is engineered to be experimentally accessible [139].
Annealing systems into their ground state has been made possible through advances
in the materials used to prepare the nanoisland arrays [127, 128, 140, 141], freezing
21 Artificially Engineered Magnetic Materials 1063
Fig. 9 Artificial spin ice lattices. (a) The square (a) and kagome (b) lattices that have been
extensively investigated. The short-island shakti (c) and long-island shakti (d). The darkened
islands in c,d define a plaquette of the lattice, which is the basis for understanding its topologically-
induced emergent frustration. [133].
a thermalised state to become athermal and stable for imaging. Careful control of the
energy barriers and temperature range studied experimentally has allowed the direct
observation of thermal fluctuations and relaxation as artificial spin ices explore their
energy landscape using time-resolved imaging [142, 143, 144, 145].
The ability to design lattices to embody a particular Hamiltonian means that
it is possible to engineer novel emergent phenomena [146], which in many cases
are absent in ‘naturally-occurring’ systems. Examples include the ‘shakti’ lattice
(Fig. 9), which displays topologically induced emergent frustation [133], the
‘tetris’ lattice, which exhibits an emergent reduction in dimensionality [147], spin
fragmentation in the kagome lattice [148], sublattice decomposition in Penrose
patterns [149], and artificial charge ices that display promise as novel data storage
media [150].
1064 C. H. Marrows
The signature feature of the electronic structure of an atom is its discrete energy
spectrum. By a suitable choice of material and size, nanoscale structures can
also be engineered to display a discrete set of energy levels, causing them to be
dubbed ‘artificial atoms’ [151, 152]. The usual way to probe these energy levels
is through electrical measurements, using tunnel contacts so as not to perturb the
electronic structure within the artificial system. This leads to a phenomenon known
as the Coulomb blockade (CB), which is the central feature of single electron
electronics [153]. When combined with magnetic materials, this leads to the field
of nanospintronics [154, 155], in which spin-polarised electrons are manipulated
one-by-one.
Coulomb blockade
and cotunnelling (correlated transfer of more than one electron) events are ignored
[153]. This last assumption is a reasonable one if the tunnel contact conductances
are e2 /h.
When a gate electrode is added to the island to increase the number of terminals
to three, the device is known as a single electron transistor (SET). This can be used
to apply a voltage Vg to the island to shift its energy levels. The conditions for
the four energies exceeding zero now form four slanted lines in a Vg -V diagram,
surrounding a diamond shaped area. A similar set of conditions pertains to each
charge state, leading to a chain of corner-sharing ‘Coulomb diamonds’.
Cotunnelling effects
As described above, below the Coulomb gap (EC /kB > T and EC /e > V ), sequential
tunnelling processes are blocked by the Coulomb charging effects. Nevertheless, a
small current may still flow, even in the ideal case of no leakages, by considering
higher order processes [176], the most commonly discussed of which is known as
cotunnelling. It was predicted by Takahashi and Maekawa that in this cotunnelling
regime the TMR can be substantially enhanced when the magnetisation of the
central island is switched against the outer electrodes. This is because this coherent
process leads to the overall resistance of the double arising from the product of
the individual junction resistances, whereas it follows the usual series resistor sum
21 Artificially Engineered Magnetic Materials 1067
rule in the sequential regime. It can be shown within the Jullière model that the
TMR in the cotunnelling regime should be enhanced by a factor of 2/(1 − P2 ),
where P is the electrode spin polarisation. These effects were explored in some
detail using a conventional double junction stack with granular CoFe deposited
between two outer pinned CoFe electrodes [177]. At 7 K the TMR ratio was 24 %
at zero bias, roughly double the value measured beyond the gap at V = 100 mV. The
effective spin polarisation P was estimated to be 32 % from the non-enhanced TMR,
leading to a prediction from the 2/(1 − P2 ) expression of an enhanced TMR of 23 %,
in agreement with the observed value. Another magnetic configuration is double
magnetic tunnel junctions with conventional free and pinned outer electrodes, in
which superparamagnetic NiFe nanoparticles form the central electrode sandwiched
between alumina barriers [178]. Whilst the TMR in the CB regime is a little
lower than that for a control sample lacking the NiFe islands, the cotunnelling
enhancement in the TMR was clearly observed at biases small enough to lie
within the Coulomb gap for the double MTJ. This shows that spin information
can be propagated through the fluctuating NiFe island moments. This is reasonable
since typical tunnelling times are of the order of femtoseconds, much shorter than
typically superparamagnetic fluctuation lifetimes, which are ∼ 0.1-1 ns.
Kondo effect
The Kondo effect arises when the spin of a magnetic impurity interacts with
the surrounding free electrons to form a singlet state. The earliest studies of the
Kondo effect considered the situation of doping a conductor, such as copper, with
a magnetic impurity [179]. As a result, the conductivity saturates when reducing
the temperature. The maximum value of the conductivity is achieved for the so
called Kondo temperature (TK ) [180]. This value directly depends on the number
of defects introduced in the conductor. In single electtron devices, the a net spin
in the artificial atom can interact with the electrons in the leads to form the Kondo
singlet [181]. In tunnel junctions with magnetic nanoclusters in the insulating layer,
the Kondo effect can produce an enhancement of the resistance or its reduction
depending on the exact location of the clusters within the layer. For instance,
Kondo resonances were suggested to be be the cause of a rise in the resistance
at low temperature and low bias when introducing thin Cr(< 0.4 nm)/Co(< 0.6 nm)
impurities in one of the electrode/barrier interfaces of a magnetic tunnel junctions
[182]. On the other hand, the Kondo effect produces an increase of the conductance
if the insulating tunnel barrier is doped with a magnetic material [183] or some
magnetic nanoclusters are placed within this layer [184]. In the CB regime, where
nanoclusters are intentionally placed within the insulator, some theoretical work
[185, 186], and recent experimental results [187], show that the Kondo effect
in TMR can be important even if the magnetic moments have large magnetic
anisotropy [188]. A theoretical discussion of the Kondo effect in single-electron
devices can be found in Ref. [189]. The crossover between Kondo TMR suppression
and co-tunneling enhancement of TMR in double magnetic tunnel junctions with
CoFe nanoclusters within the MgO barrier is discussed in [187]. For all CoFe
thicknesses the tunnelling is dominated by sequential tunnelling at high temperature
1068 C. H. Marrows
and bias voltage. However, when the temperature is reduced, some typical Kondo
signatures can be observed: a zero bias anomaly (ZBA) in the conductance versus
bias voltage curve; the temperature dependence of the ZBA; and suppression of the
TMR at low bias below a particular temperature. From each of these experimental
features, the Kondo temperature can be determined. The crossover from the two
effects, Kondo and CB, was found to be correlated with the fluctuations of the
magnetic moments of the nanoclusters. A related experiment using high-anisotropy
CoPt nanoclusters found a gradual competition between cotunneling enhancement
of the TMR and the TMR suppression due to the Kondo effect, with both effects
having been found to coexist even in the same sample. It is possible to tune between
these two states with temperature [190].
painstakingly. This means that materials can be engineered at the fundamental limit
imposed by the discreteness of matter.
The STM can also be used to investigate magnetism at the atomic scale, for
instance by measuring the magnetisation curve of a single atom [201]. Doing so
for individual Fe atoms on a Cu (111) surface, combined with inelastic scanning
tunneling spectroscopy revealed that the typical moment of such an atom is 3.5 Bohr
magnetons with a magnetic excitation lifetime of 200 fs [202]. The findings were
quantitatively explained by the decay of the magnetization excitation into Stoner
modes of the itinerant electron system. Longer timescales of between 50 and 250 ns
were found using STM-based pump-probe methods [203].
Combining these measurement methods with the ability to engineer nanos-
tructures specified atom-by-atom, including the exchange coupling between the
moments on neighbouring atoms (by controlling the interatom distance to yield
the selected value of the oscillatory indirect exchange) between them [201], has
led to the ability to make all-spin logic gates from atomic chains [204], control the
ground states of chains (depending on even or odd numbers of constituent atoms),
engineer magnetic frustration within arrays [205], and excite coupled arrays with
spin transfer torques arising from spin-polarised currents injected from a magnetic
STM tip [206]. Quantum tunnelling between Néel states of antiferromagnetic chains
has been observed [207]. Building a chain of Fe atoms on a superconducting Pb
surface has allowed for the detection of Majorana fermion-like collective excitations
in a condensed matter system [208], manifesting themselves as zero-energy states
at the ends of the chain.
The thermal stability of any magnetic moment arises from its magnetic anisotropy
energy . At the atomic scale, this comes from the ligand crystal fields (Chapter ANI),
the electrostatic energy arising from the shape of the orbitals of both the magnetic
adatom and its neighbours in the substrate. Spin-orbit coupling locks the adatom
spin moment to its orbital moment, which is subject to these ligand fields, generating
the anisotropy. From this we see that the three factors needed for a strong anisotropy
are strong spin-orbit coupling , a large orbital moment, and a strong ligand field. The
last two are usually inversely correlated to each other, since the ligand field tends to
quench the orbital moment.
Single cobalt atoms deposited onto platinum (111) were found to have a giant
magnetic anisotropy energy of 9 meV per atom, determined using x-ray magnetic
circular dichroism [209]. Here the large unquenched orbital moment of 1.1 Bohr
magnetons and strong spin-orbit coupling induced by the heavy metal substrate
combine to yield this large value. The use of STM-based methods described
above show that even such large anisotropy energies are not enough to thermally
stabilise individual atomic moments on a metallic substrate [210, 203, 202], due to
21 Artificially Engineered Magnetic Materials 1071
spin-flip scattering of electrons in the substrate. Partially isolating the the adatom
electronically from the susbtrate using interlayers such as copper nitride [211] or
magnesium oxide [212] was found to boost the anisotropy considerably: indeed in
the latter case a record anisotropy energy of 60 meV for Co, close to the free atom
value, was achieved. Tuning the strength of the interactions between adatom and
substrate allows the strength of the anisotropy, in turn, to be controlled [213].
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Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
Magnetic Field Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
Permanent Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1085
Electromagnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1087
High-Field Magnet Facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
Magnetic Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1104
Magnetic Field Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105
General Technical Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1107
Magnetic Field Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1109
Bulk Magnetic Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
Stray Field Mapping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1139
Calibration and Metrology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1141
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1143
O. Portugall ()
LNCMI-CNRS (UPR3228), EMFL, Univ. Grenoble Alpes, INSA Toulouse, Univ. Toulouse 3,
Toulouse, France
e-mail: [email protected]
S. Krämer
LNCMI-CNRS (UPR3228), EMFL, Univ. Grenoble Alpes, INSA Toulouse, Univ. Toulouse 3,
Grenoble, France
e-mail: [email protected]
Y. Skourski
Hochfeld-Magnetlabor Dresden (EMFL-HLD), Helmholtz-Zentrum Dresden-Rossendorf,
Dresden, Germany
e-mail: [email protected]
Abstract
Introduction
Magnetic fields and, more generally, magnetism are associated with a vast number
of physical phenomena as well as a number of misbeliefs and superstitions that
continue to defy scientific evidence right into the twenty-first century. It is therefore
appropriate to recall that magnetism basically just describes interactions involving
two specific properties of matter, charge and spin. Moving charges and spins are
both at the origin of, and affected by, magnetic fields. Their physics thus determines
the construction of magnets as well as magnetic measurements that are the principal
subjects of the present chapter.
The co-existence of two distinct properties of matter associated with magnetic fields,
charge and spin, finds its counterpart in the existence of two distinct classes of
magnets, electric and permanent. Each class consists of numerous types and has
its specific practical strengths and weaknesses as far as energy consumption, field
strength, and the modulation of the magnetic field in time and space are concerned.
The specific restrictions of different magnets nevertheless have a common origin,
namely, the limited capability to procure, sustain, and contain the magnetic energy
stored in the field. In this respect, the foremost difference between permanent and
electromagnets is that the first provide the magnetic energy by themselves, whereas
the second depend on an external source.
22 Magnetic Fields and Measurements 1085
Permanent Magnets
Permanent magnets make use of hard magnetic materials that generate a stable
magnetic flux distribution and, consequently, magnetic energy in the surrounding
free space without the need of an external energy source. In terms of applications,
they are widely used as sources of uniform and non-uniform magnetic fields that
can be static or time dependent. With the currently available materials, permanent
magnets are fully competitive with electromagnets for magnetic fields up to 2 T with
record values near 5 T [27]. They are most commonly used as part of a magnetic
circuit composed of permanent magnets with optional soft ferromagnetic materials
that channel the flux to a region of free space where the usable magnetic flux is
generated. The latter is often called the air gap. Therefore, the natural description of
permanent magnets uses the magnetic field strength or flux density B, since flux is
conserved and interactions of electric charges and magnetic moments all depend on
B [27, 39].
the B-H hysteresis loop are chosen. Permanent magnets are either available as
oriented sintered magnets, which show the best performance but are expensive and
complicated to manufacture, or bonded magnets that involve the usage of a non-
magnetic matrix. The latter are cheaper to produce, but their performance is limited.
Materials for permanent magnets can be divided into four groups according to their
maximum energy product and their cost [39]:
Ferrites: Discovered in the 1950s, ferrites are used for traditional and mass
market applications (90% in weight), since they are easily available at low
cost (about 1 US$ per Joule of magnetic energy). They provide good long-
term stability and corrosion resistance. Their disadvantage is their low magnetic
energy product due to their low remanent magnetization.
Neodymium-iron-boron (NdFeB): Discovered in the 1980s, this family is used
for high-performance and miniaturized applications, as they provide the highest
magnetic energy product (above 400 kJ/m3 ; for comparison, lodestone, or natural
magnetite, has a magnetic energy product of 0.7 kJ/m3 ) at still reasonable price
(less than 10 US$ per Joule). Limitations are low Curie temperature and easy
oxidation in air that cause grains to become noncoercive. As these magnets have
the greatest potential for wider applications, intense research is conducted to
improve their properties [156].
Aluminum-nickel-cobalt alloys (AlNiCo): This type of magnets became available
in the late 1930s. Their production cost is almost ten times higher in comparison
to ferrites, yet they provide excellent thermal stability and high Curie tempera-
tures making them ideal for high-temperature and high-precision applications.
Samarium-cobalt magnets (SmCo): SmCo-based magnets were discovered in the
1960s and are high-performance magnets due to their high-temperature behavior
and their compatibility with corrosive environments. SmCo magnets are widely
used in spatial and military applications. Their disadvantage is their high price.
that provide highly homogeneous magnetic fields for nuclear magnetic resonance
(NMR) spectroscopy and imaging [133, 31]; single-sided magnets for ex situ
high-resolution NMR spectroscopy [120] and other sensor applications; and
motion and position sensing using magnetic induction or Hall probes [39]. As
permanent magnets generate strong magnetic field gradients, they can also be
used for stray field magnetic resonance imaging in solids (STRAFI). Here, the
magnetic field gradient used for spatial encoding is also generated by the main
magnet, in contrast to conventional magnetic resonance imaging techniques. In
complement to STRAFI methods in solenoids [146,82], their use with permanent
magnets has recently opened the possibility of compact and mobile NMR [31],
as permanent magnets require no external energy source and provide strong
gradients (up to 100 T/m) [27].
Magneto-mechanical applications: Magneto-mechanical assemblies are charac-
terized by forces and torques produced by direct interaction between different
magnets or between magnets on the one hand and magnetic materials on the
other hand. As the magnetic force is given by the spatial gradient of the
magnetic energy, its value depends on the square of the spontaneous polarization
Js . Important magneto-mechanical applications are magnetic gears, bearings,
shock absorbers, magnetic levitation, as well as magnetic separation systems for
paramagnetic and ferromagnetic particles [27].
Electro-mechanical applications: Electro-mechanical applications are charac-
terized by forces and torques produced by interaction between magnets and
devices carrying external or induced electrical currents. The interaction strength
of the forces and torques is proportional to I J , where I is the current and
J is the polarization of the magnet. Electro-mechanical applications represent
the biggest application area, since they comprise motors, loudspeakers, and
actuators involving external currents as well as devices involving eddy currents
as separators for non-magnetic metallic particles [27] and counters for speed or
current consumption [39]. Another important electro-mechanical application is
the use of permanent magnets in beamlines and accelerators in order to guide the
charged particles or to generate curved paths in wigglers and undulators in order
to generate narrowband intense synchrotron radiation [20].
For further discussions of permanent magnets and their applications, see also
Chap. 28, “Permanent Magnet Materials and Applications,” of this book.
Electromagnets
Electromagnets are current driven and thus governed by the Biot-Savart law relating
the current density j (r) and the magnetic field strength B(r).
μ0 r − r 3
B(r) = j (r ) × d r. (1)
4π V |r − r |3
1088 O. Portugall et al.
As the field varies linearly with the current density, electromagnets are particularly
useful when a magnetic field has to be switched, swept, or tuned. They can also
generate higher fields than permanent magnets and tend to be more practical to
cover larger volumes.
The performance of electromagnets is fundamentally limited by dissipation and
magnetic pressure. These problems as well as advanced technical strategies to
overcome them will be discussed in the next section on high-field magnet facilities.
Here, we limit our attention to common laboratory magnets whose operating
regime gives rise to thermal and mechanical constraints that can be controlled with
relatively basic means. This is the case for resistive magnets providing fields up to
about 5 T and superconducting magnets reaching 23–25 T.
Laboratory magnets are used in physics, chemistry, biology, and material science.
They permit measurements of field-dependent physical properties of matter like
magnetization, Hall effect, magnetoresistance, optical properties, specific heat, ther-
mal transport, and magnetic resonance. Other possible uses include the alignment
or separation of magnetic objects or domains and the manipulation of chemical
reactions and biological processes. Typical industrial applications comprise motors,
loudspeakers, generators, and actuators.
The design of laboratory magnets is subject to application-related requirements
such as the desired maximum field value, homogeneity, a particular spatial field
profile, or geometric constraints like the need of openings for optical access. The
basic approach is to start from the Biot-Savart law (Eq. 1) and to place current
sections such that the desired field profile is obtained. The usage of different circuits
operating at different current levels, of ferromagnetic materials, and of permanent
magnets provides additional degrees of freedom for field shaping. Whereas simple
magnets or magnet assemblies can be calculated by analytical methods [163, 56],
numerical approaches including finite-element techniques have to be used for more
complex arrangements. In addition, constraints given by the magnetic pressure and,
in the case of resistive electromagnets, the energy dissipation may be modelled
numerically.
The most commonly used laboratory electromagnets are resistive and supercon-
ducting solenoids for variable fields, Helmholtz coils providing high homogeneity,
and solenoids equipped with a magnetic core to amplify and bundle magnetic flux.
In the following, these three types will be briefly discussed:
Fig. 1 Left: graph showing the relation between upper critical field Bc2 , the critical temperature
Tc , and the critical current density jc of a technical type-II superconductor. The superconducting
phase is limited to points below the surface. Right: comparison of critical current densities (at 4.2 K
unless otherwise stated) available in strands and tapes of more than 100 m. (Adapted from [93])
Helmholtz Coils
Helmholtz coils are a special form of electromagnets that generate a highly
homogeneous field. They consist of a pair of identical solenoids that are thin and
short and placed on a common axis in a distance that equals their radius. These
conditions ensure that the series expansion of the magnetic field in the geometric
center only starts with a fourth-order term.
Main laboratory applications of Helmholtz coils using DC currents are low-field
NMR and electron paramagnetic resonance (EPR) experiments as well as sensor
calibration. Alternatively, Helmholtz coils may also be driven with AC currents in
order to study the effect of time-varying magnetic fields, for example, on biological
systems. Arrangements of three orthogonal Helmholtz coils are furthermore used to
calibrate three-axis sensors and to cancel unwanted magnetic fields and in particular
the earth magnetic field for applications such as zero-field NMR.
this respect, as it exhibits a high saturation field of 2.16 T at room temperature and
does not remain magnetized at zero field.
Magnetic cores are used in various devices such as laboratory magnets, trans-
formers, electro-motors, magnetic switches, and recording heads. For most of these
applications, the maximum field is about 2 T. However, rare-earth materials have
also been used to boost high-field resistive magnets [144].
A widely used scheme for magnets with magnetic core consists of two solenoid
coils filled with iron cylinders that are aligned on a common axis. Close to the
symmetry plane, the iron cylinders are shaped into pole pieces in order to guide
magnetic flux into the air gap where the experiment is placed. The shape of the
pole pieces can be optimized to provide a suitable compromise between the highest
possible and the most homogeneous magnetic field in the air gap [48, 42, 13, 14].
Magnets of this type are commercially available up to 5 T and require electric power
of the order of 10 kW and water cooling. They are extensively used for a variety
of laboratory applications including most notably electron paramagnetic resonance
(EPR) measurements in the L-, S-, and X-Bands (1–2 GHz/0.06 T, 2–4 GHz/0.12 T,
and 8–10 GHz/0.3 T). For this application, high-class and high-stability power
supplies are required, typically with a stability of less than 10 ppm.
A very useful method for the design of electromagnets with magnetic core is
provided by the concept of the magnetic circuit analogy to the electric circuit [78].
The term C H · dl = S J · dS (Ampere’s law) defines a magnetomotive force
F (MMF) that takes the role of a “voltage.” In the case of a coil with N turns
and a current I , the MMF becomes NI. The “current” of the magnetic circuit is
represented by the magnetic flux Φ = S B · dS. The equivalent of the resistance
is the reluctance R = F /Φ. For a magnetic circuit in a magnetic material of
permeability μ that has a length l and a cross section A, the reluctance R equals
l/(Aμ). Using this concept, one can find analogs of Kirchhoff’s law in order to
describe circuits containing electromagnets and magnetic materials.
The expression B 2/2μ0 quantifies both the local magnetic energy density
associated with a field B and the pressure exerted on a boundary separating a parallel
field on one side from a field-free region on the other. It is implicitly understood
that such boundary has to be magnetic or contain a net current in order to satisfy the
macroscopic Maxwell’s equations.
Magnetic pressure is primarily a practical quantity that provides a simple upper
limit for the net force a magnet has to sustain. More detailed analyses of local
mechanical constraints make use of the force density that can be evaluated either
via the divergence of the Maxwell stress tensor f = ∇σ where σij = (2Bi Bj −
B 2 δij )/2μ0 or, more commonly, via the Lorentz-force density f = j × B that
refers explicitly to a conductor segment carrying a current density j . In a solenoid,
f gives rise to axial compression and tangential hoop stress j rB where r is the
radius of the current loop. The hoop stress attains its maximum in midplane and
represents the primary limitation for the mechanical integrity of solenoidal magnets.
Under realistic conditions, its magnitude is comparable with the magnetic pressure
of the center field which explains why the latter is often used as a simplified
criterion in design studies. Figure 2 gives an impression of the order of magnitude
of the magnetic pressure and energy density encountered in advanced high-field
magnets.
Dissipation makes it necessary to apply an electric field E that maintains the
current density j in a magnet. The respective power density j · E = j 2 of a
conductor with resistivity ρ gives rise to Joule heating which is quadratic in j
and hence B. Figure 3 gives an idea of the actual power conversion inside a high-
field electromagnet, i.e., the electrical power that has to be provided to maintain
the field and the thermal power that has to be either evacuated (DC magnets) or
temporarily stored (pulsed magnets). The total magnetic energy stored in the coil,
Fig. 2 Conversion scale between magnetic field (lower), pressure, and energy density (both
upper). Arrows indicate the maximum field for different types of magnets (lower) and, for compar-
ison with the magnetic pressure, the ultimate tensile strength of high-strength materials (upper).
Horizontal bars indicate the maximum energy density obtained with electrostatic (capacitors),
electrochemical (batteries), and chemical (fuel) storage. For electrochemical storage, the absolute
maximum obtained in non-rechargeable Li batteries is distinguished from typical values for large-
scale storage in Pb-acid batteries. Although the magnetic pressure and the maximum hoop stress
inside a magnet are not a priori equal, both tend to be similar for most practical magnet geometries
22 Magnetic Fields and Measurements 1093
Fig. 3 Dissipation and the energetic requirements of electromagnets featuring constant current
density, a quadratic cross section parallel to the axis, and a bore size of either 2 cm (solid lines)
or 1/10 (dashed lines) of the outer diameter: (a) required power as a function of magnetic field
and coil size (assuming the resistivity of Cu at 300 K); (b) respective power density and associated
heating if the dumped energy is not evacuated (assuming the heat capacity of Cu at 300 K); (c)
total field/inductive energy stored in the magnet. (a) and (c), respectively, permit the dimensioning
of power supplies for DC magnets and energy storage for pulsed magnets. (b) permits estimates
of the cooling requirements for DC magnets and the maximum field duration for pulsed magnets
depending on the admissible temperature. As a guide to the eye, blue and red circles mark the
approximate parameter space for state-of-the-art DC and pulsed high-field magnets. For real
magnets, power requirements have to be corrected to account for finite filling factors (<100%
Cu content) or the use of high-strength conductors with slightly larger resistivity
B 2/2μ0 integrated over all space, which is just the inductive energy 1/2 LI 2 , is also
shown. The figure permits simple estimates of the operational parameters of DC and
pulsed magnets as shall be discussed below.
In practice, the thermal and mechanical properties of advanced high-field mag-
nets cannot be optimized independently. This statement holds for both the choice of
materials and the general layout. The ideal material for high-field electromagnets
should thus combine high electric conductivity with high mechanical strength,
two properties that tend to be mutually exclusive [162]. The mechanical strength
of a conductor such as Cu can be improved either by work hardening, i.e.,
repeated deformation beyond the elastic limit, or by adding small amounts of
other metals such as Al (Glidcop™) or Ag. Either process, however, reduces the
electric conductivity and hence increases dissipation. The same is true if part of
the current-carrying elements of a magnet are replaced by reinforcing materials,
whence the reduced effective conductor cross section has to be compensated by
higher current densities. Inversely, integrating cooling channels to evacuate the
dissipated heat invariably affects the mechanical properties of a magnet. The design
of high-field electromagnets therefore represents a complex optimization problem
in typically three steps: (a) an initial design choice depending on the basic operating
conditions, the available technical infrastructure, and the envisaged application, (b)
a preliminary concept based on scaling rules and analytic methods [67, 91] that
assume idealized conditions and treat thermal and mechanical constraints separately,
1094 O. Portugall et al.
and (c) extensive finite-element calculations covering the entire magnet assembly
and taking into account the interplay of mechanical, thermal, and in many cases
additional constraints such as the electric behavior of insulating parts or the aging
of all involved materials [180, 5, 171].
Apart from their optimization to obtain the highest field in the largest possible
useful volume, high-field magnets are often subject to additional performance
criteria regarding homogeneity and stability. Relatively good homogeneities are
generally a by-product of the mechanical optimization of magnets as smaller spatial
variations of the field are also necessary to limit stresses. The small but inevitable
radial increase and axial decrease of the saddle-shaped field in the center of a
solenoid can be furthermore flattened by increasing the length h which, however,
implies that more magnetic energy and power is needed. If necessary, correction
coils can also be used to obtain the desired field profile which, however, concerns
almost exclusively NMR applications. Stability usually depends on the power
supply rather than the magnet itself. An exception are superconducting magnets
in persistent mode where spurious losses become important.
Technical details notwithstanding, electromagnets can be divided into categories
depending on their maximum field range, duration, and their approach to overcome
problems related to Joule heating and magnetic pressure. Figure 4 gives an overview.
DC magnets require a robust construction to contain the applied pressure, yet
the principal concern is their isothermal operation. In resistive magnets, heat
has to be constantly evacuated, while electrical energy is reinjected at the same
rate. In superconducting magnets, spontaneous dissipation has to be avoided that
occurs when the kinetic energy of Cooper pairs becomes sufficient to break their
bond and the magnet turns resistive. DC magnets are therefore primarily, if not
exclusively, heat-limited.
Pulsed magnets are operated adiabatically. Their heat capacity buffers a limited
amount of dissipated energy as the field duration is adjusted to keep temperature
changes at a subcritical level. The principal challenge for pulsed magnets thus
becomes the quasi-static containment of magnetic pressure which makes them
mostly force-limited.
Megagauss generators limit the momentum transfer to the magnet in virtually
the same way in which conventional pulsed magnets limit the transfer of
heat, namely, by further reducing the pulse duration. Magnetic pressure is thus
contained dynamically, or, in simple terms, a high magnetic field is generated
before the magnet has time to disintegrate (which it ultimately does). Megagauss
generators are therefore speed-limited.
Fig. 4 Performance, operation regime, and categories of high-field electromagnets. The classifi-
cation in heat-, force- and speed-limited magnets indicates a general tendency rather than a hard
fact. In practice, the thermal and mechanical properties of DC and pulsed magnets always need to
be optimized simultaneously
Table 1 State of the art magnets in major high field facilities in 2019. A visual impression of
different magnet types is given on the right. For better comparison a coloured bar in the background
D C - m a g n e t s
Bmax Bore Power Type Fac.
(T) (mm) (MW)
31 50 19 Bitter Ta
31 50 18 Bitter Nij
31 50 24 Polyh. Gre
35 50 24 Bitter Hef
33 32 15 Bitter Tsu
35 32 19 Bitter Ta
36 34 24 Polyh. Gre
38 32 21 Bitter Nij Florida-Bitter principle
38 32 28 Bitter Hef
41.5 32 36 Bitter Ta
36.2 40 14 SCH Ta
38 32 15 Hybrid Tsu
40 (45) 32 28 (>28) Hybrid Hef
45 32 30 Hybrid Ta
42 34 24 Hybrid Gre
45 32 20 Hybrid Nij
P u l s e d m a g n e t s
Buse /Btest Bore FWHM Cool Type Fac.
(T) (mm) (ms) (min)
35/35.8 22 1500 120 mono Wu
43.5 30 1000 240 mono To
64 22 10* 30 flat-t Wu Polyhelix principle
60/65 33 300 120 mono Wu
60 18 35 20 mono To
60/62 28 90 75 mono Tls
65 21 80 35 mono Wu
65 20 10 60 mono Dre
65/67 15.5 20.1 37 mono LA
70/71 24 59 240 mono Dre
70/74 13 55 50 mono Tls
75/85.8 15 4 20 mono To
80/82 13 40 240 mono Tls
83/85 16 5 240 dual Dre
85/90.6 12 23 240 dual Wu
90/91 8 13 90 dual Tls
93/95.6 12 4 240 dual Dre Distributed fibre
95/98.8 8.5 11.8 120 triplex Tls reinforcement
95/100.8 10.5 10.5 180 multi LA
M e g a g a u s s g e n e r a t o r s
Buse Bore FWHM Type Fac.
(T) (mm) (µ s)
To,Tls
150/300 10 5-7 STC LA
650/1200 6-10 2 EMFC To Single-turn coil
22 Magnetic Fields and Measurements 1097
Bitter-type magnets consist of radially slotted copper disks that are vertically
stacked and separated by insulation foils enabling an electrical contact only via a
small segment next to the slit. As the position of the slit and the contact changes
by an azimuth angle along the stacking direction, a series connection of all disks is
established that gives rise to a helical current and hence a magnetic field. Cooling is
ensured by holes that allow a vertical flow of water [15,151]. The shape of the holes
is optimized so as to provide the best possible compromise between heat exchange
and flow resistance. Their radial distribution furthermore anticipates local heating
due to the non-homogeneous current density, while their azimuthal arrangement
close to the bore avoids the radial transmission of forces [9, 10].
Polyhelix magnets consist of a set of (up to 14) concentric cylinders with
individual wall thicknesses of about 1 cm. Each cylinder has a helical slit that is
produced by electroerosion and subsequent gluing with an insulating material. The
entire set of cylinders is connected in series and generates a magnetic field along the
axis of the cylinder. Cooling is ensured by narrow hydraulic channels between two
neighbouring cylinders [149, 33]. Polyhelix magnets are more difficult to fabricate
than Bitter magnets but provide more design freedom as far as the spatial control of
the current density is concerned.
Resistive high-field magnets have reached values between 36 and 41.5 T (cf.,
Table 1) giving rise to stresses up to 400 MPa, a value which exceeds the tensile limit
of Cu (cf., Fig. 2) and comes close to that of other currently available low-resistance
materials featuring conductivities of 45 to 58 MS/m. Although the midplane tensile
stress undoubtedly represents the most crucial limitation for such magnets, their
design also has to pay heed to axial compression that may in turn create shear forces.
Further complications are due to the mechanical robustness of insulating materials
that have to sustain at least part of the applied forces.
Taking into account the finite filling factor of real magnets, i.e., the fraction
of the volume actually occupied by conductor material, one obtains slightly larger
power values than those in Fig. 3. Large facilities therefore operate power supplies
providing 15 to 25 MW giving rise to power densities of typically 2 W/mm3 inside a
magnet. This causes heat flux densities up to 5 W/mm2 at their surface, a value about
one order of magnitude higher than in pressurized vessels of steam generators. The
Table 1 (continued) of each table-cell relates the displayed value to the maximum in the
respective class of magnets. Blue and green colours are used to highlight groups of magnets with
similar features. The last column indicates the facility as explained below. DC-magnet table: SCH
stands for series-connected hybrid. Magnets under construction are in italics. Pulsed magnet table:
Buse /Btest distinguishes fields that are available for users from records obtained with the same
magnet. For nested coils (dual, triplex, multi) the pulse duration (FWHM) refers to the shortest
pulse of the innermost coil. The starred value for flat-top magnets (flat-t, see explanation in the
text) indicates the duration of the plateau. Megagauss table: user fields depend on minimum bore
size. Dre: HLD Dresden [73], Gre: LNCMI Grenoble [92], Hef: HMFL Hefei [71], LA: NHMFL
Los Alamos [110], Nij: HFML Nijmegen [70], Ta: NHMFL Tallahassee [110], Tls: LNCMI
Toulouse [92], To: ISSP Tokyo/Kashiwa [80], Tsu: NIMS Tsukuba [173], Wu: WHMFC Wuhan
[188]
1098 O. Portugall et al.
Fig. 5 (a) Historical image of the Bellevue electromagnet built in 1928 to generate 5–7 T (©CNRS
photothèque, with kind permission); (b) modern triplex-pulsed magnet with 700 mm outer diameter
producing close to 100 T (©LNCMI, with kind permission); (c) hydraulics tubes around the chassis
of a resistive DC magnet (©Steffen Krämer); (d) 50 MJ capacitor bank for generating pulsed fields
(©HZDR, with kind permission)
penetration depth is related to, but not identical with, the ordinary skin effect that
only applies for stationary oscillations.
More recently, pulsed magnets have also been equipped with cooling channels,
not to evacuate heat during shots but in between [53]. This gives rise to considerably
enhanced duty cycles which represent an important factor for applications in user
facilities.
Realistic estimates for the heating of pulsed magnets can be obtained by integrat-
ing both sides of the expression j 2 (t) dt = D(T ) cp (T )/ρ(T ) dT that associates
the application of a current density j for a short interval dt with a temperature
rise dT in a conductor that is characterized by its temperature-dependent mass
density D, specific heat cp , and resistivity ρ. For most conductors, this so-called
action integral becomes more favorable at low temperatures which is one of the
reasons why advanced pulsed magnets are pre-cooled with liquid nitrogen. A base
temperature of 77 K also leaves a larger margin with respect to the relatively limited
heat tolerance of many insulating materials. The heating of pulsed magnets during
a shot can easily exceed 100 K.
In complete analogy to resistive DC magnets whose heat limitation motivates
the integration of cooling channels, pulsed magnets require reinforcing elements
to contain the applied magnetic pressure. First-generation pulsed magnets were
therefore reinforced externally. Their design was based on analytic calculations and
the destructive testing of downsized prototype coils followed by the application
of scaling rules to build larger specimens to be operated below the destructive
limit. The main shortcoming of this approach is that the magnet is regarded as
a mechanical continuum rather than a complex structure composed of helical
windings, isolations, reinforcements, and impregnations which cannot be easily
scaled simultaneously.
With one exception [89], modern pulsed magnets or pulsed magnet inserts
attaining the highest available fields are all based on the same basic concept of
distributed fiber reinforcement [17]. The principle is that of a wire-wound magnet
whose conducting layers are individually stabilized with layers of high-strength
fibers, a technique that has the additional benefit of electrically insulating adjacent
conductor sections. The material of choice is a synthetic polymer fiber commonly
known as Zylon™ whose tensile strength comes close to that of carbon fiber albeit
without the disadvantage of being conductive. The thickness of each reinforcement
section is adjusted such that neither a substantial transmission of forces between
successive layers occurs nor a separation when the coil is elastically deformed.
In recent years, the perfection of finite-element methods has shifted the design
focus from the comparably simple question of how to contain maximum stresses
in midplane to problems related to aging and local forces caused by the imperfect
cylinder symmetry of real magnets. In the latter respect, current terminals and the
transition points at either end of the magnet where wire is guided from one layer to
the next are potentially weak spots. Aging, on the other hand, can be due to either
repeated deformation beyond the elastic limit if a magnet is operated close to its
maximum, or thermal cycles and, in some cases, also the electric or mechanical
deterioration of insulating materials.
22 Magnetic Fields and Measurements 1101
Fig. 6 Voltage, current, and coil heating for different configurations of capacitor-driven pulsed
field generators. Violet, generator with a simple closing switch S and no crowbar CB; Red, thyristor
switch but no crowbar; Orange, modern crowbar circuit. The thyristor-and-crowbar option has the
advantage that the capacitor bank is discharged at the end of the pulse. The smooth decay is also
favorable for measurement applications, and the heating can be tuned via the crowbar resistance
1102 O. Portugall et al.
pulsed magnets are limited to 25 kV, a range where corona and other partial
discharge phenomena can still be controlled with relatively simple technical means
and where self-healing metallized film capacitors for pulsed power applications are
widely available on the market.
Although state-of-the-art capacitor banks in large facilities feature energies
exceeding 10 MJ, a variety of smaller sizes exists ranging from transportable
systems in shipping containers over mid-sized installations for special applications
[2, 52, 81] down to tabletop and even microscopic generators [96]. Special architec-
tures have also been developed to produce repetitive [79] and flat-top magnetic fields
[85]. As far as alternative energy sources are concerned, inductive storage has been
successfully tested in the past [6], but the project has been discontinued. Flywheel
generators originally built for other high-power applications have been recycled by
some facilities in order to obtain energies approaching the gigajoule range and the
possibility to implement controlled waveforms [147, 90].
Although generating the highest possible fields for scientific research remains at
the center of development efforts, pulsed magnet technology has started to expand
into other directions. Recent innovations for scientific purposes include split coils
providing lateral access in order to combine high fields with intense radiation
sources [40, 81] and pulsed dipole magnets for investigating the quantum vacuum
[7]. Pulsed magnets have also found their way into industrial applications where
they are used for magnetizing permanent magnets, electromagnetic forming, and
magnetic pulse welding.
Fig. 7 Electromagnetic flux compression principle: red arrows indicate magnetic flux, blue arrows
the current in the single-turn coil (STC, grey) and the copper liner (orange). (a) Flux generated by
the STC induces eddy currents in the liner and diffuses only partially through to the center. The
liner is compressed by the pressure associated with the larger flux density between its outer surface
and the STC. (b) As the liner starts to implode, flux in its center is compressed, while the flux
outside is decompressed; when the flux densities inside and outside are equal, the sense of the net
current in the liner and the pressure are inverted; however, the liner is now in full motion and thus
carries on through its own inertia. (c) The inertial movement continues to compress flux captured
in the center until the kinetic energy of the liner is fully converted into field energy
Magnetic Measurements
Measuring a magnetic field means to observe its effect on charge and spin. The
surprising diversity of magnetic field sensors results from the transformation of this
initial influence in three steps: Firstly, atomic, molecular, and solid-state interactions
alter the behavior of charges and spins and hence the way in which they respond
to an applied field; secondly, a given microscopic phenomenon affects different
22 Magnetic Fields and Measurements 1105
macroscopic state variables and response functions; and thirdly, few sensors are
simple transducers that convert the applied field directly into a standard voltage
output.
In this section, we start with a brief outline of magnetic field effects that can
be exploited for sensor applications. The principal mechanisms shown in Fig. 8
reappear in diagrams explaining the operation principles of different sensor types
in the subsequent paragraphs.
Upmost in the hierarchy of influences affecting the behavior of charges and spins are
atomic and solid-state interactions that regroup both in three categories. Quasi-free
charge carriers that give rise to Amperian currents exhibit single-particle behavior
while being characterized by their linear momentum. Likewise, magnetic moments
refer to charges or spins that behave individually but whose prominent dynamic
feature is their angular momentum. The combined effect of Coulomb repulsion and
Pauli principle finally generates effective exchange interactions that are at the origin
of collective magnetism.
Formally, the kinetic momentum of a system composed of charged particles
and electromagnetic fields, p − eA, represents the unique origin of magnetic field
effects in both classical and quantum theory. Here p, e, and A denote the canonical
momentum, charge, and vector potential. Spin-related field effects occur when
the expression is introduced into Dirac’s equation. In non-relativistic theories, the
respective terms are introduced ad hoc.
The well-known classical magnetic forces and equations of motion can be
deduced from p − eA through the Lagrange-Hamiltonian formalism. As part of
the Schroedinger or Heisenberg equations for quasi-free particles, p − eA produces
additional quantum√ effects, namely, a spatial modulation characterized by the
magnetic length h̄/eB that is at the origin of Landau quantization and Aharonov-
Bohm like quantum interference effects. Under realistic conditions, B < 103 T, this
is the only case where a magnetic field is quantizing in the sense that it generates
new quantum numbers.
For magnetic moments an external field only lifts the orientational degeneracy,
unless it reaches B ∼ 105 T, and the magnetic length is reduced to the order of the
atomic radius. All other cases are adequately described by the Zeeman Hamiltonian
and higher-order corrections that are the result of p − eA being expanded in terms
of angular momentum operators. Although magnetic fields do not generate new
quantum numbers in this case, their competition with, for example, a weak spin-
orbit interaction may nevertheless tip the balance between different sets of angular
momentum eigenstates. The Zeeman shift may also change the ordering of quantum
states and thus affect the ground state of a system.
In exchange-coupled systems, the situation is similar, except that the field
also has to compete with existing directional constraints due to the spontaneous
alignment of magnetic moments. The result varies substantially with the type of
1106 O. Portugall et al.
Larmor
Gradient precess. Class.
Torque
force cyclotron
(micro)
motion
Hall
effect
Magnetic
moment Lorentz Force on
force conductor
bound
Mobile
Spin Charge free
charge
EMF
Faraday
induct.
exchange coupled
Magnetic
Collective length
magnetism
Landau
quant.
S-ferro: Quantum
H-ferro: domain interf.
object dynam. Flux
dynam. concentr.
Spin-
Magneto- polariz.
Macrosc. striction
motion
Fig. 8 Scheme of effects that may be used in magnetic sensors. The formation of field-sensitive
media is represented inside the shaded area. The first bubbles outside indicate how magnetic fields
affect the respective equations of motion. H-ferro and S-ferro denote hard and soft ferromagnets.
The first react as macroscopic objects to a magnetic field, while the second change their internal
structure. Gray bubbles represent effects that are not generally used for sensing purposes
22 Magnetic Fields and Measurements 1107
magnetism and is in general subject to threshold and other nonlinear effects. In the
following, we limit our attention to hard and soft ferromagnets. In the first case,
the alignment force is effectively transferred to the macroscopic object, while in the
second, it affects the orientation of domains and thus gives rise to magnetization
changes.
the input signal required to produce a significant output compared to artifacts and
perturbations. The ubiquitous effect of noise in magnetic √ sensors, for example, is
characterized by a noise-equivalent field expressed in T/ Hz.
Slightly less specific, resolution is defined as the smallest input variation that
produces changes in a sensor’s output. Originally a key parameter for instruments
relying on discrete internal references (e.g., frequency in NMR) or featuring digital
output, resolution is also used in a wider sense to characterize a sensor’s lower
detection limit.
Sensors operating as transducers in larger setups where a certain output level
is mandatory are frequently characterized by their input-output signal ratio or
responsivity. Unlike all previously discussed parameters, responsivity provides no
real indication of relevant detection limits as it does not take into account intrinsic
perturbations.
dynamics are material dependent and ultimately limit the frequency range that can
be covered. This is particularly important in flux concentrators.
Magnetic sensors have been reviewed in books [141, 175] and articles [43,
94, 143, 176] often with emphasis on specific techniques, applications, or recent
advances. The present section presents a brief overview over the principal sensor
types, their measurement principles, performance, and practical importance. Further
information may also be found in Chap. 31, “Magnetic Sensors,” of this book.
1110 O. Portugall et al.
Table 2 Operation and performance limits for different sensor technologies. The parameter ranges
refer to sensor families as opposed to individual sensors whose specifications are generally much
more restrictive
Type Range [T] Bandlimit [Hz] Noise [T/Hz1/2 ] Practical importance,
specifications & references
Induction coil 10−13 –10+3 10−3 –10+9 10−13 @ 20 Hz, Highly adaptable, flexible
air design;
10−12 @ 1 Hz, easy to fabricate; [140, 174]
ferro
Fluxgate 10−11 –10−3 <10+3 10−12 Standard solution for
10−9 –10−12 T;
commercial products;
[127, 139, 142]
Hall effect 10−5 –1050 <10+6 10−7 Standard solution for
>10−3 T;
commercial products,
chip-integration
GMR, TMR 10−9 – <10+9 10−8 Standard solution for
AMR 10−3 <10+7 10−9 –10−3 T;
commercial products,
chip-integration; [167, 101]
SQUID 10−15 –10−2 10+9 @ 4.2 K 10−15 @ 4.2 K Standard solution for
10+4 @ 77 K 10−13 @ 77 K <10−12 T;
commercial products;
[170, 16]
NMR 10−10 –50 <10+2 10−6 , standard Absolute
10−12 , measurement/calibration
optimized standard;
sensitivity gain with
Overhauser effect (×10−1 )
or ESR/optical pumping
(×10−2 ); [76, 59, 61, 112]
Faraday effect 10−8 – <10+9 10−12 Electromagnetic
10+3 compatibility & remote
sensing;
10−11 T in advanced
laboratory tools
Lorentz force 10−9 –1050 <10+3 10−9 Emerging technology,
& other mostly Lorentz-force;
MEMS power-free sensing with
magnetostriction, torque;
[43, 69]
Magnetoelectric 10−10 –10−5 10−9 Emerging technology,
power-free sensing;
different device sizes;
[98, 179]
22 Magnetic Fields and Measurements 1111
Table 2 lists operation and performance limits for different sensor technologies.
The device specifications of individual sensors are generally much more restrictive
as both their size and architecture may differ substantially. This is particularly true
for induction coils. The fact that different scientific domains have produced their
characteristic architectures also explains why certain sensor types are assessed quite
differently in literature.
dB 0 Faraday
V
dt induction
dB 0 dB μ Faraday
Magnetization V
dt dt induction
Fig. 9 Working principle of induction coils with air (top) and soft ferromagnetic core (bottom).
B 0 is the external field, B μ the field associated with the core magnetization, and V the induced
voltage
1112 O. Portugall et al.
Table 3 Transfer function of induction and fluxgate sensors. For induction sensors a harmonic
time dependence of either the external field B0 or the coil area A was assumed to illustrate the
frequency dependence. V is the readout voltage, μr the core permeability, N the demagnetization
factor, ω the angular frequency, and i the imaginary unit representing a π/2 phase shift. The
fluxgate equation refers to the residual permeability μr that oscillates between 0 and μr
Type Transfer function Modulation
Air core V /B0 = iωA B0 ∼ eiωt (or A)
Magnetic core V /B0 = iωA μr [1 + N (μr − 1)]−1 B0 ∼ eiωt (or A)
dμr −2
Fluxgate V /B0 = A dt (1 − N ) 1 + N (μr − 1)
fixed and the wire cross-section is cut in half to accommodate a second winding,
hence Rnew = 4Rold .
Whenever small coil areas are mandatory, the resolution of induction sensors can
likely be improved with a ferromagnetic core producing an approximately constant
gain of ∼ N −1 as long as N μr 1 (cf., Table 3). Signal amplifications of close
to 103 may therefore be obtained while avoiding, at least partially, the nonlinearity,
temperature dependence, and Barkhausen noise associated with the permeability
μr . In return, the saturation and magnetization dynamics of ferromagnetic cores
respectively give rise to a material-dependent reduction of the upper field and
frequency limits.
Air core coils exhibit substantially larger upper bandlimits caused by the onset
of nonlinear behavior close to their resonance frequency. The latter arises from
parasitic capacitances between close-packed windings or the wiring between coil
and voltmeter. The input impedance of preamplifiers or low-pass filters used to
integrate transient signals may alter the frequency response further and thus have
a strong effect on sensor performance [29, 141, 174]. Since the output of induction
sensors depends on frequency, their lower band offset and resolution are correlated.
As a rule of thumb, air core coils provide extreme sensitivities, field, or frequency
ranges, whereas ferromagnetic cores are the best option for optimizing resolution in
a restricted volume.
Their simple architecture makes induction sensors a popular choice in science
and industry. They use basic materials (wire), are easy to manufacture (winding),
and do not require sophisticated readout technology (voltage measurement). Air
core coils can be made extremely large for applications such as traffic control
or geomagnetic measurements. Coils with 2 m diameter, 16,000 turns, a lower
frequency limit of 0.004 Hz and a resolution of 10−12 T have been reported [164].
Pick-up coils for measuring Megagauss fields, on the other hand, consist of a
single winding with less than 3 mm diameter and an upper frequency limit of
0.1–1 GHz that is determined by readout electronics rather than the coil itself.
The design flexibility of induction coils has also given rise to a variety of special
developments such as gradiometers, Rogowski coils for current sensing, or packs
of three orthogonal coils for vector measurements. Gradiometer coils, i.e., pairs of
compensated induction coils, can reach sensitivities of 10−13 T while remaining
compact enough for biomedical applications such as magneto-cardiography [46].
Planar thin-film coils (e.g., [58]) are an interesting alternative for producing simple
22 Magnetic Fields and Measurements 1113
Fig. 10 Fluxgate principle. The upper and lower halves, respectively, represent the transforma-
tions of the measured field B 0 and the modulation field B ω . After driving the ferromagnetic
core periodically into saturation, the modulation field is eliminated by compensation or frequency
filtering. Likewise, the constant measured field does not produce an induced voltage. However, the
flux it generates via the time-dependent residual permeability μr gives rise to an output voltage
that is proportional to the measured field
devices on a large industrial scale while avoiding the use of winding machinery
with moving parts. Due to their inability to detect constant fields, induction coils
rarely serve as stand-alone general-purpose sensors. They are mostly fabricated for
specific applications or to form part of a larger device. Simple pick-up coils are,
however, the standard monitoring tool for pulsed magnetic fields.
Fluxgate magnetometers [127, 139, 142] combine the rugged technology of
induction sensors with the capacity to measure constant fields. Figure 10 illustrates
their principle: a drive coil forces a ferromagnetic core periodically into saturation
thereby restricting its capability to respond to the external field. With respect to
the latter, the core exhibits a residual permeability that has maxima whenever the
drive field vanishes, i.e., at twice the drive frequency. Taking into account symmetric
distortions, the output of an induction coil that captures the total flux permeating the
core thus consists of odd harmonics caused by the drive field, whereas all even
harmonics are due to the external field.
The use of phase-sensitive detection techniques to recover the relevant second
harmonic from a fluxgate signal is relatively straightforward except that the
background of odd harmonics occupies most of the dynamic range and hence limits
the sensitivity. Advanced sensors are therefore designed such that the induction coil
does not capture any net flux from the drive field. As shown in Fig. 11, this can
be done by either magnetizing the core perpendicular to the induction coil axis
(orthogonal type) or using a double or ring core whose antiparallel flux contributions
cancel each other (parallel type). Still more sophisticated second-harmonic feedback
magnetometers make use of an additional compensation coil to operate as null-
detection devices.
The technical improvement of fluxgate magnetometers usually comes down to
a trade-off between the strict optimization of parameters determining the transfer
function in Table 3 and the control of secondary effects associated with these
optimizations. In complete analogy to induction coils, the addition of windings to
increase the effective area A of the sense coil is thus limited by the creation of
1114 O. Portugall et al.
Fig. 11 The basic parallel (left) and orthogonal (right) fluxgate configurations. Arrows indicate
the external field (red) and the magnetization of the core (yellow)
parasitic capacitances that ultimately affect the sensor response. Likewise, the shape
of the core influences not only the transfer function via the demagnetization factor
N but also the noise and modulation properties of the sensor. In the latter respect,
racetrack-shaped cores provide one of the best combinations of low noise and high
sensitivity [142]. Their layout resembles the parallel configuration in Fig. 11, except
that both cores are connected at the top and at the bottom so as to form a closed
magnetic circuit.
The core material enters the transfer function only via the residual permeability
μr and its time derivative, yet its choice is crucial for a variety of properties
including sensitivity, noise, linearity, field range, and power requirements. Materials
featuring a high permeability provide good sensitivity, but rapid magnetization
changes during operation tend to introduce noise associated with the domain
dynamics. The latter can be material-specific but ultimately also depends on the
technical quality of the core, in particular its homogeneity. Another important
material property is the saturation magnetization that determines not only the upper
limit of the measurable field range but, together with the coercivity, also the energy
consumption of the device. As fluxgate sensors are mostly optimized to provide best
sensitivity, the saturation field is usually kept small and the coercivity consequently
minimized. Suitable core materials should furthermore exhibit the least possible
magnetostriction to avoid vibrational perturbations during operation and have a high
resistivity to minimize eddy currents. While the criteria associated with different
applications may still motivate the choice of specific core materials, the majority of
fluxgate sensors nowadays make use of Co-based amorphous alloys or other metallic
glasses [142].
Being active devices, fluxgate magnetometers also depend on operating param-
eters. Square modulation generally assures the highest fluxgate output and hence
the best sensitivity. However, it also implies a relatively high energy consumption
depending on the core’s coercivity and saturation field. A possible work-around is
22 Magnetic Fields and Measurements 1115
to operate the fluxgate on a minor hysteresis loop, albeit at the price of sacrificing
part of the sensitivity [43]. Needless to say, the maximum modulation frequency
depends on the magnetization dynamics and eddy currents in the core.
Although their historical application range continues to be reduced by more
recent technologies, fluxgate sensors still represent the most appropriate choice for
measuring fields between roughly 10−9 and 10−12 T. The lower limit is associated
with their capacity to replace SQUIDs whose technology and operating conditions
are substantially more cumbersome, while the upper limit denotes their substitution
by even simpler magnetoresistive devices. While the technological optimization
of classical macroscopic fluxgate devices may be nearly exhausted, their minia-
turization using modern micro-fabrication techniques still shows some promise
[169]. Interestingly, the combination of deposition and etching in advanced MEMS
production techniques can replace coil winding which represents an undeniable
advantage for mass production.
Space charge
formation:
B0 Boundary Hall effect
Lorentz force:
conditions, V
charge deviation
I composites* Scattering on a
longer trajectory:
geom. MR, EMR*
Spin-orbit
I Direction
scattering:
control: I, M
AMR
Torque: magnetic
B0 V
scattering centers
Spin-dep. scatt.,
Magn. super-
& accumulation:
structures
GMR, TMR
Fig. 12 Hall and magnetoresistance sensor principles. Hall effect and geometrical MR are caused
by the Lorentz force in combination with suitable boundary conditions. EMR makes additional use
of composite structures. AMR, GMR, and TMR all refer to the intermediate effect of a magnetic
field on localized d states that subsequently act as scattering centers
1116 O. Portugall et al.
I
B
B B
Fig. 13 Hall bar (left) and Corbino disc (right). In the Hall bar, the deviation of charges by the
Lorentz force is limited by lateral boundaries and thus creates space charge regions on either side.
In a Corbino disc, the same effect produces a magnetic field-dependent circular current component
that prolongs the trajectory between the inner and outer disc radius and hence gives rise to MR
Lorentz force. In the first case, charges accumulate near the edges of a conducting
strip thus giving rise to a transverse electric field E that compensates the effect of the
Lorentz force, v × B. The Hall voltage V = Ew across a bar of width w therefore
provides a measure for the applied magnetic field. In Corbino discs, the situation
is different: here, the Lorentz force adds a circular component to the radial current
flow that prolongs the charge trajectory and hence increases the effective device
resistance. The so-called geometrical MR thus relies on the amount of scattering
albeit without influencing its origin. The same is true for the extraordinary MR
(EMR) that occurs in planar composite structures when the Lorentz force pushes
currents from low-resistance into high-resistance areas or vice versa [159, 72].
In order to generate significant effects, the Lorentz force has to produce a notable
curvature in the trajectory of charges between successive scattering events. Devices
are therefore based on high-mobility materials featuring long mean-free paths, while
their application is normally restricted to fields exceeding 10−5 T.
In magnetic materials, MR effects occur at substantially lower fields. Here,
the same, relatively localized, transition metal d-states that give rise to magnetic
properties also contribute to the scattering of delocalized states that govern the
charge transport. It is via these d-states that a magnetic field produces simultaneous
changes in the magnetization and MR whose phenomenological appearance can
be similar. The resistance changes nevertheless refer to microscopic scattering
processes and not just the flux-concentrating effect of the demagnetizing field.
The perturbative nature of scattering makes it generally difficult to pinpoint
microscopic mechanisms that govern a particular macroscopic behavior. Under
different conditions, similar mechanisms may even have opposite effects. Spin-flip
scattering thus accounts for the anisotropic MR (AMR) which is in principle a bulk
effect but tends to destroy the giant MR (GMR) that occurs in thin-film structures.
22 Magnetic Fields and Measurements 1117
Table 4 Transfer function of Hall sensors in its usual form depending on the current density j ,
the Hall constant RH and the Hall bar width w, and an equivalent description in terms of the
mobility μH , the charge carrier concentration n, and the power density P /V
Type Transfer function
√ √
Hall effect U/Bex = j RH w = μH /ne P /V w
cases, devices are therefore equipped with small coils to re-magnetize relevant
components.
Their simple architecture and linearity makes Si-based Hall sensors an all-
round solution for measuring fields down to 10−3 T, a limit that can be extended
further to approximately 10−7 T with high-mobility materials such as InSb. The
principal factors that determine the theoretical performance of Hall sensors are
defined by the transfer function shown in Table 4, which depends on mobility, carrier
concentration, size, and the applied electrical power density. The optimization of
real devices is obviously more complex. For example, increasing the power density
not only raises the signal level but also affects the device temperature and stability.
Likewise, the choice of materials, suitable geometries, and advanced electronic
circuits for controlling, biasing, stabilizing, and readout may have an impact on
performance [175, 119, 124]. Ongoing research and development activities are
furthermore concerned with complex integrated devices such as miniature three-axis
sensors, making use of the self-positioning effect of micromachined strained-layer
structures [169].
MR devices can measure substantially lower fields than Hall sensors and gener-
ally dominate in applications between 10−3 and 10−9 T. Their intrinsic nonlinearity,
however, tends to restrict their operating range. Therefore, most MR sensors are
either taylored to fit specific applications and parameter ranges or constructed as
null-detection devices. A frequently stated performance criterion is their relative
resistivity change Δρ/ρ which can be misleading as it does not determine their
ultimate performance: AMR exhibits a Δρ/ρ of only 2–4% as opposed to values
exceeding 100% for GMR and 500% for TMR at room temperature. However, all
three MR types have comparable low-field detection limits around 10−9 T. The latter
criterion also explains why EMR has not achieved more practical importance despite
a Δρ/ρ approaching 106 %: here, the measured MR change refers to fields of the
order of 1 T [159]. Similar restrictions apply for intrinsic MR properties such as
colossal and “unstoppable” MR that have been observed in some materials [134, 3].
Minor strengths and weaknesses notwithstanding, there is no striking difference
between the overall performance of AMR, GMR, and TMR, and the choice of one
or another is usually motivated by application-specific requirements [176, 165].
AMR sensors are simple, cheap, and robust, and their use and technical devel-
opment continues despite the rapid evolution of GMR and TMR and the fact that
their physical properties were comprehensively analyzed a long time ago [101, 97].
To eliminate their resistance offset and temperature instability, AMR elements with
±45◦ current orientation are often combined in two differential pairs forming a
Wheatstone bridge [86]. A remaining disadvantage is their sensibility to orthogonal
22 Magnetic Fields and Measurements 1119
fields which should not exceed 10%. Notable recent developments of AMR sensors
include flexible devices [86] and μm-sized structures where the current flows
straight through a wide zigzag-shaped permalloy band that produces an alternating
±45◦ magnetization [30].
GMR and in particular TMR sensors are primarily used in information tech-
nology. As far as sensor applications are concerned, their integrated circuit com-
patibility and small size make GMR devices interesting for applications requiring
high speed and spatial resolution [167]. Other notable developments include GMR-
based integrated systems for 3D magnetic sensing or high-temperature applications
[84, 86]. TMR has all but replaced GMR in information technology and is also
advancing in sensor applications. Despite their inherent problem with shot noise
in the tunnel barrier, TMR-sensor prototypes reaching 10−10 T have been reported
[95]. A remaining disadvantage of TMR is that its functioning depends crucially on
the integrity of the insulating layer: pin holes destroy the device.
GMI (giant MI) [122] refers to magnetic field-induced changes of the driving
voltage that is necessary to maintain a radio-frequency (RF) current through a
ferromagnetic conductor. The mechanism can be easily understood on the basis of
Ampere’s circuital law: the RF current is associated with a magnetic field BRF ,
and both are subject to the same skin effect. The penetration of BRF , however,
is determined by the polarizability of the medium, i.e., its permeability that, in a
ferromagnet, depends on the applied magnetic field B0 . Changing B0 thus tunes the
effective conductor cross section and hence the RF impedance. The effect becomes
“giant” in the vicinity of characteristic time constants of the medium that may be
associated with, for example, collective excitations, relaxation mechanisms, or the
domain dynamics.
GMI sensors use rather simple probe heads that essentially consist of a small
length of amorphous wire but inevitably require RF circuitry for their operation.
Industrial applications exist [74], and substantial research effort is dedicated to
the development of new GMI materials [122]. On the other hand, the precise
mechanisms giving rise to GMI are not yet fully understood, and theoretical
predictions promise much larger effects than those actually observed. GMI thus
remains an emerging technology, albeit with interesting perspectives: its response
ρ/(ρB) can reach
5000%/mT as opposed to
10%/mT for GMR devices [122].
superconductors to overlap but gives rise to a phase drop. If the phase drop is
nonzero, the junction is penetrated by a persistent current, not exceeding, however,
a critical value IC (Fig. 14).
Magnetic flux penetrating a closed superconducting circuit is quantized and can
only take values of integer numbers of flux quanta:
h
Φ = nΦ0 , where Φ0 ≡ ≈ 2.068 · 10−15 Wb (2)
2e
2π n = Δφ + 2π Φ/Φ0 (3)
Fig. 15 DC-SQUID operation: (a) Schematic circuit. (b) Screening current j (Φ). (c) SQUID
critical current ICSQU I D (Φ). (d) I − V curves for integer and half-integer flux quanta. (e) V (Φ)
the two extrema (Fig. 15d). If we now set the bias current in between, then the
corresponding voltage will oscillate with the period of one flux quantum (Fig. 15e).
RF SQUID. The setup with two J J s described above is called DC-squid, as it
is biased by a DC current. Opposed to this, an RF-SQUID is a superconducting
loop interrupted by only one J J and inductively coupled to an RLC “tank” circuit
(Fig. 16a). The tank is fed with a radio-frequency (rf) current at frequencies close
to the resonance of the circuit. Typically, the SQUID is designed so that it is able
to compensate about one flux quantum before the critical current IC is reached.
Let us assume that initially the SQUID contains an integer number of flux quanta
nΦ0 . If we now apply the rf-flux by ramping Irf of the tank, the SQUID has to
compensate it to maintain the flux in the circuit. As long as the screening current is
lower than IC , the corresponding voltage Urf will grow linearly as the SQUID is
in a fully superconducting state and does not affect the tank impedance. Once the
screening current reaches IC , the SQUID will change the state to n+1 or n−1. As
this transition takes place, the energy is drained from the tank, and it takes some time
(several RF periods) to recover the energy. As the energy is restored, the transition
takes place again. If Irf is increased, the tank energy recovers faster, so the flux
transitions in the SQUID are more frequent. Averaged over many flux transitions,
1122 O. Portugall et al.
Fig. 16 (a) RF SQUID inductively coupled to a “tank.” (b) V − I curves of the tank at integer
and half-integer flux quanta. (c) Tank voltage VT (Φ)
Fig. 17 Quantum (left) and classical (right) NMR principle. Left: Zeeman energy of discrete
energy levels of a spin-1/2 system in the presence of a magnetic field B0 . At the Larmor
frequency ω = γ B0 , a resonant absorption occurs due to a magnetic dipole transition. Right:
The magnetic moment associated with angular momentum precesses in an external magnetic field
with the Larmor frequency. This precession can be excited and detected by a pick-up coil oriented
perpendicular to the external field
Zeeman
splitting PSD (V )
induction
Faraday
at ωn
B0 M (t) dM
dt
torque, or
precession FFT (V )
ωn = γB0
hν Cyclotron motion
Projection
Intensity
Larmor precession
hν hν hν V
Circular magnetic
hν birefringence
Fig. 19 Magneto-optical detection principle (Faraday and Kerr effect). Red arrows indicate the
polarization at different stages of the measurement process
1128 O. Portugall et al.
Table 5 Transfer function of a Faraday rotator with ϑ as the rotation angle, V the Verdet constant,
l the length of the optical path, I0 the incident intensity, and ΔI the intensity change. In the
second formula, sin ϑ ≈ ϑ has been assumed. With standard optical detectors, the intensity change
translates directly into a voltage
Type Transfer function Condition
Rotation angle ϑ/B0 = V l Below magnetic saturation
Intensity change (I0 /2 + ΔI )/B0 = I0 V l 45◦ -polarizer, B0 (V l)−1
left- and right-hand circularly polarized normal modes. Depending on whether their
polarization vector revolves with or against the circular motion of free charges or
magnetic moments, the modes are subject to different phase shifts that ultimately
rotate the original linear polarization. To identify the rotation angle ϑ ∼ B0 ,
Table 5, an optical detector measures the relative radiation intensity transmitted
through a polarizer. This is proportional to ∼ cos2 (ϑ + ϑ0 ) where ϑ0 is the angle
of the polarizer relative to the polarization of the incident radiation. The polarizer
orientation determines how much intensity is transmitted at B0 = 0 and how it is
affected when the field is raised. In the particular case of ϑ0 = 45◦ , the change
of transmission associated with a sufficiently small magnetic field evolves linearly
around half the value of the incident intensity and depends on the direction of the
field.
Faraday rotation is material and wavelength dependent as characterized by
the Verdet constant. The latter becomes large in the vicinity of absorption lines
where the refractive index exhibits strong dispersion. Absorption must, however, be
avoided in order to guarantee that intensity changes are solely due to polarization.
Popular materials for Faraday rotators include terbium gallium garnet (TGG,
Tb3 Ga5 O12 ) featuring a large Verdet constant of −134 rad/T·m at 632.8 nm wave-
length [177]. Like all magnetic materials, TGG is subject to saturation and hence
becomes nonlinear at higher fields [178]. Typical Verdet constants of dielectric
materials are substantially smaller but, for all practical purposes, constant. CdS has
been reported to possess a particularly high Verdet constant around 125 rad/T·m at
632.8 nm [130] while evolving linearly up to about 500 T [38]. This corresponds to
one full rotation every 50 T over a length of 1 mm.
Faraday rotators can have extremely fast response times as the process itself is
only limited by the speed of light. Sensitivities may vary substantially depending
on the complexity of the setup [43]. The lower field limit in Table 2 represents an
average in this respect.
Modern fiber-optic technology has permitted the production of compact Faraday
rotation devices by integrating both polarizing and magnetically birefringent ele-
ments in a single fiber [166]. The latter are obtained by local terbium doping. The
practical importance of Faraday rotators as magnetic sensors remains nevertheless
limited compared to mass products such as Hall and MR devices. A notable
exception are applications where electromagnetic compatibility or remote sensing
over large distances is required. The frequency bandwidth, resolution, and noise
22 Magnetic Fields and Measurements 1129
Opt. deflection
I Lorentz
Demodulation (optional)
force
Opt. diffraction
B0
Interferometric
B op Compass ε V
Capacitive
Piezoelectric
Magneto-
B op striction
Tunneling
Fig. 20 Mechanical sensing principles in MEMS. Any mechanical sensing principle can in
principle be combined with any readout method. B op stands for an optional bias or modulation
field. The phase-sensitive detection step (PSD) is also optional
1130 O. Portugall et al.
While bias fields can still be implemented with permanent magnets, modulating
the field requires electromagnets which also reduces the sensor’s autonomy. On the
other hand, mechanical sensors featuring tunable bias magnets can also make use of
feedback loops to operate at constant deflection.
Mechanical deflection can be measured with a variety of methods whose
suitability depends on the required sensitivity and the practical context [69].
Detecting the actual torsion or deflection with a deposited layer of piezoresistive
material represents the most direct approach. Other methods refer to the tilting
of a lever or the displacement of a platform with respect to a fixed reference.
Electric measurement techniques thus make use of planar capacitors in a resonant
LC-circuit whose electrodes are respectively attached to the flexible structure and
a static support. Alternatively, the tunneling current through tips mounted in the
same way can be measured. A variety of optical methods refers to the reflection,
diffraction, and interference of light beams. In the first two cases, position-sensitive
detectors determine the deviation of a beam by either a mirror or a grating. Here,
the detector arrangement typically consists of two receptors capturing different parts
of a comparably large diffuse light spot. Interferometric measurements make use
of mirrors forming a Fabry-Perot cavity between the flexible structure and a static
reference.
Mechanical sensing without moving parts is possible with flat, typically
centimeter-sized, sheets of magnetoelectric composites that consist of alternating
layers of magnetostrictive and piezoelectric materials [192, 179]. The mechanical
coupling transmits field-induced strain from the magnetostrictive to the adjacent
piezoelectric layers where it produces a voltage that can be measured with a
simple two-terminal setup. Magnetoelectric sensors thus also have the advantage
of zero power requirements. Some single-phase materials exhibit magnetoelectric
properties albeit at a level that is too weak for sensor applications.
Compared to other sensor types, mechanical magnetometers are an emerging
technology based on either the advent of MEMS fabrication techniques or recent
developments in the area of magnetoelectric laminates. Lorentz force-based devices
are slightly less sensitive (cf., Table 2) but have the advantage of being linear,
easy to modulate, and capable of covering a relatively large field range. The use
of magnetoelectric composites, on the other hand, has the potential to provide √better
sensitivities over a limited field and frequency range. Noise levels of 10 pT/ Hz or
less have been reported for both stand-alone laminates and thin films on cantilever
structures which make these devices a likely candidate for biomedical applications
[83]. MEMS devices and magnetoelectric laminates are likely competitors for
fluxgate magnetometers that dominate the field range between 1 pT and 1 nT. Their
frequency bandwidth is, however, limited.
effect of these fields in order to gain insight into the magnetic (spin) and electronic
(charge) properties of the object.
Induction Magnetometers
In Sect. “Induction and Fluxgate Sensors”, the induction method for measuring
on Faraday’s law, V = −∂Φ/∂t, where
magnetic fields was introduced. It is based
the magnetic flux Φ is defined as Φ = B·dS. In the presence of a magnetic
object, B = μ0 μr H, or, otherwise, B = μ0 (H + M). Here, μr is the relative
magnetic permeability, and M is the magnetization of the material, defined as the
magnetic moment of a unit volume of the material: M = dm/dV; m is the net
magnetic moment of the sample originating from atomic dipole moments.
Generally, the magnetic permeability is a complex second-rank tensor: μ =
μ0 μr = μ + iμ . In order to define it, all the components of magnetic moment
vector should be measured for a given field direction. Appropriate devices called
“vector magnetometers” exist, yet, for most purposes, it is enough to measure
the magnetic moment along the field direction. This covers both isotropic and
anisotropic cases, when the permeability tensor is diagonal. Thus, scalar magne-
tometers will be assumed further in the text unless explicitly specified otherwise.
Magnetic flux then can be split into two parts:
Φ = ΦH + Φ M = (μ0 H + M) · dS (4)
S
mz ∝ Vind (t)dt (5)
1132 O. Portugall et al.
Fig. 21 Possible pick-up coil arrangements: (a) single coil, also called ‘magnetometer’, (b) first-
order gradiometer, (c) second-order gradiometer, (d) planar first-order gradiometer, (e) coaxial
gradiometer
The method described above is used in practice, yet, it is subject to noise due
to vibrations of the measurement coil and variations of the external magnetic field.
To cancel those spurious contributions, a pair of identical coils, connected in series
with opposite polarity (first-order gradiometer), is used. The sample is moved from
one coil to another, and the resulting integral is roughly twice the value of the
single-coil case. The coils are designed to provide flat parts on the sensitivity profile
in order to reduce dependencies on the positioning accuracy (Fig. 22). For certain
coil geometries, the sensitivity profile S(z) and the calibration constant C can be
calculated [193]. In practice, the whole device is calibrated with a known sample.
The particular time dependence of the sample movement is not important. There
are only technical limitations due to the speed of extraction: the movement should
be fast enough to provide an induced voltage in a comfortable range, and not too fast
to avoid disturbance of the integration. This allows for various types of drivers for
transporting the sample: electromagnet, stepper motors, or pneumatic pistons. An
extraction magnetometer can be conveniently built as a vector magnetometer [41],
22 Magnetic Fields and Measurements 1133
in which case, three orthogonal pairs of pick-up coils are used. Further improvement
can be achieved by averaging multiple extractions. The sensitivity can reach 10−8
Am2 [131].
Vibrating sample magnetometer: The vibrating sample magnetometer (VSM),
also commonly named Foner magnetometer after its inventor [51], utilizes a similar
principle of displacing the sample with respect to the measurement coils. However,
instead of taking the full integral of the sample flux, the sample is vibrating between
the coils in a time-harmonic manner:
z = A sin(ωt), (6)
where mz is the projection of the sample moment on the coil axis and C is the
calibration constant.
The vibration frequency ω appears as a factor in the effective sensitivity.
However, as considerable masses are involved in the motion, the frequency typically
lies within the range of 30–300 Hz, and the corresponding displacement amplitudes
vary from a few millimeters to a fraction of a millimeter. Phase-sensitive detection
(PSD) procedures are applied in order to convert the time-dependent induced voltage
to a quasi-DC signal proportional to mz . The oscillatory motion of the sample is
tracked by a dedicated sensor in order to feed the PSD with a proper reference
signal: it can be a small magnet attached to the driving rod, inducing a voltage in a
coil placed nearby.
The pick-up coil system is optimized to ensure a linear sensitivity region fully
covering the vibration amplitude [18]. It can be realized in both axial [75] and
transverse [51] geometry. In the former case, a first-order gradiometer is typically
used as pick-up coil. In case of transverse magnetic fields, the pick-up coil system
consists of a coplanar pair of flat gradiometers with the coil areas normal to the
magnetic field (see Fig. 23).
In most cases, the pick-up coil system is fixed with respect to the environment,
and the sample is moved. Alternatively, it is possible to fix the sample and move the
sensing coils. This is called then vibrating coil magnetometer, or VCM [158]. It is
more sensitive to inhomogeneities of the external field but allows measurement of
mechanically unstable samples such as loose powders and liquids. The sensitivity
of a VSM can reach 10−9 Am2 .
AC susceptibility measurements: The magnetization M can be defined as dM =
χ dH. The susceptibility χ thus is given as dM/dH. It can be measured in practice
by applying an alternating magnetic field (AC field): H = H0 sin ωt that should
be small enough to provide a linear response ∂M/∂H . The sample is located in a
pick-up coil that is part of a first- or second-order gradiometer. The entire system
is surrounded by an excitation coil generating the AC magnetic field (Fig. 24). In a
perfectly compensated pick-up coil system, the induced voltage will then be given
by:
∂Φm ∂M
Vind = − =C = Cωχm H0 cos(ωt + φ) = CωH0 (χ cos ωt + χ sin ωt)
∂t ∂t
(8)
A phase shift φ or, otherwise, nonzero parameter χ contains information on
the relaxation time of the spin system of the sample, as well as on dissipative
processes such as eddy currents or domain wall motion. Measurements of Vind are
typically performed with a lock-in amplifier (i.e., PSD), yielding both χ and χ
simultaneously. The AC field can be superimposed on an external DC magnetic
field, thus providing the field-dependent susceptibility χ = χ (H ). Integrating the
latter, the whole magnetization curve can be reconstructed. The AC susceptibility
technique is rather easy to implement in a compact size, and it is suitable for an
extremely wide temperature range of 1 mK up to 1000 K. The sensitivity of the
technique reaches 10−11 Am2 [190, 131].
Pulsed-field magnetometer: As described in the magnet section, magnetic fields
above 45 Tesla can only be achieved by pulsed magnets with typical durations of
10−6 –1 s. This is too short for a sample movement, and sometimes not even long
enough for AC-susceptibility measurements. Also, the requirements for compen-
sating gradiometers are extremely high. Unlike their DC counterparts, where the
22 Magnetic Fields and Measurements 1135
Torque Magnetometers
In an external magnetic field, a magnetic dipole is subject to (i) torque, trying to
orient the dipole along the field direction, and (ii) force, acting in the direction of
the field gradient.
τ = μ0 (m × H)
F = μ0 (m · ∇)H (9)
22 Magnetic Fields and Measurements 1137
Fig. 28 Torque
magnetometer
1138 O. Portugall et al.
dH dH
F = μ0 m = μ0 V χ H , (11)
dz dz
Fig. 29 Magnetic scales based on the Faraday (a) and Gouy (b) methods
with magnetic field H , the respective change of the magnetic energy U gives rise to
the force
dU 1 d(BH V ) 1 dV 1
F = = = μ0 χ H 2 = μ0 χ H 2 A (12)
dz 2 dz 2 dz 2
The sensitivity of the method is to a large extent defined by the mechanical balance
and can reach ∼10−12 Am2 [121].
Magnetic balance methods have given rise to numerous modifications, one of
the most important being the Evans magnetic balance [47], as its principle is
implemented in a number of commercial devices. There, the force acting on the
sample is counterbalanced in the other arm of the balance by a coil placed in a field
gradient.
Alternating gradient technique: Magnetic scale methods provide good sensitivity,
yet their performance can be spoiled by mechanical noise of the environment. A
typical approach to improve signal-to-noise ratio is modulation of the excitation
parameter and synchronous detection of the signal. Gradient modulation techniques
have first been introduced by Zijlstra [194]. The field gradient is produced by a pair
of coils fed with an AC current, and the force acting on the sample oscillates in
phase with this current. In a vibrating reed magnetometer, the sample is attached to
an elastic reed and forms a cantilever (Fig. 30). The force is read by a strain gauge
attached to the reed. In order to increase the sensitivity, the excitation frequency
is chosen close to the resonance of the system. The sensitivity of conventionally
sized devices (as opposed to microcantilevers from [107]) is about ∼10−9 Am2
[50, 138].
There are many cases where it is important to map the spatial variation of the stray
field of a magnetic structure. A prominent example is the study of domain walls in
magnetic materials [28]. With the development of magnetic devices for data storage,
1140 O. Portugall et al.
or the absence of stray fields. The best accuracies that can currently be achieved
under these conditions are of the order of 1 ppm and generally refer to the mT-range
[183,118]. At μT-fields, the relative accuracy inevitably gets worse as the resonance
frequency drops and the screening of stray fields becomes increasingly difficult.
As primary standards exist in highly specialized metrology institutes only, their
dissemination is achieved via different levels of subordinate standards. At the
bottom of the hierarchy are working standards used to calibrate equipment locally,
on a day-to-day basis. These can be either artefacts or measurement devices with a
traceable relationship to the relevant primary standard.
Since NMR has become a relatively conventional and affordable technique, its
use as a working standard is no longer an exception: commercial NMR-based
Teslameters generally promise accuracies of 5–10 ppm. Cheaper and more widely
used are Hall probes which provide less accuracy but have the additional advantage
of small size and a relatively wide field range.
Another alternative that can in principle be homemade are field coils in con-
junction with accurate (and precise) current sources. When designing a field coil
standard, special attention has to be paid to (i) the field homogeneity across the
measurement volume that must be better than the accuracy target; (ii) the choice
of an operating regime that avoids heating and deformation; (iii) the compensation
of parasitic effects associated with, for example, the current leads that connect the
coil; and (iv) the accuracy and precision of the current source. To provide sufficient
homogeneity, most field coil standards are based on long, thin-walled solenoids,
Helmholtz-coils, or more complex Helmholtz-like arrangements such as Braunbek
or Barker coils. For practical reasons, very large specimen may be polygonal rather
than circular [57].
When calibrating one device by another, accuracy is inevitably lost. An interest-
ing study in this respect has been performed by seven European metrology institutes,
each measuring the field-current ratio of the same coil with their respective
instruments and procedures [184]. While the weighted and averaged measurement
uncertainty gave an overall agreement within 50 ppm in this study, individual
results still showed deviations of up to 0.5%. In this respect, it is safe to assume
that a simple, possibly homemade, working standard will usually not permit field
calibrations of much better than 1%. To obtain higher accuracies, only certified
instruments with documented relationship to the respective primary standard should
be used.
Despite their inherent inability to measure absolute field values, SQUIDS
represent a useful tool in metrology. Their unrivaled capacity to detect field vari-
ations with outstanding spatial resolution makes them highly suitable for mapping
inhomogeneities that limit the accuracy of, for example, field coil standards. In
this case, their complete insensibility to a constant background field turns into an
advantage as the offset doesn’t reduce the dynamic range of the measurement.
While Tesla standards are important for calibrating fields and field sensors, they
are of limited use for devices designed to measure absolute magnetic properties. The
preferred technical solution in this case are certified reference materials (CRM).
A CRM for bulk magnetic measurements typically consists of a piece of material
22 Magnetic Fields and Measurements 1143
Acknowledgments The authors are grateful to Carlo Rizzo for helpful discussions on metrology
issues.
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22 Magnetic Fields and Measurements 1151
Contents
Thin Film Growth: General Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1155
Phase Transition Out of Equilibrium, Surface Kinetics and Growth Modes . . . . . . . . . . . 1155
Choice of Substrate and Role of Buffer Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1159
Molecular Beam Epitaxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
The Ultrahigh Vacuum Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1165
Control of Molecular Beam Fluxes and Substrate Temperature During Growth . . . . . . . . 1167
The In Situ Monitoring of the Film Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
The Applications of MBE in Novel Functional Materials . . . . . . . . . . . . . . . . . . . . . . . . . 1169
Comparison with Other Deposition Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1178
Pulsed Laser Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1179
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1179
Target Preparation and Manipulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1181
Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1181
Ablation Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1182
Optics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1183
Thickness Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1183
Substrate Heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1184
Selected Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1184
Magnetron Sputtering Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1186
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1186
Material Targets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1186
Abstract
The growth of thin films relies on an effective condensation of atoms from the
vapor (or liquid) phase onto a solid surface. While it may seem a straightforward
statement, the real scenario is much more complex: the atoms undergo several
competing kinetic processes when they arrive to a particular surface. These kinetic
processes – such as adsorption, diffusion, or desorption – are strongly dependent on
material parameters, but they can also be efficiently steered by adjusting external
conditions such as the atomic flux or the surface temperature. The way the atoms
arrange on the surface has been classified according to their morphology – the so-
called growth modes – and is a key factor to determine the physical properties of the
films. In most of the cases, the arrangement of the atoms at the surface can be hardly
reversed because the vapor-solid phase transition occurs out of thermal equilibrium,
such that special attention to the growth conditions needs to be paid at the very early
stage of growth. In that regard, the properties of the substrate play a decisive role,
and a right substrate choice is often the clue to develop the thin film growth of new
materials or a good starting platform to achieve unprecedented film properties. A
brief review about the concepts of vapor-solid phase transition out of equilibrium,
surface kinetics, and growth modes and the role of the substrate and buffer layers
will be described in the following sections.
The central concept of thin film growth under high vacuum conditions is to achieve
a controlled phase transition of atomic entities (either elements or molecules) from
the vapor to the solid phase, in a thermodynamic regime out of equilibrium. For
this process to occur, the pressure of the atomic or molecular beam pbeam has to be
higher than the vapor pressure at thermal equilibrium peq of the element. From a
more general perspective, the tendency of a system to undergo a phase transition
can be described by the Gibbs free energy G = U + p V – T S, where U is the
internal energy, S is the entropy, and p,V is the pressure and the volume of the
system (in our case, the growth region), respectively. A positive balance of the Gibbs
free energy between initial and final state (G > 0) will lead to a phase transition,
while for a negative G, the system will remain in the same phase. To apply these
concepts to a thin film growth experiment, one has to assume an infinite material
reservoir providing a constant gas pressure (pbeam ) and a thermal bath providing a
constant temperature to the growth zone (Tsubstrate ), conditions which are reasonably
fulfilled in a typical experiment. In that way, a calculation of the entropy S and
enthalpy H (H = U + pV), leading to the Gibbs free energy, can be performed to
judge if the solid-state growth of certain substances is thermodynamically possible
at all. A more detailed theoretical roadmap to calculate these quantities can be found
in [1]. These considerations are particularly relevant if one aims to grow a particular
1156 A. Bedoya-Pinto et al.
element or compound which does not exist yet in thin film form. Otherwise, it is
always useful to look at existing phase diagrams.
While the first step is to assess that a vapor-solid phase transition is thermo-
dynamically accessible within reasonable conditions of temperature (Tsubstrate ) and
vapor pressures (pbeam ), it is of paramount importance for the film properties to
determine how this vapor condenses at the surface. To this end, one has to consider
the following kinetic processes experienced by the atoms once they arrive to the
surface:
Adsorption and desorption are opposite processes, which generally occur when
the atoms either stay at or leave the surface. Adsorption occurs when the atoms get
immobilized due to attractive potentials at the surface (chemical, electrostatic). This
is likely to occur at defect sites/dangling bonds, step edges, or electrostatic potentials
from polar substrates. One specific example of adsorption (and which is desired
in a thin film growth experiment) is when the impinging atom chemically binds
and incorporates to the surface lattice. This process can be conditioned by proper
surface functionalization of the substrate, e.g., by constructing a particular atomic
termination and dangling bond configuration which is energetically favorable for the
atom to bind. Desorption is the reverse process, when immobilized atoms (either
chemically bound or unbound) are released from the surface to the vapor phase,
usually happening after some amount of energy (mostly thermal) is given to the
system. Another very relevant case is when the atoms do not have the amount of
energy needed to leave the surface, but still enough to overcome surface potentials
and remain mobile at the surface: the diffusion regime. Surface diffusion is a
key parameter to control the growth morphology of the thin films. Under some
circumstances, the diffusion of atoms is not restricted to the surface. Especially
light elements can diffuse underneath the surface through the crystalline substrate
or underlayer (bulk diffusion), until they find a trapping potential in the solid. One
has to be aware of this phenomenon, as it may alter the properties of the substrate
or the underlayer, being the latter especially relevant when growing multilayers
or heterostructures. Aggregation occurs when an atom prefers to stick next to
another atom already residing at the surface instead of finding its own way. The
first atoms sticking on the surface are thus called nucleation centers, from which
the material growth should develop. The aggregation process can be two- or three-
dimensional: A 2D aggregation is needed for a layer-by-layer growth, whereas a 3D
aggregation will lead to the formation of islands or clusters. Last but not the least,
the decomposition process, which happens when a compound or molecule loses one
or more of its constituents, can occur both on the surface and on the vapor phase side
(thermal cracking). Decomposition is generally unwanted, as the fragmentation of
23 Material Preparation and Thin Film Growth 1157
molecules or substrate bonds releases new species that enter the kinetic scenario and
thus re-arrange the formation of phases. However, there are some unusual routes
that rely on controlled decomposition to achieve, for instance, doping or surface
templating. All these relevant processes, only briefly described here for a general
understanding and depicted schematically in Fig. 1a, are extensively discussed in
specialized books and reviews [1–3].
Since it is extremely difficult to account for a full theoretical description of
the kinetic processes due to the large number of variables, an empiric approach is
routinely applied to develop thin film growth recipes. However, a good understand-
ing of the growth kinetics and the knowledge of some material parameters (e.g.,
surface energy, cohesion forces) is very useful to start a thin film growth experiment
within a reasonable parameter window. The interplay of the aforementioned kinetic
processes will determine the growth mode of the film, which can range from a
two-dimensional, layer-by-layer growth to a fully three-dimensional (island) or
columnar growth. These are summarized schematically in Fig. 1b, along with the
morphology evolution during the initial stage of growth. A layer-by-layer growth,
also known as Frank-van der Merve growth, generally sets in when the atoms
have a stronger affinity to stick to the surface than to aggregate to each other. In
the absence of nucleation centers, i.e., in a perfectly flat and defect-free surface,
the atoms would find available spots on the surface until the first monolayer is
completed. But in reality, the first atoms reaching the surface will get pinned at
defects, step edges, or any type of attractive surface potentials, from which the
nucleation and crystal growth process will start, provided that the atoms (either
within the same of different species) have a natural affinity to bind and form a
(crystalline) structure. Important for the Frank-van der Merve growth regime is
that, regardless of the number of nucleation centers, the growth of the second layer
does not start until the full surface coverage is accomplished by the first layer.
Diffusion plays here an important role, as the atoms might move sideways until
they find their energetically most favorable position. In cases where the substrate
surface present a regular terrace structure (originated by a slight miscut angle during
preparation, see Sect. “Choice of Substrate and Role of Buffer Layer”. for details),
Fig. 1 (a) Kinetic processes occurring in a solid surface upon exposure to gaseous molecular
beams. (b) Schematic representation of the main growth modes and the arrangement of the atoms
at the early stage of growth. (Taken from [4])
1158 A. Bedoya-Pinto et al.
the Frank-van der Merve growth manifests in the homogeneous atomic coverage
of each terrace, provided that the diffusion length of the atoms in the surface is
longer than the terrace width. This special case, favoring a layer-by-layer growth
over regular step terraces, is often denoted as step-flow growth. In particular, where
the substrate step terraces have monoatomic height similar to the lattice parameters
of the growing crystal, the subsequent layers will accommodate on top of each
other without building stacking faults and yielding a high crystalline order. Thus,
the step-flow layer-by-layer growth is one of most sought-after conditions for a
defect-free and high-quality epitaxy on substrates displaying a finite miscut angle.
On the other hand, a layer-by-layer growth is disrupted if the cohesion forces
between the atoms are larger than the affinity for them to bind to the surface.
This will lead to a volumetric (3D) aggregation of atoms at distinct nucleation
centers of the surface, denoted as Volmer-Weber or island growth. Depending on
the interplay between diffusion and aggregation, these islands might coalesce at a
particular film thickness. Even if the islands merge with each other, the Volmer-
Weber growth mode generally leads to a high surface roughness and large structural
mosaicity, which is usually unwanted for thin film applications. Interestingly, there
is a special case within the Volmer-Weber regime when the coalescence of islands
is energetically not favorable, such that the growth evolves perpendicular to the
surface (columnar growth). This directional growth regime has been proven useful
to achieve the bottom-up growth of nanowires/nanowhiskers of high crystalline
quality [5, 6], as each column will not experience much strain forces during the
directional growth. The diameter of the nanowires can be controlled by (artificially)
setting the density of nucleation centers on the surface. Last but not the least, a
combination of layer-by-layer and island growth can also occur during a growth
process, denoted as Stranski-Krastanov (mixed type) growth. It happens usually
when the growth starts in a layer-by-layer fashion, but later turns to aggregation
and three-dimensional growth, as exemplified in Fig. 1b. One reason is simply that
when the growth starts, the undergoing kinetic processes happen at the substrate
surface, while the situation changes as the growth evolves and the substrate is fully
covered by the material under study, constituting a “new” surface for the impinging
atoms. One route to overcome this is to change the growth parameters (e.g.,
temperature, atomic flux) after the first layer(s) covers the substrate surface, such
that conditions for layer-by-layer growth can be re-established (two-step growth).
In the case of homoepitaxy (a thin film grown on a substrate of the same kind),
although less common, a Stranski-Krastanov growth may set in if the surface energy
or the lattice parameters experience a change as the thickness of the grown layer
increases.
The knowledge of the kinetic processes and resulting growth modes, their
identification, and the correlation with the growth parameters lie at the heart of a thin
film growth experiment (typically, the growth modes and its resulting morphology
are assessed via in situ methods such as electron diffraction or surface topography
scanning probes). In this regard, a decisive role is played by the substrate surface,
as in many practical cases, a bad choice of the substrate or a deficient surface
preparation cannot be compensated by adjusting the growth parameters. Therefore,
23 Material Preparation and Thin Film Growth 1159
the next subsection will be devoted to the role of substrates; and in the cases where
optimal substrates cannot be found or prepared, the preparation of a buffer layer as
a n alternative solution will be underlined.
One important aspect for a successful epitaxial growth is the choice and preparation
of the substrates. As a rule of thumb, the following criteria need to be taken into
account:
It should be noted that for many cases, it is not so easy to find substrates that
fulfill all these requirements. One can still achieve epitaxial growth even if not all
these conditions are strictly met, but one has to be aware that additional actions need
to be implemented, adding more complexity to the substrate preparation process.
For instance, the problem of lattice matching between substrate and film can be
overcome, to a certain extent, by the growth of an intermediate buffer layer. On
the other hand, the temperature stability and chemical reactivity of the substrate
are more critical parameters, as the substrate surface might undergo irreversible
structural changes upon heating or exposure to particular atomic fluxes. The
matching of thermal expansion coefficients is important to avoid inhomogeneous
compression/expansion or substrate and film upon heating/cooling cycles, which
might lead to cracking and rippling of the grown layers. Last but not the least, the
preparation of a substrate with an atomically flat surface (via chemical or thermal
treatment) reduces the diffusion barriers driven by topography and thus facilitates a
layer-by-layer growth mode.
Typical substrates that are used for epitaxy (besides Si-wafers, which are one
of the most popular ones due to CMOS compatibility) are oxides and nitrides.
They have the advantage to be, in general, chemically inert due to a strong ionic
and/or covalent bonding and thermally stable up to relatively high temperatures.
In addition, there is a vast knowledge about surface preparation recipes on these
compounds [7], to get rid of surface contamination as well as to achieve an
atomically flat topography. Figure 2 shows an example of how chemical cleaning
and high-temperature annealing procedures impact the surface topography of
commercially available substrates, such as Al2 O3 (0001). While a modified RCA
(named after Radio Corporation of America, originally developed for Si-wafers)
cleaning treatment is able to get rid of surface adsorbates (Fig. 2b), an additional
high-temperature annealing (1150 ◦ C) under O2 atmosphere results in an ordered,
1160 A. Bedoya-Pinto et al.
Fig. 2 Atomic-force microscopy images of Al2 O3 (0001) substrates (a) as received from the
commercial supplier, (b) after modified RCA cleaning of the substrate, and (c) after RCA cleaning
and high-temperature annealing (1150 ◦ C) in a furnace under oxygen atmosphere. The chemical
cleaning step is efficient in removing all the impurities on the substrate surface, and atomically thin
step terraces are visible after the annealing procedure
atomically flat surface, featuring step terraces as thin as one unit cell of the Al2 O3
(0001) crystal (Fig. 2c). This example shows how chemical and heating treatment
recipes are key to produce a substrate surface with ideal conditions to initiate a
controlled layer-by-layer, step-flow growth.
Most of the commercially available substrates are produced as bulk crystals with
extremely large structural coherence and a low number of defects and dislocations;
and then they are mechanically cut to a particular size and surface-treated via
chemical-mechanical polishing (CMP) procedures. Both of these characteristics
from surface-finished bulk substrates (low defect density and surface flatness) are
favorable conditions for thin film epitaxy. However, there are cases where bulk
crystal synthesis of substrates is extremely difficult and can be only performed under
extreme conditions. For example, gallium nitride (GaN), a very common compound
used in III–V semiconductor applications and a popular substrate for nitride
epitaxial growth, can only be synthesized at 1700 ◦ C and at pressures (20 kbar)
to overcome the low solubility of N in the molten Ga liquid [8]. An alternative to
bulk crystal substrates that has been developed is the fabrication of “freestanding”
substrates, which result from the epitaxial growth of a given material on a foreign
substrate (heteroepitaxy) and its subsequent detaching from it. In the case of GaN,
freestanding substrates are usually prepared by epitaxial growth of a very thick
GaN layer (>100 μm) on sapphire or SiC substrates, followed by a delamination of
the GaN layers from the substrates via a laser-induced separation method [9]. One
important issue to consider here is that the quality of the freestanding thick layer is
determined from the growth procedure on the initial substrate. Thicker freestanding
substrates have usually superior structural quality, since in heteroepitaxial systems,
the number of dislocations reduces with film thickness; but the production costs are
also higher. Another – less expensive – alternative for epitaxial growth that does not
involve delamination is to use the layers still attached to their foreign substrates, also
called heteroepitaxial “templates. ” The structural quality and surface morphology
23 Material Preparation and Thin Film Growth 1161
Fig. 3 Surface topography of different GaN (0001) substrates. (a) GaN (0001)/Al2 O3 (0001)
template grown by MOCVD, showing atomically sharp terraces and a low number of dislocations
(black areas). (b) Bulk GaN synthesized by high-temperature and high-pressure methods. Although
it presents a low roughness, no atomic steps are visible. (c) GaN (0001) template grown on Si (111),
showing the highest roughness and the largest amount of dislocation densities. (d) Rocking curve
of the asymmetric (104) GaN reflection, showing that the bulk crystal has the lowest full width at
half maximum and thus the best crystallinity. (Courtesy: Christian Zube, University of Göttingen)
of these templates vary depending on the lattice matching to the substrate and the
thickness and the thermal expansion coefficients. Figure 3 shows an example on
how different substrate production strategies affect their surface morphology and
structural quality. While the bulk GaN (0001) substrates synthesized with high
pressure and temperature methods display the lowest roughness (Fig. 3b) and best
rocking curve widths, a measure of the crystalline coherence (Fig. 3d), the surface
does not present atomic step terraces. On the other hand, the GaN(0001) “templates”
grown on Al2 O3 (0001) and Si (111) (Fig. 3a, c) both present a surface featuring
step terraces but display wider rocking curve widths indicative of more structural
defects. Comparing only the two heteroepitaxial templates, the GaN (0001) grown
on Si (111) exhibits a larger structural defect density (the widest rocking curve
width, Fig. 3d), which, in turn, manifests also in an irregular surface step terrace
pattern and a higher surface roughness (Fig. 3c). This difference is attributed to
the large lattice mismatch (17%) between Si (111) and GaN (0001) and dissimilar
thermal expansion coefficients, and although this has been partially mitigated by the
insertion of AlN/GaN buffer layer superlattices in up-to-date industrial processes,
the substrate quality is still moderate. The GaN (0001) template on Al2 O3 (0001), on
the other hand, has an overall good performance in terms of surface roughness, step
terrace homogeneity, and crystalline quality, added to the advantages of low cost
compared to freestanding substrates. These are the usual benchmarks to consider
for a proper choice of substrate provider.
In the last years, the accelerated discovery of materials with exotic properties
gave rise to an ever-increasing demand to grow thin films of complex crystalline
structures and atomic compositions, for which a substrate fulfilling the optimum
requirements – listed at the beginning of Sect. “Choice of Substrate and Role of
Buffer Layer” – is difficult to find. One of the biggest problems in this regard is
the structural lattice mismatch of the material structure to the available substrates.
However, there are some strategies to overcome this limitation, such as:
1162 A. Bedoya-Pinto et al.
(i) To find a geometrical overlap of multiple surface unit cells into a single one
(e.g., multiple cubes into one rectangle)
(ii) To find a lattice matching by allowing the rotation of substrate and film surface
unit cells under specific angles
(iii) To grow one (or more) buffer layer(s) with lattice parameters in between the
values of substrate and film, effectively reducing the lattice mismatch
All these strategies are not mutually exclusive, and they can be implemented in
the same growth procedure if required. In the following, the rational use of these
strategies will be exemplified with the help of two novel topological materials, WP2
and NbP, each of them having a peculiar crystal structure which makes it difficult
to lattice-match with commercially available substrates. WP2 has an orthorhombic
structure (non-symmorphic Cmc21 space group) with very dissimilar a (3.17 Å),
b (11.16 Å), and c (4.97 Å) lattice parameters, but which is highly interesting
to explore in thin film form, due to its exotic electron transport properties which
resemble the ones of a hydrodynamic fluid [10]. Among insulating substrates, which
are desirable to explore the intrinsic transport properties of the films, one of the very
few options is to use AlN (in the wurtzite structure), but using the (1–100) plane,
unlike most of the epitaxial processes which rely on the hexagonal (0001) plane. In
this configuration, the a and c lattice parameters of AlN match well with the ones
of WP2 (mismatch of 1.7% and −0.16%, respectively), as depicted schematically
in Fig. 4a. This example shows that a careful search on non-conventional crystal
faces among the large substrate database is often the key to find the solution of an
epitaxial growth problem. However, this provides only a solution for an epitaxial
growth along the b-axis of WP2 (a–c plane on the surface). As many physical
properties depend on the crystalline orientation (for instance, a large crystalline
anisotropy of the magnetoresistance has been measured in WP2 bulk crystals [11]),
it is often required to pursue the epitaxial growth along different orientations. For
an orthorhombic structure with dissimilar lattice parameters like WP2 , this can be
a real challenge. A strategy to grow WP2 along c-direction (which means a basal
plane of a = 3.17 Å and b = 11.16 Å) is found by the geometrical fitting of multiple
surface unit cells onto a given structure. As depicted in Fig. 4b, this condition can
be achieved by fitting three rectangular a–b units into a non-integer multiple of a
hexagonal surface lattice, such as the GaN (0001) or NdGaO3 (011) plane. This
yields a lattice mismatch of 0.8% and 2.1% in a and b of WP2 , respectively. Such
an unusual geometrical lattice fit like WP2 on GaN is usually more challenging to
achieve in a real growth experiment; however, they shall be mentioned for the sake
of completeness and to encourage the reader to think also about these possibilities
for a lattice-matched epitaxial growth.
A second example, where the lattice mismatch is reduced by the rotation of the
unit cell in the surface plane and a subsequent growth of a buffer layer, is highlighted
by the growth of NbP thin films on insulating oxides. NbP, a recently discovered
topological semimetal with ultrahigh electronic mobility [12], crystallizes in a
tetragonal structure (space group I41 md) with lattice parameters a = 3.34 Å and
c = 11.37 Å, as depicted in Fig. 5a. Although it features a square lattice in the
23 Material Preparation and Thin Film Growth 1163
basal a-a plane – and thus a less complicated case than orthorhombic WP2 – the
available palette of lattice-matched cubic and perovskite substrates is scarce. For
square surface lattices, one intuitive strategy to account for a lattice matching
is to consider a rotation of 45◦ between substrate and growing film. Hence, by
choosing either MgO (a = 4.29 Å) or rutile TiO2 (a = 4.59 Å) and rotating it
45◦ to get a lattice distance of 3.02 Å and 3.24 Å in (110) direction, respectively
(Fig. 5b), one approaches the lattice constant of NbP. While for the case of TiO2 ,
the mismatch to NbP (3.34 Å) is still reasonable (<3%) to proceed with an epitaxial
growth experiment, the growth of NbP on MgO substrates will require additional
efforts to improve the lattice matching: the growth of a buffer layer. Cubic Nb
(100), with a lattice parameter of a = 3.30 Å, lying in between substrate and film,
appears as a good buffer layer candidate: in fact, high-quality epitaxial films of
NbP have been grown using this strategy [13]. The role of the buffer layer, or
sometimes called sacrificial layer, is to reduce the lattice mismatch at expenses of
sustaining a large amount of structural defects, thus improving the situation for the
subsequent growth of the layer of interest. The defect density typically reduces
with increasing buffer layer thickness, so that it has to be individually adjusted
for each epitaxial growth process – the initial mismatch is also different in each
case. In situ characterization techniques, such as reflection high-energy electron
diffraction (RHEED) and scanning tunneling microscopy (STM), are of great help
to judge whether the surface quality of the buffer layer of a particular thickness
is good enough for the subsequent epitaxy of the layer of interest. Figure 5c
describes the growth evolution of NbP (001) on MgO (001) using a Nb (001)
1164 A. Bedoya-Pinto et al.
Fig. 5 (a) Tetragonal, non-centrosymmetric crystal structure of NbP. (b) Surface unit cell of MgO
(001), highlighting the lattice distances a100 and a110 upon 45◦ in-plane rotation that can be used
for epitaxial growth. (c) Schematic description of a growth experiment of NbP on MgO using a Nb
buffer layer, along with in situ RHEED patterns of the growth evolution. The 45◦ in-plane rotation
between MgO and Nb (NbP) can be visualized in the top view diagram on the right, yielding an
in-plane epitaxial relationship MgO(100)//NbP(110). (d) Transmission electron microscopy image
of the grown MgO/Nb/NbP stack, where the structural quality of film and buffer layer can be
visualized. Panels (c) and (d) are adapted from [13]
buffer layer, highlighting the crystal structures and epitaxial arrangement in cross
section and top view, along with in situ electron diffraction (RHEED) patterns of
the crystal structures at the various growth stages. Several important features shall
be underlined here: (i) the in-plane rotational growth strategy between MgO and Nb
(NbP) lattices has been successfully implemented in the experiment, as evidenced
by the coincident RHEED patterns of MgO (100) and Nb (110), (ii) a small deviation
of the RHEED streak positions between MgO (100) and Nb (110) – indicative
of a slightly different lattice parameter – hints that the Nb buffer layer surface is
not strained but has relaxed to its natural lattice constant, and (iii) the Nb buffer
layer presents broad, modulated RHEED streaks, whereas the NbP layer grown on
top presents a more sharp and streaky RHEED pattern, indicative of an improved
crystalline quality and surface flatness. To provide the reader with a real-space
visualization of the growth outcome, Fig. 5d shows a cross-sectional transmission
electron microscopy (TEM) image of the MgO/Nb/NbP stack, where a flat, highly
ordered NbP layer can be observed, at expenses of a more structurally defective
Nb buffer layer. Hence, this particular experimental example is very instructive
both from the point of view of growth strategy and choice of substrate (45◦ in-
plane rotated epitaxy on a commercially available, chemically robust substrate)
and the role of buffer layer (“buffering” the structural damage arising from lattice
mismatch).
Introduction
instance, the effusion cells usually work at the vapor pressures of 10−4 –10−6 Torr,
which correspond to molecular mean free paths from several centimeters to several
meters, comparable to the distance between the effusion cells and the substrate
(∼20 cm). A typical growth rate of III–V semiconductors is 1 monolayer (ML)
per second, or ∼ 1 μm/h [12]. In some latest applications of ultrathin film growth,
such as topological insulators [21] and transition metal dichalcogenides [22], the
growth rate can be as low as 1 ML/min or even 1 ML/h. An extremely clean
environment is required to avoid unintentional doping at such low growth rates.
For example, the number of O2 molecules impinging on a surface per second is
1/2
NA
given by = p 2π Mk B T , in which p is the partial pressure of O2 , M is the molar
mass of O2 , NA is the Avogadro’s constant, kB is Boltzmann’s constant, and T is
23 Material Preparation and Thin Film Growth 1167
the absolute temperature. When growing Bi (111) films at the rate of 1 ML/s in a
vacuum environment with an oxygen partial pressure of 10−8 Torr, assuming 10%
of the oxygen molecules react with bismuth, then the impurity level in the bismuth
film is 0.07%, which is much higher than the one found in commercially available
bulk materials (0.0001% – 0.001%). Therefore, most MBE applications must be
carried out in ultrahigh vacuum, typically 10−9 – 10−12 Torr.
MBE chambers are designed to maintain UHV environments during the depo-
sition. The pumping system of an MBE chamber usually combines rotary, turbo
molecular, ion getter, and titanium sublimation pumps. Cryogenic pumps are often
installed in the medium- to large-scale MBE systems. The chamber is built with non-
magnetic stainless steel, usually with full metallic sealing. In order to quickly pump
out the water molecules, which adhere to the chamber walls and desorb very slowly
at room temperature, the chamber is baked at 150 – 200 ◦ C for several tens of hours
after every exposure to atmospheric conditions (e.g., for maintenance). Besides,
during the growth, liquid nitrogen or cold gas flows through the cryoshrouds inside
the chamber. The cryoshrouds serve as another cryopump, absorbing the residual gas
molecules and further reducing the pressure. All the heating elements, including the
sample stage and the effusion cells, are water-cooled or shielded in order to avoid
strong outgassing.
The substrates are introduced through a load-lock, which is a small chamber that
can be quickly pumped to 10−7 –10−8 Torr before transferring the substrates into the
growth chamber. In some MBE systems that are highly sensitive to impurities, there
is an additional substrate preparation chamber between the load-lock and growth
chamber. Those “dirty” jobs, such as substrate degassing and annealing, capping
layer growth, etc., can be carried out in the preparation chamber.
The molecular beam fluxes can be obtained from the pseudo-Knudsen cells hosting
ultrapure solid, liquid, or gas sources. A Knudsen cell is a closed crucible with a
small orifice, through which the vapor of the material heated in the crucible leaks
out as a molecular beam. The beam flux from such a cell is solely determined by the
vapor pressure of the material, and the vapor pressure can be easily controlled by the
temperature of the crucible. In order to get higher molecular beam flux, the realistic
effusion cells used for MBE usually have large orifices. The vapor pressure required
for MBE growth is typically 10−4 –10−6 Torr. For the materials that can reach the
required vapor pressure at 100 – 2000 ◦ C, normal effusion cells with crucibles
(usually made of hBN, Al2 O3 , graphite, W, or Ta) and filament radiation heating can
be used. For those materials that require temperatures higher than 2000 ◦ C, electron
beam evaporators must be applied. The filaments in the effusion cells are connected
to PID control loops in order to stabilize the temperature. On the other hand, to
handle the gas sources, or the solid or liquid sources that already have high vapor
pressure at room temperature, one should use effusion cells with leak valves. All
1168 A. Bedoya-Pinto et al.
The most important in situ and real-time monitoring tool is reflection high-
energy electron diffraction (RHEED), through which the lattice parameters and
reconstructions of the sample surface can be determined [23]. Especially, when
the growth is layer-by-layer (Frank-van der Merve growth), the intensity of the
diffractive pattern oscillates with time (Fig. 7). The RHEED pattern intensity
reaches a maximum at each time a new complete layer is finished, by when the
surface has fewest steps thus smoothest. Since the growth rate and surface condition
can be precisely determined from the RHEED oscillation, a technique named phase-
locked epitaxy (PLE) was developed for the growth of superlattices with atomically
sharp interfaces [15]. In PLE, the shutters only switch molecular beams when the
RHEED pattern intensity reaches a maximum; thus the intermixing at the interface
is minimized.
Since the MBE chamber is compatible with most surface analysis techniques
working in UHV, many other in situ analysis tools can be integrated with MBE, such
as X-ray photoemission spectroscopy (XPS), Auger electron spectroscopy (AES),
low-energy electron diffraction (LEED), ultraviolet photoemission spectroscopy
(UPS), and secondary ion mass spectrometry (SIMS). These techniques provide the
ability of both lattice structure and chemical composition analysis. In recent years,
many MBE systems are also combined with powerful real-space and momentum-
space imaging techniques, such as scanning tunneling microscopy (STM) and
angle-resolved photoemission spectroscopy (ARPES).
23 Material Preparation and Thin Film Growth 1169
Fig. 7 (a) The RHEEDpattern of Si(111) substrate with 7 × 7 reconstruction. Incidence azimuth:
[112]. (b) The RHEED pattern of 4 QL (1 QL = 5 atomic layers) thick Bi2 Te3 films grown on the
Si substrate. (c) The oscillation of the intensity of the zeroth-order reflected electron beam, with
different growth rates [21]. (With kind permission from Wiley)
As mentioned in the first section, MBE has been very fruitful in the growth of
semiconductor thin films and heterostructures. There has been an ample literature
spectrum reviewing the contribution of MBE in these fields. Limited by the length
of this chapter, we will focus on the MBE growth of novel functional materials that
developed in the recent decade. For the MBE growth of traditional semiconductors,
we recommend the readers to refer to the literature [14–16], [23–26].
It is worth mentioning a core principle for the stoichiometric growth of not
only traditional semiconductors but also most of the novel materials – the “three-
temperature method. ” This method typically applies to binary compounds but can
also be extended to the ternary ones. Take a binary AB film, which is grown by the
co-deposition of A (usually a metal) and B (usually a nonmetal) molecular beams,
as an example: A is a low-vapor-pressure element that evaporates at the temperature
TA , while B is a high-vapor-pressure one that requires TB < TA to evaporate. At
a certain substrate temperature TS , B molecules desorb much faster than A from
the surface of the substrate. Therefore, it is recommended to choose a substrate
temperature TB < TS < TA , at which only the B molecules that bond with A stay
at the surface. Excessive B flux is provided to achieve stoichiometric growth, and
the growth rate is controlled by the A flux. For ternary compounds A1 A2 B, one
just needs to supply excessive B flux and control the flux ratio between A1 and A2 ,
thus greatly simplifying the optimization of growth parameters. It is easy to realize
that the three-temperature method is suitable for the growth of the most B-rich
compound on the A–B phase diagram, which is also true for most of high-quality
MBE-grown materials, from the traditional III–V, II–VI, and IV–VI semiconductors
to the novel functional materials that will be introduced below.
[27, 28]. Importantly, recent efforts on molecular beam epitaxy of these magnetic
layered materials are currently bringing new insights on the fundamentals of
low-dimensional magnetism, such as the direct observation of stacking-dependent
magnetism in atomically thin CrBr3 [29] or the realization of a nearly ideal 2DXY
magnetic system in monolayer CrCl3 [30]. In this context, it is worth mentioning
that a vast number of MBE growth experiments of classical 3d magnets (such as
Fe, Co, and Ni) on highly crystalline substrates have been pursued down to the
monolayer limit (a comprehensive review can be found in Ref. [31]). However, in
all these highly crystalline systems, the coupling to the substrate is so strong that the
system can be hardly regarded as two-dimensional. Layered materials, on the other
hand, have a higher affinity to build two-dimensional structures than to bind to the
underlying substrate. In particular, when they are grown onto substrates with low
surface energy, such as graphene [30] or highly ordered pyrolytic graphite (HOPG)
[29], they can attain large two-dimensional grain sizes, chemically decoupled from
the substrate by a van der Waals gap. Despite the weak coupling, the choice of the
substrate will have an impact on the growth of van der Waals materials. An example
is given in Fig. 8, where a CrCl3 monolayer, a recently discovered 2D-XY magnet,
is grown on graphene/6H-SiC (0001) and directly on 6H-SiC (0001) substrates. As
Fig. 8 (a) Cross-sectional view of a CrCl3 monolayer grown on graphene/6H-SiC (0001). (b, c)
Scanning tunneling microscopy images and RHEED diffraction patterns of a CrCl3 monolayer
grown on graphene/6H-SiC and directly on 6H-SiC(0001) substrates, showing the influence on the
substrate on the in-plane orientation of crystalline domains. Twisted in-plane domains are attained
for the growth on graphene as evidenced by the dissimilar moiré patterns, while on 6H-SiC, the
CrCl3 layer grows in a single-crystalline fashion, following the in-plane symmetry of the substrate.
(d–f) Growth of Fe3 GeTe2 on Al2 O3 (0001). A layer by-layer growth is evidenced by streaky
RHEED patterns and intensity oscillations over time (e), and the epitaxial orientation is visualized
by X-ray diffraction spectra (f). (Panels (d–f) are taken from [32])
23 Material Preparation and Thin Film Growth 1171
expected, the CrCl3 grows in a (0001), i.e., c-axis orientation in both cases, but
the differences rely on the in-plane epitaxial relationships: while CrCl3 present in-
plane twisted rotational domains (as evidenced in the multiple streaks appearing
in the RHEED pattern and diverse moiré patterns on different grains observed by
scanning tunneling microscopy (STM); see Fig. 8b), the growth of CrCl3 on 6H-SiC
results in a single-crystalline orientation, the same as the underlying 6H-SiC (0001)
surface, characterized by a single-streak RHEED diffraction pattern (Fig. 8c). CrCl3
evaporates as a molecule, such that a single source is used for the MBE growth,
and the growth conditions are governed by the flux and substrate temperature
[30]. Another two-dimensional ferromagnet which has been successfully grown by
MBE is the ternary compound Fe3 GeTe2 , both on Al2 O3 (0001) and GaAs (111)
substrates [32]. Here, the growth has been carried out using the previously described
generalized three-temperature method: high-purity Fe (99.99%), Ge (99.999%), and
Te (99.999%) were co-evaporated from standard Knudsen cells at the temperature
of 1165 ◦ C, 1020 ◦ C, and 285 ◦ C, respectively [32], and the optimized substrate
temperature (340 ◦ C) lies in between the low-vapor pressure materials Fe and
Ge and the high-vapor pressure one (Te). Figure 8 (e, f) shows the structural
characterization of the films by in situ RHEED and ex situ X-ray diffraction,
evidencing epitaxial, layer-by-layer growth.
Topological Insulators
Topological insulators (TI) are a category of materials in which the electronic
structure in their k-space have a nontrivial symmetry-protected topological order.
Their electronic band structure features an inversed band sequence and a spin-orbit
interaction opened band gap. Although they have a bulk band gap like ordinary
insulators, there are symmetry-protected surface or edge states that are metallic
and contain massless Dirac fermions (linear E-k dispersion) [33]. Time-reversal
symmetry-protected 2D TI was first predicted in quantum spin Hall (QSH) systems
[34–36], and later Bi2 Se3 , Bi2 Te3 , and Sb2 Te3 were predicted to be 3D TIs with
Dirac surface states [37]. MBE has pioneered the early exploration of topological
insulators. The QSH edge states were discovered in HgTe/Hg0.3 Cr0.7 Te quantum
wells just 1 year after the prediction (Fig. 9a, b) [38]. The Dirac surface states were
also quickly confirmed from STM and ARPES experiments on the MBE-grown
films (Fig. 3c, d) [20], [39–41].
The 3D TIs are especially suitable for MBE growth because of their van der
Waals layered structure. The low interaction between the 3D TIs and the substrates
makes the requirement of lattice matching much weaker and hence broadly expands
the selection of substrates. Since 3D TIs can be grown on almost any atomically flat
surfaces, different choices of substrates can introduce different functions to the TI
films. For example, various TI/superconductor heterojunctions are grown in order to
search for Majorana bound states (MBS), which is an important candidate conceived
for quantum computation [42]. Such heterojunctions include Bi2 Se3 /NbSe2 [43],
Bi2 Te3 /NbSe2 [44], Bi2 Se3 /Bi2 Sr2 CaCu2 O8+δ [45], Bi2 Se3 /Nb (Nb as capping
layer) [46], etc. Another usage of the substrate is gating dielectric, such as
SrTiO3 (111), which has a high dielectric constant at low temperature. Quantum
1172 A. Bedoya-Pinto et al.
Fig. 9 (a) A schematic diagram of a typical HgTe quantum well [39] (With kind permission
from Wiley). (b) The quantized conductance in 7.3-nm-wide HgTe quantum wells, in which band
inversion happens (curves III and IV). From [38]. (Reprinted with permission from AAAS). (c)
STM topography (0.5 μm × 0.5 μm) image of an 80-nm-thick Bi2 Te3 film grown on Si(111)
surface. Inset, atom resolved STM image (2.5 nm × 2.5 nm). (d) Dirac surface states on the Bi2 Te3
film with linear band dispersion, resolved by in situ ARPES [20]
anomalous Hall effect (QAHE) was realized on the Cr0.15 (Bi0.1 Sb0.9 )1.85 Te3 films
grown on SrTiO3 (111), in which the bulk carriers are depleted by back-gate tuning
through SrTiO3 ; thus, the quantum conductance through the QAHE edge states
is revealed [47]. In GaAs/QAHE TI/superconductor heterostructures, half-integer
quantized conductance plateaus were observed, which is probably an evidence of
Majorana fermion modes [48]. MBE grown TIs are also promising for spintronic
applications: in Bi2 Se3 /permalloy and Bi1−x Sbx /MnGa heterostructure, spin Hall
angles as large as 3.5 and 52 are observed, much larger than those in elemental
heavy metals (< 1) [49, 50].
As the topological material family expands quickly in recent years, MBE is also
applied to the growth of topological materials beyond TI. Topological crystalline
insulators (TCI) are a category of materials in which their Dirac surface states are
protected by the crystalline symmetry, rather than the time reversal symmetry in TIs
[51] [52]. Dirac fermions are confirmed on the (111) surface, which is difficult to
obtain from single crystal cleavage, of the MBE grown TCIs: Pb1−x Snx Te [53] and
SnSe [54] in rock-salt structure.
23 Material Preparation and Thin Film Growth 1173
Fig. 10 Examples of Dirac semimetals grown by MBE. (a) Crystal structure of Na3Bi, highlight-
ing the two non-equivalent Na sites in the unit cell. (b, c) RHEED patterns of the Si (111) – 7 × 7
substrate along [11-2] and of the Na3 Bi film along [110]. (d, e) Complementary RHEED patterns of
the Si (111) – 7 × 7 substrate along [110] and of the Na3 Bi film along [11-2], indicating an epitaxial
growth with an in-plane rotation of 30◦ between film and substrate. (f) Electronic bandstructure of
Na3Bi along -M, showing a clear linear dispersion characteristic of Dirac semimetals. (Taken
from [56] (With kind permission from Elsevier))
1174 A. Bedoya-Pinto et al.
Fig. 11 (continued)
23 Material Preparation and Thin Film Growth 1175
High-Temperature Superconductors
Despite more than 30 years of intensive studies, the mechanism of high-temperature
superconductors (HTC) is still a mystery. Both the copper- and iron-based super-
conductors have layered tetragonal structures, which are naturally suitable for
MBE growth. Nevertheless, since most of the HTCs contain four to five elements
(e.g., Bi2 Sr2 CaCu2 O8+δ , Ba1−x Kx Fe2 As2 ), the growth of high-quality HTC films
requires sophisticated control of beam fluxes.
The most successful MBE growth of cuprate HTCs was performed by I. Božović
and his colleagues in Brookhaven National Laboratory, where a technique called
atomic-layer-by-layer MBE (ALL-MBE) is applied [59]. ALL-MBE is developed
based on the fact that each atomic layer in a cuprate HTC only contains oxygen
and one metal element. In ALL-MBE, the real-time signals from the atomic
absorption spectroscopy (thickness measurement) are fed to the shutter controller,
which switches the molecular beams exactly at the time that one atomic layer is
finished. ALL-MBE can tune the compositions of complex cuprate HTCs freely
and can create atomically sharp interfaces between different cuprate materials [60].
Thanks to the excellent reproducibility of the growth, the scaling law between
superconducting critical temperature Tc and the 2D superfluid phase stiffness can
be revealed in a statistical way, which shows deviation from the standard Bardeen-
Cooper-Schrieffer description of superconductivity (Fig. 12c) [61].
Comparing with cuprate HTCs, the MBE growth of iron-based superconduc-
tors was realized much faster after their discoveries, such as FeSe, KFe2 Se2 ,
Sr1−x Kx Fe2 As2 , Ba1−x Kx Fe2 As2 , SmFeAs(O,F), LiFeAs, etc. [62–65]. However,
the early MBE grown films did not show better performance than their bulk
counterparts. A major breakthrough happened on the monolayer FeSe films grown
on SrTiO3 (100) substrates, in which the superconducting Tc (onset 53 K) measured
from ex situ electric transport experiments is much higher than the bulk material
(9.4 K) (Fig. 12d–g) [66]. Later, an in situ 4-probe transport experiment in UHV
environment implies a Tc higher than 100 K in as-grown monolayer FeSe films
(Fig. 12h) [67]. The mechanism of the Tc enhancement in monolayer FeSe is still
under debate and has attracted intensive research interests since its discovery [68].
Fig. 11 Weyl semimetals grown by MBE. (g) Crystal structure of Nb(Ta)P and schematic cross
section of MgO substrate and Nb-buffer layer used for growth. (h–k) RHEED pattern of MgO
substrate and NbP film, indicating an epitaxial growth with an in-plane rotation of 45◦ between
film and substrate. (l) Momentum-resolved photoemission spectra of NbP along A-A direction,
where the Weyl points are expected. A linear band dispersion is observed. (m) Fermi-surface of
NbP, with four electronic pockets along X and Y directions, ascribed to topological surface states.
(Taken from [13] (© ACS, with kind permission))
1176 A. Bedoya-Pinto et al.
Fig. 12 (a) Schematic diagram of a cuprate HTC sample grown by ALL-MBE [37]. (b) Scanning
transmission electron microscopy of a cuprate metal-insulator bilayer. Inset, a magnified image of
the interface (arrowed) [60]. (c) The dependence of superconducting Tc on the zero-temperature
2D superfluid phase stiffness ρ S0 in La2−x Srx CuO4 [61]. (d) STM topography and (e) atom
resolved images of monolayer FeSe film grown on SrTiO3 (100). (f) A dI/dV spectrum showing
a superconducting gap in monolayer FeSe. (g) Ex situ electric transport experiments of monolayer
FeSe capped with amorphous Si [66]. (h) In situ 4-probe transport experiments on monolayer FeSe
[67] (b, c, and h reprinted with permission from Springer Nature)
Fig. 13 (a) The lattice structure of 2H-MoSe2 . Three atomic layers form a monolayer 1H-MoSe2 .
(b) The ARPES data shows the VBM of MoSe2 changes from Γ point to K point as the thickness
decreases from bilayer to monolayer, which leads to an indirect-direct band gap transition. The
spin-orbit splitting of the bands at K point is also resolved [22]. (c) The 1D CDW at the twin
boundaries of monolayer MoSe2 [73]. (d) The lattice structure of 1T’-WTe2 . (e) The QSH band
gap of 1T’-WTe2 resolved by ARPES. The sample surface is K-doped. (f) The dI/dV spectra
measured by low-temperature STM showing enhanced density of states at an edge of 1T’-WTe2
[79] (a, b, and f reprinted with permission of Springer Nature)
with spin-orbit splittings as large as 180 meV (MoSe2 ) and 475 meV (WSe2 )
at the valence band maximums (VBM) (Fig. 13b) [22] [71]. Compared with the
CVD grown films, the MBE-grown semiconducting TMDC films have much higher
density of 180◦ twin boundaries, which are found to be metallic and hosting one-
dimensional charge density waves (CDW) (Fig. 13c) [72] [73].
On the other hand, various CDW orders and superconductivity are discovered in
the metallic monolayers of 1H-TiSe2 [74], NbSe2 [75], and TaSe2 [76]. The super-
conductivity in NbSe2 is especially interesting because of its Ising pairing, which
leads to an in-plane upper critical field much higher than the Pauli paramagnetic
limit [77].
The 2D TMDC materials also exhibit topological orders. 1T’ structured mono-
layer TMDC (Mo/W)(S/Se/Te)2 are predicted to be QSH systems, in which
spin-orbit interaction opens a band gap in the inversed bands and leads to QSH
edge states [78]. QSH band gaps are confirmed in the MBE-grown 1T’-WTe2 and
1T’-WSe2 films by ARPES experiments (Fig. 13e, f) [79] [80], while 1T’-MoTe2
turns out to be a semimetal due to its insufficient spin-orbit interaction [81].
Furthermore, two-dimensional ferroelectricity has been discovered in MBE-
grown monolayer chalcogenides very recently. Monolayer SnTe grown on graphene
is found to be ferroelectric with in-plane polarization [82]. Such 2D ferroic materials
are considered to be essential for the conception of future full-2D-material memory
devices.
1178 A. Bedoya-Pinto et al.
In this section, we will make a brief comparison between MBE and the other
thin film deposition techniques and discuss about the future development of MBE
technique.
When growing those binary compounds with group V or VI nonmetals, with
extremely clean environment, slow growth rate, and precise beam flux control,
MBE can usually achieve the best film or heterostructure quality among the
common thin film growth techniques, such as magnetron sputtering, pulsed laser
deposition (PLD), chemical vapor deposition (CVD), and electrochemical liquid
phase deposition. The chemical stoichiometry can be almost perfect in these MBE
grown films, thanks to the three-temperature method mentioned above. The growth
of pseudo-binary compounds, in which several metal or nonmetal elements can
freely substitute each other in the crystal lattice, such as (Al/In/Ga)(N/P/As),
also follows this principle. With specially designed effusion cells, growing the
compounds with group IV or VII nonmetals is also possible. In ALL-MBE, despite
the complicated chemical composition of cuprates, the three-temperature method is
still valid when growing each atomic layer (one metal element plus oxygen).
However, when the desired material is not in a layered structure and possesses
multiple metal elements, such as Heusler compounds (chemical composition XYZ
or X2 YZ, in which two or three metal elements are involved), it becomes difficult
to match the beam fluxes. Unlike sputtering or PLD, which typically uses a single
target to get all the metal elements, it is often impossible to obtain stoichiometric
metal element fluxes from a single effusion cell in MBE, because in this case, the
whole source material in the crucible is in a thermal equilibrium, and the vapor
pressures for each metal element are different at a certain temperature. Depositing
compound films from a single effusion cell is only possible when the source
material evaporates as stoichiometric compound molecules, such as NaCl, MgO,
Pb1−x Snx Te, etc. On the other hand, a target under the local bombardment/heating
in sputtering or PLD is far away from thermal equilibrium; thus, the elements at the
sputtered/heated spot can be evaporated altogether. It should be noted that although
the growth of Heusler compounds is relatively difficult for MBE, there are indeed
considerable amount of reports on MBE-grown Heusler compound thin films, whose
magnetic properties are close to the bulk materials [83] [84].
Comparing with the other thin film growth techniques, another drawback of
MBE is its relatively low flexibility of changing the source materials. Since UHV
environment can only be achieved after a bake-out process, it usually takes several
days to change source materials in MBE systems.
From the scientific research’ point of view, two future prospects of MBE
can be immediately recognized as important: (i) As next-generation electronics
is pursuing 3D structures, heterostructures beyond stacked thin films become
important recently, for example, lateral p-n junctions at the boundaries between
monolayer WSe2 and MoSe2 [85], and (ii) all in situ growth and characterization
in UHV environment have been proven to be a powerful approach in developing
novel functional materials. This includes not only surface science techniques (STM,
23 Material Preparation and Thin Film Growth 1179
ARPES, XPS, etc.) but also electric transports (local 4-probe), optical measurements
(photoluminescence, Raman spectroscopy, microwave impedance imaging, etc.),
and magnetic measurements (two-coil mutual inductance).
Introduction
Pulsed laser deposition (PLD) is one of the most used techniques for depositing thin
films. It is a physical vapor deposition technique which is ideally suited to deposit
thin films of complex or multicomponent oxides onto a substrate as this technique
congruently transfers the composition of the target to the film. PLD technique gained
enormous popularity following the discovery of high-temperature superconductivity
in perovskites [86] when it was demonstrated that high-quality perovskite thin films
with bulk-like properties could be deposited with PLD [87]. During PLD process,
the target material is vaporized/ablated with a high-intensity excimer radiation pulse
whose width is of the order of tens of nanoseconds and whose energy is of the order
of joule. As a result, a jet of particles, commonly denoted “plume” due to its form
(see Fig. 15), is ejected from the target surface and expands away from the target
with a strong forward-directed velocity distribution. The ablated particles condense
on a substrate usually placed opposite to the target; this process takes place in a
vacuum chamber – either in the high vacuum range or in the presence of some
background gas. The laser pulses are guided to the vacuum chamber by means of
optical devices, such as mirrors and lenses, which in addition focus the beam to the
target, optimizing the energy density of the laser pulses. While the laser pulses are
hitting on its surface, the target is usually rotated with a constant speed to achieve
a homogeneous ablation process. The possibility of a multi-target rotating wheel
in the vacuum chamber enables more efficient and complex processes: multilayers
and alloy films can be grown from elementary targets by moving them alternately
into the laser focal point. The high energy density used in a typical PLD process
is able to ablate almost every material, and by controlling the process parameters,
high-quality films can be grown reliably at a much faster rate compared to other
growth techniques such as MBE. Another known advantage of the PLD technique
is the stoichiometric material transfer from target to film, such that compounds with
highly complex compositions can be grown using only one target source.
Although the pulsed laser deposition process is conceptually simple, controlling
the dynamics of the film growth is not necessarily a straightforward task, because
of the large number of interacting parameters that govern the growth process and
hence the film properties, such as:
• The laser parameters (working wavelength, pulse energy, width, and repetition
rate)
• The substrate temperature and rotation speed
• The structural and chemical composition of the target material
1180 A. Bedoya-Pinto et al.
• The chamber pressure and the chemical composition of the buffer gas
• The geometry of the experiment (incident angle of the laser, incident angle of the
plume, distance between target and substrate)
Being able to control the laser and deposition parameters for a given system is the
clue to profit the advantages of the PLD technique. In practice, parameters such as
the experiment geometry are usually optimized for a given system and kept constant,
while other parameters such as laser flux, substrate temperature, chamber pressure,
and background gas are systematically varied in order to investigate their influence
on the film growth. The PLD chamber base pressure is typically in high vacuum
range. The PLD is not well suited to grow films from highly thermally conducting
or metallic targets as the incident laser energy into the target is quickly dissipated
leading to a low deposition rate. A schematic view of a typical configuration of a
PLD apparatus is sketched in Fig. 14.
The two important criteria which determine the quality of the PLD targets are their
density and stoichiometry. It is important that the density of targets is close to or
better yet exceed 90% of the theoretical value. Such dense targets are fabricated by
hot or cold pressing/sintering of powders of material with requested stoichiometry.
During the PLD process, the elemental ratio of the target constituents except the
oxygen content is transferred to the substrate, and hence it is essential that target
has the appropriate stoichiometry. The ablation of the target is localized to the laser
spot incident on it, and the target utilization is improved by rastering the laser spot
on the target surface or by target rotation or by combination of both laser rastering
and target rotation. The PLD targets are routinely resurfaced by polishing away
surface asperities created during extensive target use. Dry polishing with a fine-grit
sandpaper or wet polishing with an alcohol-based polishing mixture is preferred.
Aqueous polishing mixtures are avoided to minimize any risk of any water retention
within the targets, especially so for porous targets. The metallic targets for PLD are
fabricated by similar processes to those used for sputtering targets and are described
in the sputter deposition section.
Laser
Excimer lasers are most widely used to ablate material during PLD process as they
provide laser beam at higher power, higher repetition rate, and superior flat-top-
beam profile. Excimer is an acronym for EXCIted diMER. diMER is a misnomer
in some cases where KrF is used as a halogen gas but is used because of historical
reasons (emission in first excimer lasers was from dimers of Xe). Also note that
KrF is not a stable molecule in its ground state and is only formed in the excited
state within high-energy electrical discharge in the laser cavity. The excimer lasers
used halogen gas-filled cavity and laser with wavelength of 157 or 193 or 248 or
308 or 351 nm depending on the halogen gas used, F2 or ArF or KrCl or KrF or
XeCl or XeF, respectively. These lasers do require expensive gas handling system
due to health concerns with the use of halogen gas. The most common wavelength is
248 nm generated using KrF. The shorter-wavelength photons have higher energy, so
they have higher ablation efficiency and thus result in a higher deposition rate. The
pulse width of 25 ns is typical for an excimer laser, and they can deliver power of
over 1 J per pulse. An alternate to the excimer laser is the solid-state Nd:YAG laser
as it is relatively inexpensive and easier to maintain. The fundamental wavelength
of the Nd:YAG laser is 1064 nm, and hence its optical frequency can be doubled,
tripled, quadrupled, or quintupled. Though, the most common setup with this laser
is to use a wavelength of 266 nm (frequency quadrupled) or 355 nm (frequency
1182 A. Bedoya-Pinto et al.
tripled) with this laser. Excimer lasers (KrF, ArF, XeCl) are widely used to deposit
oxide films because of the larger absorption coefficient and small reflectivity of
materials at their operating wavelengths.
Ablation Process
The energy density within the focused laser beam spot is extremely high (range
of 0.1–2 J/cm2 ) and which due to the short pulse duration (∼10 ns) corresponds
to instantaneous power densities in the range of 107 –108 W/cm2 . The high power
density can locally heat the target material to temperatures of even few thousand
Kelvin causing thermal evaporation of the target material in the initial stages [88].
During laser ablation process, a dense cloud of vaporized material is formed which
contains a mixture of ions, molecules, atoms, and even small particulate in extreme
cases. This material cloud continues to absorb energy from the laser beam and
consequently undergoes a sudden expansion into a background gas or vacuum to
form the laser plume (Fig. 15). This laser plume expands away from the target
and travels toward the substrate surface leading to the eventual deposition of a thin
film of the target material. The kinetic energy of the plume species from metallic
targets ranges between a few to ∼100 eV in vacuum [89]. Use of background
gas (pressures greater than mTorr) reduces the kinetic energy of the plume species
and also increases the number of chemical reactions between plume species and
the gas molecules. The mean kinetic energy of the species being deposited in
background gas is of the order of 10 eV which is comparable to that during
sputter deposition. Some of the lighter elements like oxygen or nitrogen tend to
have higher kinetic energy and different angular distribution [90], and hence it is
customary to supply these elements via the background gas so as to deposit film of
the desired composition. The background gas broadens the plume, and the extent
of this broadening depends on the gas pressure. If it is essential to maintain a low
background gas pressure, then it is possible to obtain thin of desired composition by
adjusting the target composition.
Fig. 15 Photographs of different plasma plume shapes generated in a laser ablation process. The
size, shape, and color depend on the laser parameters and the target material. Examples of widely
used material targets such as carbon (middle panel) and ZnO (right panel) are highlighted
23 Material Preparation and Thin Film Growth 1183
Optics
The laser beam is typically focused and incident on the target at angle ranging from
30 to 45◦ from its surface. The laser is focused using a focusing length needed
to focus the laser beam on to the target. In some PLD systems, raster mirror is
added in the beam path downstream of the focusing lens to deflect the partially
focused beam on the target. The raster mirror is motorized to change the deflection
angle during deposition such that the beam spot scribes a line on the target surface.
This line is offset from the center of the target which is continuously rotated
during deposition. This laser beam rastering improves chemical compositional and
thickness uniformity and target usage. During rastering of the laser beam, the laser
beam incidence angle on the target varies which affects the laser beam energy
density on the target consequently causing a variation in ablation. This disadvantage
can be partially overcome by substrate rotation during deposition. Though laser
output energy of the incident laser beam on the target can be controlled by changing
the high voltage used during the emission process, this is not preferred as it also
changes the beam profile which in turn affects the incident laser intensity on the
target. It is better to operate the laser at constant energy and reduce the beam energy
using an attenuator mounted external to the laser. The attenuator has minimal impact
on the laser beam profile, and consequently a better control of the laser ablation
is achieved. Sometimes optical slits are used to remove inhomogeneous parts of
the laser beam. All the optical components are coated with anti-reflection coating
appropriate for the wavelength of the laser to improve light transmitivity by virtually
eliminating unwanted reflections.
Thickness Monitoring
gas pressure during the PLD process tends to be several orders of magnitude higher
(ranging from 1 to 500 mTorr) which necessitates the use of a two-stage differential
pumping to maintain high vacuum in proximity of the tungsten filament. Such
differentially pumped RHEED is called high-pressure RHEED. The scattering of
the electron beam by background gas is minimized by locating the exit aperture
of the high-pressure RHEED and also the phosphor screen close to the substrate
(roughly within few cm). Moreover, a shutter is used to protect the phosphor screen
when the RHEED is not in use. A quartz crystal microbalance (QCM) can also be
used to monitor the growth rate of the PLD process. These monitors can be used
prior and post deposition to measure the growth rate.
Substrate Heating
Selected Applications
Growth of VO2 using PLD. VO2 is an archetypal correlated oxide with a metal
to insulator transition (MIT) near room temperature, and hence it has been exten-
sively explored to develop novel electronic devices. Excellent quality epitaxial,
single-crystalline, and stoichiometric thin films of VO2 were deposited from
polycrystalline VO2 or V2 O3 targets by pulsed laser deposition (PLD) technique
on various substrates [91]. This study used a laser energy density of 1.3 J/cm2 ,
a repetition rate of 2 Hz, a target to substrate distance of ∼7.1 cm, and oxygen
deposition pressures of at least 9 mTorr. Film quality and properties were not much
affected for oxygen pressures that were varied between 9 and 15 mTorr. Growth
temperatures were substrate-dependent, and the largest change in resistance of three
to four orders of magnitude at the metal to insulator transition (MIT) was found
23 Material Preparation and Thin Film Growth 1185
for deposition temperature of 400 ◦ C, 500 ◦ C, and ∼700 ◦ C for TiO2 (001) and
(101), TiO2 (100) and (110), and Al2 O3 (0001) and (10-10) substrates, respectively
(see Fig. 16a). The dependence of MIT temperature on various substrates is a direct
consequence of a different strain state in the VO2 films. Moreover, AFM studies
indicated that with optimized growth conditions, the deposited films were smooth
and without any particulate debris typically seen in PLD films. High-resolution
XRD peaks of VO2 along with the Kiessig fringes obtained at Stanford Synchrotron
Radiation Laboratory (Fig. 16 and Ref. 92) illustrate high quality of the epitaxial
growth on TiO2 (001) and TiO2 (110) substrates. Substrate preparation also plays
an important role in determining the properties of thin VO2 films grown on such
single-crystalline substrates [93].
Growth of perovskites using PLD. High-temperature superconductors with criti-
cal temperatures higher than liquid nitrogen temperature (77 K) are based on hole-
doped cuprates having perovskite structure containing copper oxide planes [86].
PLD is the technique of choice to deposit thin films of high-temperature super-
conductors. Perovskite compounds, ABO3 , contain alternating layers of AO and
BO2 planes along its c-axis. These two planes are chemically distinct, and hence
the surface properties of perovskites are termination-dependent. Recently, high-
mobility electron gas was observed at the interface of nominally insulating LaAlO3
and SrTiO3 when the substrate was TiO2 terminated [94]. This interface was
prepared by PLD growth of LaAlO3 on SrTiO3 single crystal substrates. The
LaAlO3 films were deposited using a KrF excimer laser with fluence of 1 Jcm−2
lasing as repetition rate of 2 Hz, while the SrTiO3 substrate was at 800 ◦ C. This
study illustrates that high-quality perovskite films with precise thickness control
with single-unit cell resolution can be grown using PLD.
Fig. 16 (a) Metal-insulator transition of VO2 thin films grown by PLD on different oxide
substrates. (b) X-ray diffraction pattern of a VO2 film grown on TiO2 (001), indicating epitaxial
growth with a high crystalline quality, as evidenced by the appearance of Kiessig fringes along the
(002) reflection. (Panel (b) is taken from [92])
1186 A. Bedoya-Pinto et al.
Introduction
Sputter deposition is the most widely used thin film deposition technique as it is
capable of depositing very-high-quality films in thickness range from angstroms
to microns even on large substrates at a highly competitive cost. This technique
uses energetic gas molecules (atoms and/or ions) to dislodge atoms from a target
surface which then travel through several inches of sputter gas onto a substrate
surface. The sputtering sources are operated in high vacuum or ultrahigh vacuum
chambers depending on the process demands. Sputtering can be classified into two
primary categories: magnetron sputtering and ion beam sputtering. The discussion
here excludes DC diode and triode sputtering as their disadvantages such as
low deposition rate, high gas densities, high discharge voltages, etc. make them
impractical in modern deposition tools. The planar magnetron which included a
magnet assembly underneath a target cathode was first introduced by J. S. Chapin
in 1974 [95], and since then his original design has been significantly upgraded for
improved performance [96, 97]. The sputtering process uses an inert gas during
deposition. Argon gas is the preferred choice due to its ample availability in
ultrahigh purity (99.999%) at an affordable price and also as its atomic weight is
not too low compared to most target materials. The targets are in solid form and
conform to the magnetron source size and shape.
Material Targets
The pure metal or metallic alloy targets are fabricated by arc melting/casting
high-purity elemental metals in an inert Argon atmosphere as this method yields
targets with densities close to the theoretical values and with minimum amount
of oxygen inclusion. The metal targets can also be fabricated by sintering and
vacuum induction melting. The dielectric targets are fabricated by hot or cold
pressing/sintering of powder of dielectric materials. It is important that density of
the dielectric targets be close to or better even exceed 90% of the theoretical value.
The target fabrication method is known to influence the properties of deposited
thin films, and hence it is necessary to empirically determine the preferred target
fabrication method. During sputtering, the targets are typically water cooled to
maintain stable operation, and hence in many cases, the targets are backed with
a copper backing plate. The adhesion between the target and backing plate can be
achieved with either indium or epoxy bonding. The indium bonding is preferred as
indium is malleable which prevents its cracking. The low melting point of indium
will lead to failure of the bond if the targets get too hot during operation or bake-
out. Epoxy or elastomer bonding is used where indium bonding is not possible as
the target material is low melting or is temperature sensitive. Furthermore, the target
bonding to a backing plate also helps maintain integrity of brittle targets.
23 Material Preparation and Thin Film Growth 1187
Magnetron Sources
The magnetron sputter gun or cathode houses a series of permanent magnets whose
field lines localize the process plasma around the target surface by providing
drift paths for the electrons emanating from the target. The actual arrangement
of the permanent magnets within the sputter gun not surprisingly depends on
the gun manufacturers. The need to maintain sufficient magnetic field above the
target surface limits the target thickness particularly for target made from magnetic
materials to about half to a third of the thickness used for a non-magnetic target.
The target does not wear uniformly with use, but instead a trench or a groove is
formed in the region where most energized Argon ions impinge on the surface. In
the case of circular magnetron source, the groove is also circular and is referred to
as a “racetrack.” This groove deepens with target usage and eventually cuts through
the entire target thickness. The target utilization is low and less than 50% in the best
case. Hence, the precious metal targets are refurbished by adding fresh material to
an exhausted target. Interestingly, for difficult-to-light magnetic targets, mechanical
modification of the target to include a shallow groove promotes stabilization of the
process plasma when the target is in its pristine state. The target is clamped to the
sputter gun though a magnetic target could be just placed atop the gun without a
clamp. A negative voltage of several hundred volts is applied to the target surface
during the sputtering process. The target voltage decreases as the “racetrack” groove
deepens, and hence target wear/life can be monitored by careful tracking of this
voltage. It is essential that the target be electrically isolated from the ground/anode
surface/shield which surrounds the target. The spacing between these shields and the
gun is termed as the “dark space” gap and is around 1 mm depending on the type of
the magnetron source. This gap is adjusted to match the stable operating sputter gas
pressure. Too small a gap causes shorting, and if it is too large, then plasma is formed
within this region leading to sputtering of the clamping ring material which can
contaminate the intended thin film. Figure 17 shows a computer-generated picture
of a magnetron source and the associated components which are described in detail
below.
Magnetron Operation
During stable operation, the electrons spiraling along the gun’s magnetic field lines
ionize the sputter gas to positive ions forming a magnetron plasma confined close
to the target. This plasma emits a glow of light. The negative voltage applied to
the target attracts the positive ions which impact the surface at sufficient energies
creating a collision cascade at the target surface. As a result, photons, secondary
electrons, and target atoms/molecules are ejected from the surface. These ejected
atoms/molecules along their way toward the substrate undergo numerous collisions
with the sputter gas atoms which deflect them and result in loss of their kinetic
energy. Some of them are even backscattered to the target surface. This deflection
1188 A. Bedoya-Pinto et al.
Oxide or nitride thin films can be deposited from metal targets by addition of
oxygen or nitrogen, respectively, to the inert Argon sputter gas. This method is
referred to as “reactive” sputtering [99] and is a cheaper and more convenient
method than RF sputter to deposition of oxide or nitride thin films from dielectric
targets. During such process, the reactivity of the oxygen or nitrogen molecules
within the plasma, contained above the target surface, is enhanced and their
reaction is promoted with the target surface, forming an oxide or nitride layer
which then is sputtered away. A caveat, the dielectric layer formed during reactive
sputtering, lowers the sputtering rate with time as the surface becomes more and
more insulating and eventually leads to frequent arcing between the target and
ground shield. Pulsed DC power supplies which generate positive voltage spikes
at set frequency can be used to minimize buildup of dielectric layer on the target
surface. These power supplies also include arc suppression capability to detect and
extinguish an arc. When an abrupt fall in a target voltage of ∼50–150 V which is
associated with an arc formation is detected, the power applies a reverse voltage
pulse to quench the arc. The metal target surface can be regenerated by sputtering
the surface with pure inert gas. The composition of the oxide or nitride film (i.e.,
its oxygen or nitrogen content) can be controlled by varying the reactive sputter gas
mixture (see Fig. 19).
RF Magnetron Sputtering
Fig. 19 The composition of Mn nitride films deposited with reactive magnetron sputtering
using a mixture of Ar and N2 as sputter gas from a pure Manganese target. The composition
was determined by Rutherford backscattering (RBS). To accurately determine the composition,
200 Å films of Mn nitride were deposited on graphite substrate at room temperature and capped
with 100 Å Pt to prevent their oxidation upon exposure to ambient. The graphite substrates
which contain predominantly carbon, an element with lower atomic number than nitrogen, allow
determination of nitrogen content of the Mn nitride films to within +/−0.5%
source itself. During RF sputtering, the relative duty cycle is lower than with DC
sputtering which results in a lower deposition rate. The targets of dielectric materials
are always bonded to the Cu backing plate to facilitate removal of heat generated at
the target surface during operation.
The deposition of alloy thin films is achieved by using an alloy target from a single
magnetron source. Due to differences in sputter yields, transmitivity through sputter
gas, and the chamber geometry, the composition of the sputter deposited alloy film
never matches that of the target. The composition of the alloy thin films can be varied
by changing sputter gas pressure or target-substrate separation (mentioned above)
or in addition by changing the off-axis angle (i.e., the angle between substrate and
target normal). An alternate means for deposition of alloy thin films is the use of
multiple sputter sources arranged in a circular pattern aimed at a common focal
point, so-called “confocal” geometry (see Fig. 20). The compositional tuning and
also growth of multilayers can be easily achieved in this geometry. The uniformity
of composition and thickness of the thin films to better than +/−1% across the entire
1192 A. Bedoya-Pinto et al.
Fig. 20 Illustration of a confocal geometry with three magnetron sources and all the associated
components as installed in one of the deposition systems at the IBM Almaden Research Center.
Each magnetron source has its own individual chimney and shutter to prevent cross contamination.
A separate shutter is used to control film thickness. (Courtesy Chris Lada)
substrate can readily be achieved by rotating the substrate during thin film growth.
Sputter deposition rate can be monitored by a quartz crystal monitor (QCM) prior
and post growth or even during deposition by appropriate placement of the QCM
within the deposition chamber. Heating or even cooling of substrate to temperatures
as high as 1000 ◦ C or as low as −195 ◦ C is used to achieved desired thin film texture,
crystallinity, and smoothness. At typical magnetron sputter conditions, the ejected
target atoms arrive at substrate with kinetic energies of a few eV which is an order
of magnitude higher than in molecular beam epitaxy.
In ion beam sputtering, the target atom kinetic energy upon arrival to the substrate is
higher than in magnetron sputtering as the sputter gas pressure within the deposition
23 Material Preparation and Thin Film Growth 1193
Typical ion beam sputter source consists of a discharge chamber where plasma is
generated by radio-frequency (RF) or by direct-current (DC) discharge [100]. In
the RF source, an inductor coil surrounds the discharge chamber which is made
of dielectric material. In the DC source, the discharge chamber contains a hot
filament for electron emission as a cathode and a surrounding anode. The DC source
is cheaper but needs more maintenance as the source filament has a limited life.
The ions from the discharge chamber are extracted with either a two- or three-
grid assembly. (The discussion here ignores the grid-less sources as they lack ion
beam trajectory control and are not used for ion beam sputter deposition.) The
grid closest to the discharge chamber is referred to as the beam grid, and the
voltage (Vb ) applied to it is positive and equals the beam energy. The next grid
called the accelerator is at negative voltage (Va ) and accelerates the extracted ions.
The third grid in the three-grid assembly is the decelerator grid and is at ground
potential. The decelerator grid reduces beam divergence by almost a factor of
two, suppresses electron back streaming, and minimizes deposition of sputtered
ion within the source. Not surprisingly, the three-grid assembly is more expensive
than the two-grid assembly. The extracted ions are next bombarded with electrons
from a neutralizer to neutralize them, and this also reduces the beam divergence by
suppressing the mutual repulsion between the ions. Most grid assemblies are made
from molybdenum or graphite. The molybdenum grids are structurally more stable
and can be dished to shape the beam (i.e., focusing or defocusing optics). These
grids are used in thin film deposition application. The graphite grids are flat and
structurally fragile and are used in application where a collimated beam is desired.
The beam current (Ib ) measured at the beam grid is related to the etch or sputter
rate of the target. The beam current at fixed beam energy (Vb ) can be increased by
increasing the accelerator voltage (Va ). The sputter/etch rate is material-dependent
and shows a weak relationship to the melting temperature of the target material.
The IBD geometry requires several considerations. The grid assembly is designed
such that almost 99% of ion beam extracted from the source is incident on the target.
1194 A. Bedoya-Pinto et al.
Fig. 21 Computer-generated picture illustrating the ion beam deposition geometry from a RF
source as mounted along with the associated components in a deposition system at the IBM
Almaden Research Center. The target manipulator houses five targets each 3 inches in diameter.
(Courtesy Chris Lada)
The incident angle of this beam on the target maximizes the sputter yield and is
usually between 40 and 50◦ from target surface. The substrate is located to close to
or along the target normal as the maximum amount of sputtered material is ejected
along this direction. There is a forward lobe along which contains atoms sputtered
at higher energies and intensity, and it is desirable that this lobe is not incident on
the substrate. The shutter used to control thickness of the deposited thin film has to
be placed such that no incident ion beam impinges on top of it as this will sputter
the shutter material on to the substrate. The neutralizer is mounted to the side of
the IBD source with its axis orthogonal to the source axis. Figure 21 shows the
IBD geometry which is used for ion beam sputter deposition in a sputter deposition
system at the IBM Almaden Research Center.
The IBD target are usually circular and tend to be significantly larger than the
source size due to geometric considerations and the inevitable beam divergence. The
targets are clamped to the target holder by grabbing them along their edges to avoid
sputtering of clamping material which will contaminate the deposited thin films. The
targets are actively cooled to conduct away the energy dumped into the target during
the sputtering process. During the ion beam sputtering, neutral atoms are directed
23 Material Preparation and Thin Film Growth 1195
to the target surface, and hence this process is equally effective for deposition of
dielectric films. The targets may be bonded to the copper backing plate and usually
are for dielectric or brittle materials. The IBD targets wear uniformly with use, and
life of the target is significantly longer than in magnetron sputtering. This is highly
advantageous for deposition of precious materials.
The source parameters which are controlled during operation are beam voltage,
accelerator voltage, and the sputter gas. The sputter/etch rate of a target is given by
Child’s law [101] which relates the beam current to the total voltage (Vb + Va )3/2 .
Thus, for example, at a set beam energy, the etch/sputter rate can be increased by
raising the accelerator voltage. Such voltage variation allows change in etch/sputter
rate by over two orders of magnitude. The beam divergence is related to the Va /Vb
ratio, and the beam divergence almost doubles as the ratio increases from 0.1 to
1.0 [100]. The operation of the source at high ion currents causes wear to the
accelerator grid as part of the extracted ion beam collides with this grid instead of
passing through it. The alignment of the ion optics (i.e., grid apertures) is important
to minimize grid wear due to direct ion impingement. The etch/sputter rate is only
weakly influenced by the type of inert gas used during the process (i.e., argon versus
krypton or xenon). Reactive IBD is only possible with the RF source and is achieved
by introducing a premixed inert plus either oxygen or nitrogen gas into the discharge
chamber. The ratio of inert gas to oxygen/nitrogen gas is adjusted to deposit
oxide/nitride films of desired composition. Tuning of film composition during IBD
from an alloy target is also possible by changing target-substrate distance and by
changing the off-axis deposition angle.
Selected Applications
Sputter deposition has been the method of choice for deposition of thin films
in numerous industrial branches such as magnetic storage, semiconductor, opto-
electronics, automotive, and solar energy. Several generations of hard disk drive
products have entirely relied on magnetron sputtering to fabricate the read head
sensor which is a key component of the drive. This was due to the fact that the
giant magnetoresistance (GMR) of magnetic multilayers deposited by magnetron
sputtering is among the highest recorded GMR values comparable even to films
deposited by MBE [102]. The magnetic tunnel junction (MTJ) with the MgO tunnel
barrier which shows giant tunnel magnetoresistance (TMR) of several hundred
percent can be grown by reactive magnetron sputtering [103], and this TMR is
comparable to the single-crystalline MgO tunnel barrier grown with MBE [104].
Of late, the highest TMR with MgO tunnel barrier used in magnetic random
access memories (MRAM) is obtained by growing this layer using RF sputtering.
In magnetic storage industry, the read head has evolved from magnetoresistive in
the early 1990s to GMR head in 1997 to MTJ head in 2008. This has led to an
1196 A. Bedoya-Pinto et al.
Fig. 22 Areal density perspective for HDD/Flash memory technology. The relatively low produc-
tion costs related to sputtering processes of GMR/TMR devices have been essential to introduce
such products in the market while triggering a boost in magnetic storage capacity. (Courtesy: Ed
Grochowski [105])
exponential increase in the magnetic storage areal density per inch square, as shown
in Fig. 22, where HDD and Flash technology are compared. This is perhaps the most
technologically relevant impact of the sputtering deposition technique. Its affordable
cost compared to other deposition methods has triggered the successful introduction
of magnetic storage units in the industrial market.
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Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1206
Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1207
Transmission Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1208
Scanning Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1213
Scanning Probe Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217
Spin-Polarized Scanning Tunneling Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1219
Magnetic Force Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1223
X-Ray Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1227
X-Ray Magnetic Circular Dichroism: A Contrast Mechanism . . . . . . . . . . . . . . . . . . . . . . 1227
TXM: Quick Full-Field Imaging in Transmission Geometry . . . . . . . . . . . . . . . . . . . . . . . 1232
STXM: Optimized for Dynamic Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1233
PEEM: Imaging Surfaces of Bulk Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1233
CXI: Zero Drift and Femtosecond Temporal Resolution . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
SP-ARPES: Microscopy in Momentum Space . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1237
Medical Magnetic Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1238
Magnetic Resonance Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1238
Nuclear Magnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1239
Nuclear Quadrupole Resonance Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1243
Magnetoencephalography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1244
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1246
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1246
Abstract
List of Abbreviations
List of Symbols
V Bias voltage
N Counts
τ Delay time
D() Density of states
δ Dirac delta function
Seff Effective Sherman/sensitivity function
e Electron charge
ε Energy
M0 Equilibrium magnetization
c∗ Experimental constant
εF Fermi energy
f (ε) Fermi function
f Frequency
dFm
dz Gradient of the magnetic force
γ Gyromagnetic ratio
m, n Integers
wL Larmor angular frequency
flor Lorentz force
B Magnetic flux density
M Magnetization
Orbital quantum number
ml Orbital angular momentum magnetic quantum number
q Orbital angular momentum of photon
r0 Origin position vector
r Position vector
Q Quality factor
T1,2 Relaxation times
f0 Resonance frequency
PS Sample spin polarization
s Spin quantum number
A Spin asymmetry
1206 R. M. Reeve et al.
Introduction
relevant and due to the large range of systems that it is possible to image, there is no
universal best technique, and it is necessary to carefully select the most appropriate
approach based on the particular requirements of a given application or experiment.
Furthermore, since different techniques are sensitive to different magnetic properties
such as the stray field or magnetization, it can be best to combine multiple options
for a more comprehensive understanding.
In this chapter, we review some of the main techniques currently employed for
magnetic imaging. The aim is not to provide an exhaustive list of techniques but
rather to give an overview of some of the most widely employed options, high-
lighting some of the particular considerations that must be taken into account when
selecting an appropriate method, with the particular advantages and limitations of
the techniques highlighted. References are provided to more in-depth discussions
of particular techniques. Reviews and comparisons of multiple techniques are
provided in [1, 9, 10, 11]. Furthermore, we primarily focus on the application of
techniques to ferromagnetic systems. However, with the recent intense interest in
antiferromagnetic spintronics, there have been a number of advances in the field
of imaging of antiferromagnetic domains, as reviewed in Ref. [12]. We divide the
methods into different categories based on either the nature of the probing radiation,
such as electron beam or x-ray illumination, or in the case of the scanning probe
methods based on the principle of operation. While optical techniques such as Kerr
microscopy are also very widely applied to image domain structures and other spin
states such as magnetic skyrmion bubbles, we do not cover these in detail here
but rather refer the reader to the dedicated chapters on magneto-optic effects and
literature reviews of recent advances in the field [13, 14, 15]. Such optical methods
are generally more limited in their spatial resolution than many of techniques
presented in this chapter, yet they offer a number of advantages including being
relatively quick, inexpensive, and easy to apply. Finally, at the end of the chapter, we
briefly introduce some of the key modern magnetic imaging techniques for medical
applications.
Electron Microscopy
The first class of microscopy techniques that will be discussed uses electron beams
in order to probe the sample. The incident electron beam can interact with the
sample based on different mechanisms. In the first instance, the beam may be
deflected depending on the magnetic configuration, yet additionally, the excitation
of the sample generates secondary electrons which also carry information about
the magnetic state. Due to the mature technology in generating highly focused
electron beams, scanning approaches can offer very good spatial resolution imaging.
Electron microscopy techniques tend to be limited to conducting specimens, since
otherwise the sample becomes charged by the electron beam, leading to unwanted
deflections and distortions. This can sometimes be overcome if insulating systems
want to be investigated by coating the surface with a thin conductive layer to help
mitigate charge buildup. Furthermore, the application of magnetic fields during
imaging is often severely limited due to their deflecting and depolarizing effects
1208 R. M. Reeve et al.
Following the Bitter technique, transmission electron microscopy (TEM) was one
of the earliest techniques for revealing magnetic domain structure [19]. In TEM
imaging, the electron beam incident on the specimen is accelerated by high voltages,
resulting in highly energetic electrons with typical energies of 100–300 keV and in
some cases up to 1000 keV. The electron intensity is then detected in transmission.
One key advantage of TEM is the ease of carrying out complementary non-
magnetic characterization of samples in order to correlate the observed magnetic
configurations with the local electronic and structural properties. However, since
the signal is measured in transmission, this places considerable constraints on the
sample thickness. For scanning TEM, sample thicknesses are typically limited to
about 100 nm or less, whereas for Lorentz TEM, thicknesses up to around ∼300 nm
are possible. For bulk samples, it is necessary to apply thinning processes before
imaging, which potentially modifies the domain structure of interest. Thin-film
samples and associated lithographically defined nanostructures are more readily
imaged via TEM, but need to be deposited on suitable substrates which are
transmissive for the electrons, e.g., silicon nitride (Si3 N4 ) membranes, which take
some care in handling. Another important consideration when applying TEM
imaging to magnetic structures is that usually the sample would be subject to a
very strong magnetic field from the objective lens of the microscope. To avoid
perturbing the domain structure, strategies have to be employed to reduce this
field which may require dedicated equipment and in all cases tend to limit the
resolution of magnetic modes of TEM microscopy as compared to other forms
of TEM characterization. The existence of structural contrast even in magnetic
imaging modes can also limit the practical resolution. A review of the application
of TEM to imaging magnetic microstructure is provided in [20]. In the following,
we describe some of the different operational modes of the technique. These modes
have different advantages and drawbacks and are sensitive to varying features of
the magnetic state of the system. However, in general, a number of modes can be
combined to provide more comprehensive information and overcome the limitations
of a particular mode [21].
Lorentz Microscopy
Lorentz microscopy relies on the perturbation of an electron beam due to magnetic
fields. The resulting small angular deflections of the beam of around 10−5 −
−10−4 rad, can be classically attributed to the so-called Lorentz force:
24 Magnetic Imaging and Microscopy 1209
where e is the electron charge; υ is the electron velocity, which depends on the
acceleration energy; and B is the magnetic flux density. In quantum mechanical
terms, the sample can be considered to modulate the phase of the incident electron
wave depending on the magnetic state, leading to bright-dark contrast due to
interference. From (1), it can be seen that components of B aligned with the beam
do not contribute to the deflection and therefore samples may need to be tilted in
the case of perpendicular magnetic anisotropy systems. The technique is sensitive
to magnetic flux along the whole path of the electron beam, and hence, it is not only
the magnetization within the sample which contributes to the deflection but also
stray magnetic fields. In some cases, these two contributions can act against each
other, diminishing or even cancelling out contrast. The deflection direction depends
on the magnetization orientation and is perpendicular to it. The magnitude of the
deflection is directly proportional to the thickness and averaged magnetic induction
of the specimen.
Fresnel Imaging
The first mode of Lorentz imaging is the Fresnel imaging, or defocus mode. Since
the influence of the magnetic structure of the specimen only causes deflections of
the beam, an in-focus image of the sample normally does not contain any magnetic
contrast. In Fresnel imaging, this is overcome by defocusing the imaging lens. This
reveals magnetic features of the sample, however, at the expense of reducing the
achievable spatial resolution. For this imaging mode, the objective lens is kept
switched off to avoid the exposure of the specimen to high magnetic fields from
the lens which would result in a destruction of domain structures of interest. For
this reason, a Lorentz mini-lens is used to image the magnetic structure, and the
objective lens can be used to produce a vertical magnetic field.
The mechanism is illustrated in Fig. 1. As can be seen in the figure, the opposite
direction of deflection for neighboring beams on either side of a 180◦ domain wall
leads to either converging or diverging beams at the wall positions. Consequently,
such walls are revealed by corresponding bright or dark contrast, depending on
whether overfocused or underfocused imaging is employed, while the domains
themselves usually have uniform contrast. An exception is the case of polycrys-
talline films where due to small fluctuations in the directions of magnetocrystalline
anisotropy characteristic ripple contrast can occur which is oriented perpendicularly
to the magnetization direction of the given domain. More in-depth reconstructions
of the domain states of a sample are, however, extremely challenging in this imaging
mode. Due to the required high defocusing, there is a very strong nonlinearity
between the contrast and the magnetic state of the film. More recently, the possibility
to reconstruct the phase of the emerging electron wave has been demonstrated by
acquiring multiple Fresnel images for different values of defocus and then applying
the transport of intensity equations [22].
1210 R. M. Reeve et al.
Fig. 1 Fresnel mode of Lorentz microscopy: Schematic representation of the contrast formation in
the Fresnel imaging mode for a sample consisting of two opposing in-plane domains separated by
a 180◦ domain wall. The Lorentz force deflects the electron beams, leading to dark/bright contrast
for over- and underfocus conditions of the microscope, respectively
Foucault Imaging
In Foucault imaging, a different strategy is employed to reveal magnetic contrast in
TEM images [23]. Since the variously magnetized domains lead to different Lorentz
deflection angles of the beams, the reciprocal space image of the sample is split into
different components for these different Lorentz angles. Particular components can
therefore be selected by using an aperture to block part of this reciprocal space
pattern which is formed in the back focal plane of the imaging lens and blocking
aperture. This is illustrated schematically in Fig. 2 where two spatially separated
diffraction spots are evident due to the two magnetization directions present in the
specimen. By blocking one or other of these beams, contrast is generated in the
image. Unlike in Fresnel imaging, in the Foucault mode, the contrast is correlated
to the magnetic induction from the domains themselves and not the change in
magnetic induction between domains, resulting in an image that is easy to interpret.
Furthermore, the magnetic imaging is performed by keeping the imaging lens in
focus and thereby generating better spatial resolution of the magnetic structure as
compared to the Fresnel mode, which is usually performed with a high defocus of
the imaging lens. However, the stringent requirements on the quality and positioning
of the aperture mean that this mode is more difficult to implement.
the achievable resolution for Fresnel imaging, and both techniques offer limited
quantitative information. For more quantitative imaging, the differential phase
contrast technique is an attractive option based on scanning TEM [24, 25]. The
incident focused beam is rastered across the sample and the transmitted beam
detected by a special four-quadrant circular detector. For magnetic samples, the
Lorentz deflection leads to opposite quadrants being illuminated to a greater or
lesser extent, and hence, difference signals for the two opposing quadrant pairs
provide quantitative information concerning the two orthogonal in-plane magnetic
induction components. This is illustrated schematically in Fig. 3.
This method suffers from longer recording times than the previous modes due
to the necessity to scan the sample and furthermore has increased instrumental
and experimental complexity. Nevertheless, good spatial resolution can be achieved
from the focused beam, down to around 5 nm. One drawback is that parasitic
differential contrast of non-magnetic structural origin can also arise, in particular
for thinner samples and polycrystalline systems. However, the use of fully pixelated
detectors is a recent advance which provides much improved efficiency for enhanced
magnetic contrast [26].
Electron Holography
Whereas the modes discussed so far can conceptually be understood from a classical
picture of the electron beam, electron holography explicitly relies on the quantum
mechanical wave nature of the electrons. Holographic techniques can provide high
spatial resolution imaging, typically down to about 5 nm. Furthermore, they offer the
possibility to image stray fields outside a given sample. A wide variety of schemes
exist, including even tomography, as reviewed in [27, 28, 29]; however, the most
common mode is off-axis holography as outlined below.
1212 R. M. Reeve et al.
Fig. 3 Differential phase contrast microscopy with a four-quadrant detector: Depending on the
magnetic induction in the sample, the beam is deflected in the perpendicular direction. The
difference signal between opposite quadrants of the detector provides a differential phase contrast.
For the first case, the beam is aligned with the magnetic induction, and there is no deflection,
yielding an equal signal for the left (L) and right (R) quadrants. In the second case, the beam
passes through a domain oriented out of the plane of the page, leading to a right deflection of the
beam and L<R. In the final case, the beam passes through a domain oriented into the plane, leading
to the opposite deflection of the beam and correspondingly L>R
Off-Axis Holography
In off-axis holography, a highly coherent incident beam is split into a probe beam
and a reference beam, the first of which passes through the sample, while the latter
remains unperturbed. Due to the interaction of the probe beam with the magnetic
state, the electron wave acquires a phase shift depending on its path. When the
probe and reference beams are then recombined, they interfere to form a holographic
interference image, encoding information on both the phase and amplitude of
the transmitted wave. In the ideal case, this is directly related to the magnetic
state of the sample; however, complications arise for samples with nonuniform
composition or thickness since these can introduce other sources of phase shifts, for
instance electrical. Quantitative information can then be extracted by processing the
interference pattern to mathematically reconstruct the amplitude and phase. There
are two main imaging modes. The setup for the absolute mode is depicted in Fig. 4.
The sample is chosen such that it only partly fills the image plane, for example by
imaging the edge of a structure or a small element. Part of the beam then passes
through the specimen and part is unperturbed. In order to recombine the two beams
and form the hologram, an element called a biprism is used which consists of a thin
metallic wire or quartz fiber coated with Au or Pt and which is biased at a voltage
of typically 50–200 V. In the differential mode, two beams are created which are
both directed toward the sample, separated by a small distance, and the phase shift
between these two beams is then recorded. This imaging technique is advantageous
24 Magnetic Imaging and Microscopy 1213
for the investigation of fine structure such as the profiles of magnetic domain walls
with the resolution set by the beam diameter. It does, however, require a specially
adapted microscope and image reconstruction software [21].
Aberration Correction
In conventional TEM, there has been significant recent improvement in achievable
resolution by implementing aberration correction [30]. Electron lenses are inher-
ently much poorer than optical lenses, and their associated spherical aberration is
often a key limiting factor in determining the resolution of electron microscopes.
To counteract this, schemes have been developed to compensate for the aberration
of the TEM objective lens by incorporating a correcting element with negative
spherical aberration into the microscope. Two approaches are based on multipole
lenses called the quadrupole-octupole corrector and sextupole corrector. In the case
of magnetic imaging, the objective lens is often not used due to the impact of the
associated magnetic field on the sample; however, aberration correction schemes can
still be employed to compensate for the relevant lens in the instrument and improve
the attainable resolution of these imaging modes [31].
In a scanning electron microscope (SEM), the electron beam is scanned across the
sample, and the generated electrons are detected in reflection. When an energetic
primary electron beam interacts with a sample, a spectrum of energies for electrons
leaving the sample results. At high energies around the primary beam energy, there
is a peak corresponding to elastically scattered electrons. In the middle of the spec-
trum, small elemental specific peaks are found corresponding to Auger electrons
1214 R. M. Reeve et al.
which are typically in the 100–2000 eV range. Finally, at very low energies, below
around 50 eV, one finds the so-called true secondary electrons. These correspond to
electrons having undergone many inelastic scattering processes which are emitted
in a cascade process. Since this scattering involves states in the vicinity of the
Fermi level, the emitted secondaries are found to be spin-polarized in itinerant
ferromagnets due to the imbalance between spin-up and spin-down states [32]. For
energies above ∼10 eV, this spin polarization directly reflects that at the Fermi level,
whereas at lowest energies, an additional enhancement in polarization is observed
due to a spin-dependent scattering-induced spin-filtering effect. The interaction of
the electrons with the sample leads to different effects depending on the energy,
and these can variously be employed for magnetic imaging [33]. In the first case,
as with many of the TEM techniques, the trajectories of the detected electrons
are modified by the magnetic configuration of the sample. In the second case,
the emitted electrons may be spin-polarized, with the polarization representing
features of the spin-split band structure of the ferromagnet. If the low-energy
secondary electrons are detected, the contrast is sometimes termed “type I.” In
this case, deflection is largely due to the magnetic stray fields from the sample.
The elastically backscattered electrons are primarily affected by the magnetization
within the sample, leading to so-called “type II” contrast. In this case, the sample is
tilted with respect to the beam, and the resulting deflection of the electrons within
the sample leads to an enhancement or reduction of the backscattered electron
yield depending on whether the deflection is directed toward or away from the
surface. While the lateral resolution, at a few μm, is quite limited compared to other
magnetic imaging techniques, the deep penetration of highly energetic electrons
can be taken advantage of to image through surface layers and can probe domain
structures to depths of ∼1–20 μm depending on the incident electron beam energy.
SEMPA
Scanning electron microscopy with polarization analysis (SEMPA) or spin-SEM
takes advantage of the fact that the spin polarization of the emitted low-energy
electrons is oriented antiparallel to the magnetization in the sample [34, 35, 36].
Hence, by exciting secondary electrons point-by-point with an unpolarized scanning
electron beam and measuring the polarization of the emitted electrons, a direct
quantitative representation of the domain state can be obtained as illustrated in
Fig. 5. The polarization of the emitted electrons is measured via a spin detector.
Here, the spin-polarized electrons are focused onto a target where, due to the
spin-orbit interaction, asymmetries in scattering exist for spin-up and spin-down
electrons. By counting the number of electrons scattered in opposing directions
using electron multipliers, the beam polarization can be calculated as follows:
1 NA − NB
P = , (2)
Seff NA + NB
where Seff is the effective Sherman or sensitivity factor of the detector which
quantifies the scattering asymmetry that is obtained for a 100% polarized beam
24 Magnetic Imaging and Microscopy 1215
Fig. 5 SEMPA: Schematic representation of the SEMPA technique. An unpolarized SEM beam
excites secondary electrons from the magnetic sample, and their spin polarization is analyzed with
a spin detector. On the right, typical images are presented for an Fe whisker. Here, the technique
simultaneously acquires the topography and the two in-plane magnetization components which
can be processed to provide the full in-plane color map of the magnetization
and NA/B are the electron counts for scattering in opposite directions. Instruments
are usually equipped with two pairs of electron counters which simultaneously
provide the two orthogonal in-plane components of the magnetization which can
be combined into a single map of the 2D domain structure, as shown in Fig. 5.
Some instruments also employ a spin-rotator, in which case the out-of-plane
component can also be accessed. The sum of the signals from all four detectors
provides a secondary electron topographic image of the sample which is helpful
in distinguishing between features of magnetic and non-magnetic origin. One
advantage of SEMPA is that in general morphological details are suppressed in the
magnetic asymmetry images.
A number of designs of spin detector exist [37]; however, the two most
commonly employed in SEMPA are the Mott polarimeter and spin-polarized
low-energy electron diffraction (SPLEED) detector. The SPLEED detector takes
advantage of the spin-dependent low-energy electron diffraction from a W(100)
crystal with the asymmetries in the intensities of the (2,0) diffraction beams at
104.5 eV scattering energy employed [38]. The Mott detector is based on the spin-
dependent Mott scattering of highly energetic electrons from films of high atomic
number elements. Originally, Mott polarimeters worked at particularly high voltages
and were very bulky. Nowadays, however, much more compact instruments are
available operating around 25 kV [39], facilitating their employment in a small lab
setting [40]. Unfortunately, the inherent low efficiency of spin detectors of around
10−4 means that long acquisition times are required to obtain sufficient signal-
to-noise ratio per pixel, with typical images requiring several minutes or longer,
depending on the desired resolution, the imaging area, and the particular material.
The entire system therefore needs to be stable on these timescales including the
1216 R. M. Reeve et al.
incident beam, sample state, and mechanical vibrations. Furthermore, thermal drifts
are often problematic and can limit practical resolutions. In the case of the SPLEED
detector, the integrity of the W surface also needs to be maintained, since even
residual gas adsorption will degrade the performance [41], requiring that the surface
is periodically flash-heated to regenerate good scattering conditions.
Since the magnetic probing depth of spin-polarized electron spectroscopies is
very small [42], SEMPA has an extreme surface sensitivity of around 1 nm. On
the one hand, this places particularly stringent requirements on the cleanliness of
surfaces being measured, requiring measurement in ultrahigh vacuum (UHV). For
thin films, capping layers or non-magnetic oxide surface regions often need to be
removed in situ by, e.g., Ar+ ion sputtering, while bulk crystals are often cleaved in
situ to reveal a pristine surface. For simple 3d metals, such in situ sputtering often
yields good results, yet for more complex compounds, care needs to be taken to
ensure that different sputter rates for the different elemental components do not lead
to changes in the stoichiometry. Recently, however, it has been demonstrated that
it is possible to image through heavy metal capping layers provided they remain
thin enough [43]. An often employed strategy to mitigate the surface requirements
involves the in situ deposition of a thin dusting layer of Fe [44]. The expectation
is that this will couple to the magnetic structure of the underlying film, imprinting
the domain structure in the pristine Fe layer which can itself then be imaged. This
method can also be employed to improve the contrast for materials with low signals,
such as non-itinerant ferromagnets, and can also facilitate the imaging of insulating
systems where charging effects usually prevent investigation with electron beams.
However, it is necessary to confirm that the thickness of the deposited Fe film is thin
enough that it does not change the domain state in the material under investigation.
At the same time, the surface sensitivity confers the ability to selectively probe
the properties of the surface [45], which are often instrumental in determining
device operation and which have furthermore been taken advantage of to image
particularly thin ferromagnetic films down to just a few monolayers [46] and even
layered antiferromagnets due to the strong contribution of the uppermost atomic
layer [47].
Virtually, all SEMPA imaging to date has been static or quasi-static in nature.
The long acquisition times are a barrier to investigation of magnetization dynamics;
however, very recently, the feasibility of imaging on nanosecond timescales with
advanced signal processing based on the time of detection of the individual electron
counts has been demonstrated [48, 49]. Via careful data analysis, this also opens up
opportunities for improvements in the signal-to-noise ratio, as well as the detection
of competing magnetic switching pathways that are not accessible in conventional
pump-probe imaging [49, 50]. The high spatial resolution is a key advantage of the
technique, enabling imaging not only of domain configurations but also of domain
wall spin structures [51]. The impetus to increase the spin signal means that it
is usual to operate the SEM at large beam currents and low voltages of typically
1–3 kV, for which the emission of the spin-polarized low-energy secondaries is
increased [52]. Under these conditions, typical resolutions are around 20 nm;
however, resolution of better than 5 nm has been demonstrated [34].
24 Magnetic Imaging and Microscopy 1217
Technical Details
Chemically etched tungsten tips are the most commonly used tips for STM. Starting
from these tungsten tips, a thin ferromagnetic film evaporated on the tip apex then
serves as a ferromagnetic counter electrode. The stray field of the thin film is small
enough to avoid dipolar sample-tip interaction. Alternatively, antiferromagnetic tips
are used. In this case, Cr tips etched from thin Cr wires are advantageous. For
SP-STM, the tip must be prepared in situ in UHV, for example, by voltage pulses,
24 Magnetic Imaging and Microscopy 1221
in order to obtain high resolution and magnetic contrast. Usually, only a single
magnetization component is detected. The sensitivity axis of the tip is in many cases
not obvious and must be calibrated on known magnetization structures.
The tunneling current can be described as a sum of a spin-averaged and a spin-
dependent term [89]. Following Ref. [90], the tunneling current can be calculated
by Fermi’s golden rule:
∞
I∝ |M(ε)|2 ρT (ε − eV )ρS (ε)[f (ε − eV ) − f (ε)]dε. (3)
∞
with φ denoting the angle between tip and sample magnetization and g0 the
unpolarized conductivity. The assumption of a constant tip polarization ρT (εF ) is
realistic in the case of V > 0 probing the unoccupied states of the sample because
the tunneling current is dominated by electrons from the Fermi level of the tip. For
illustration of this case, the tip and sample density of states is sketched on a common
energy scale in Fig. 6a. In contrast, when probing the occupied sample states V < 0,
a strong convolution with the tip density of states has to be considered.
Experimental Examples
The imaging of molecular structures is an important step toward the understanding
of spin transport and scattering in hybrid organic-metallic interfaces [91]. An
example of a Cu-phthalocyanine molecule on a metallic ferromagnetic surface is
shown in Fig. 6 [92]. Figure 6c–h shows dI /dV spectra and the corresponding
spin asymmetry, defined as A = [D(↑↑) − D(↑↓)]/[D(↑↑) + D(↑↓)]. From the
spectroscopic results obtained by collecting the current at tip positions over the
molecule, one can observe the almost entire suppression of the peaks at −0.1 eV,
as compared to the clean Fe surface. In contrast, a new peak appears at +0.4 eV
1222 R. M. Reeve et al.
Fig. 6 (a) Sketch of the tip and sample density of states in a common energy scale assuming
positive sample bias. (b) Topographical image of a Cu-phthalocyanine molecule on Fe(110).
dI /dV (V )-spectra (c, e, g) and asymmetries (d, f, h) extracted from the indicated areas in
(b) on the Cu-phthalocyanine molecule deposited on Fe(110). dI /dV (V )-spectra are measured for
parallel (black) and antiparallel (red) orientation of tip and sample magnetization. Experimental
asymmetries (blue) are compared to calculated asymmetries (black lines). For comparison, the
asymmetry of clean Fe, (d) scaled by 0.5, are also shown in red lines in (f) and (h). (Reprinted
figure with permission from [T. Methfessel, S. Steil, N. Baadji, N. Grossmann, K. Koffler, S.
Sanvito, M. Aeschlimann, M. Cinchetti, H. J. Elmers, Phys. Rev. B 84 224403 (2011)] Copyright
(2011) by the American Physical Society. [92])
Fig. 7 Spin-polarized STM images obtained with a Cr tip on an ultrathin PdFe/Ir(111) film
measuring the in-plane magnetization component. Detailed view of an isolated skyrmion. With
decreasing external magnetic field, the skyrmion gradually develops an elliptical shape and finally
stretches into a spiral domain. (Reprinted figure with permission from [A. O. Leonov, T. L.
Monchesky, N. Romming, A. Kubetzka, A. N. Bogdanov and R. Wiesendanger, New J. Phys.
18 065003 (2016)] Copyright (2016) by the Institute of Physics. [95])
Technical Details
For the measurement of the magnetic forces, almost exclusively the dynamic
mode is applied, where resonance frequency shifts of the oscillating cantilever are
measured either directly or indirectly by the amplitude variation for fixed excitation
frequency. The frequency of the oscillating cantilever is given by
1 dFm
f = f0 1 − (6)
c∗ dz
1224 R. M. Reeve et al.
Experimental Examples
An example of high-resolution imaging using MFM is its employment to image
bit-patterned media with perpendicular anisotropy, where a resolution of better
than 10 nm has been demonstrated by evaluating line profiles in the images [102].
Figure 9 shows as a second example an image of a magnetic skyrmion indicating
the high resolution obtained by this method.
A considerable increase in spatial resolution can be achieved by magnetic
exchange force microscopy. The general concept of magnetic exchange force
microscopy relies on the combination of the atomic resolution atomic force
microscopy with spin sensitivity by using as a force sensor a magnetic tip mounted
on the free end of a cantilever. During scanning in the x-y plane, Δf is kept constant
by adjusting the z position of the tip relative to the surface so that the recorded
topographic image represents the condition of a constant tip-sample interaction
force. Selecting a more negative Δf set point increases the attractive interaction;
that is, the tip-sample distance is reduced. This method permits atomic resolution
24 Magnetic Imaging and Microscopy 1225
Fig. 8 Schematic of the NV center working principle. The NV center at the tip of an AFM is
rasterscanned across a magnetic surface at constant height. The stray field of an inhomogeneous
magnetization structure splits the states with mz = ±1 in proportion to the local field component
along the NV axis. By continuous illumination with green light through confocal optics, the mz = 0
state is excited and initiates red fluorescent light, detected by the same optical setup. If the ground
state is depopulated by resonant pumping with ca. 3 GHz microwave radiation into the mz = ±1
states, the fluorescent intensity will decrease. The resonance frequency is a measure for the stray
field component
Fig. 10 MFM images using the same tip at 7.9 K in 5 T on the same area. (a) Image recorded
at a constant frequency shift of −22.0 Hz. (b) Image measured at a constant frequency shift of
−23.4 Hz corresponding to a reduction of tip-sample distance of 30 pm. (c, d) Fourier transforms
of (a) and (b), respectively. (Reprinted by permission from Springer Nature: Nature (Magnetic
exchange force microscopy with atomic resolution, U. Kaiser, A. Schwarz and R. Wiesendanger),
Copyright (2007) [58])
24 Magnetic Imaging and Microscopy 1227
X-Ray Imaging
X-ray imaging is often the method of choice when studying magnetic materials in
operando conditions, primarily because x-ray absorption and scattering are largely
insensitive to the presence of other DC or AC electromagnetic fields. The resolution
is one to two orders of magnitude better than optical microscopy (see Table 1),
which makes x-ray imaging a powerful tool to study the texture and dynamics of
nanometer-scale magnetic spin structures. Moreover, compared to electron beams,
(sub-)ps x-ray pulses are often available in higher intensity and coherence. Finally,
the larger penetration depth of x-rays compared to electrons allows for imaging
of much thicker samples as compared to transmission electron microscopy. These
advantages typically come at the price of lower spatial resolution compared to
electron microscopy as well as a limited availability of laboratory-based sources.
In this section, we review the working principle as well as the strengths
and weaknesses of the most established x-ray imaging techniques. Specifically,
we discuss transmission x-ray microscopy (TXM), scanning transmission x-ray
microscopy (STXM), photoemission electron microscopy (PEEM), and coherent
x-ray imaging (CXI). Typical images of these techniques are shown in Fig. 11. In
the end, we also briefly present a technique for band structure or momentum space
imaging of magnetic materials, namely, spin-polarized angle-resolved photoemis-
sion spectroscopy (SP-ARPES). Reviews of imaging with x-ray microscopy can be
found in Refs. [104, 105].
Table 1 Comparison of magnetic imaging techniques, presenting some of the key specifications
and attributes. The quoted values are in general typical achievable values.∗ Proof of concept
recently demonstrated [48, 49, 152]
Probed Spatial Temporal
Technique quantity resolution resolution Info. depth Comments
Lorentz Stray field 10 nm 1 ns Sample Thin samples,
microscopy + average quantitative info. with
sample differential phase
induction contrast microscopy
Electron Stray field 5 nm 10 ms Sample Quantitative info.
holography + average through mathematical
sample image reconstruction
induction
SEMPA Magnetization 20 nm 700 ps∗ 1 nm Quantitative info.,
long acquisitions,
UHV required
SP-STM Magnetization Atomic 120 ps∗ Surface UHV required,
usually low
temperature,
long acquisitions
MFM Stray field 10–100 nm Low 1000 nm Potentially invasive,
long acquisitions,
few sample
requirements
NV mag- Stray field 10–20 nm Low 1000 nm Noninvasive,
netometry single spin sensitivity,
long acquisitions
TXM Magnetization 25 nm 50 ps Sample Synchrotron
average technique,
quick overview
images
STXM Magnetization 15–25 nm 50 ps Sample Synchrotron
average technique,
high repetition rates
PEEM Magnetization 40 nm 50 ps 5 nm Synchrotron
technique,
discharges possible
due to high potential
CXI Magnetization 10–30 nm fs-ps Sample Zero drift,
average synchrotron
technique,
complex sample
fabrication & image
reconstruction
MRI Proton density 1–2 mm 100 ms- 3D Low risk,
& several imaging very versatile
environment sec.
MEG Stray field 5 mm <1 ms 3D No unique solution,
imaging risk free
via
modelling
24 Magnetic Imaging and Microscopy 1229
Fig. 11 Typical images of magnetic skyrmions recorded by various x-ray imaging techniques.
(a: Reprinted by permission from Springer Nature: Nature Scientific Reports (Room-temperature
chiral magnetic skyrmions in ultrathin magnetic nanostructures, O. Boulle, J. Vogel, H. Yang,
S. Pizzini, D. de Souza Chaves, A. Locatelli, T. O. Menteş, A. Sala, L. D. Buda-Prejbeanu, O.
Klein, M. Belmeguenai, Y. Roussigné, A. Stashkevich, S. M. Chérif, L. Aballe, M. Foerster,
M. Chshiev, S. Auffret, I. M. Miron & G. Gaudin), Copyright (2016) [106]. b: Reprinted by
permission from Springer Nature: Nature Nanotechnology (Discrete Hall resistivity contribution
from Néel skyrmions in multilayer nanodiscs, K. Zeissler, S. Finizio, K. Shahbazi, J. Massey, F.
Al Ma’Mari, D. M. Bracher, A. Kleibert, M. C. Rosamond, E. H. Linfield, T. A. Moore, J. Raabe,
G. Burnell & C. H. Marrows), Copyright (2018) [107]. c: Reprinted by permission from Springer
Nature: Nature Communications (Spin-orbit torque-driven skyrmion dynamics revealed by time-
resolved X-ray microscopy, S. Woo, K. M. Song, H.-S. Han, M.-S. Jung, M.-Y. Im, K.-S. Lee,
K. Soo Song, P. Fischer, J.-I. Hong, J. W. Choi, B.-C. Min, H. C. Koo & J. Chang ), Copyright
(2017) [108]. d: Reprinted by permission from Springer Nature: Nature Nanotechnology (Field-
free deterministic ultrafast creation of magnetic skyrmions by spin-orbit torques, F. Büttner, I.
Lemesh, M. Schneider, B. Pfau, C. M. Günther, P. Hessing, J. Geilhufe, L. Caretta, D. Engel, B.
Krüger, J. Viefhaus, S. Eisebitt & G. S. D. Beach), Copyright (2017) [109].)
Fig. 12 Left: Schematic illustration of the XMCD effect. X-ray illumination of the sample excites
element-specific electronic transitions from core levels to empty states at the Fermi level. Due
to the spin-split density of states in the magnetic specimen, the x-ray absorption cross sections
are different for negative and positive helicity of the incident photons, depending on the relative
alignment of the incident wave vector and the magnetization in the sample, as shown on the right
in the case of the L2 and L3 absorption edges of Fe. (Reprinted by permission of Springer Nature:
Springer (Magnetism: From Fundamentals to Nanoscale Dynamics, Interactions of polarized
photons with matter, p. 390, J. Stöhr and H. C. Siegmann), Copyright (2016) [111])
(all in units of h̄). In particular, we will use the fact that ml changes by q and that
ms is conserved.
The 2p levels experience a strong spin orbit coupling, typically on the order
of 15 eV, which ensures that the L2 = 2p1/2 → 3d and the L3 = 2p3/2 → 3d
absorption edges do not overlap. Consider the L2 transition, schematically illus-
trated in Fig. 13. The absorption intensity is proportional to the matrix element
I ∝ i,f |f |Cq |i| , where |i = |n = 2, l = 1, j = 1/2, mj = ±1/2 :=
1 2
Fig. 13 Illustration of how to derive the relative absorption difference of positive (q = +1) and
negative (q = −1) helicity x-rays at the L2 resonance assuming that only spin-up states are
available in the 3d band. For details, see text
with the spin-up component of the initial states results in the relative absorption
intensities of 75% for negative helicity light and 25% for positive helicity light at
the L2 edge. The intensities into a spin-down 3d band are inverted with respect to q.
In general, both spin-up and spin-down states are available in the valence
band. The total absorption cross section is then proportional to the spin-dependent
absorption intensities times the spin-dependent density of available final states.
Therefore, the absorption of right circular light minus the absorption of left circular
light measures the difference of available up states minus the density of available
down states in the 3d band, which is proportional to the magnetization of the sample
along the photon propagation direction.
Imaging with XMCD contrast requires highly monochromatic, circularly polar-
ized x-rays at suitable resonant energies. Typically, these are the L (800 [∼]eV)
or M (60 [∼]eV) edges of the magnetic transition metals, a range known as
the soft x-ray or extreme UV regime, respectively. Such light is available with
high intensity at modern synchrotrons and free electron lasers (FELs), and up to
now, most x-ray magnetic imaging is performed at these facilities. However, the
development of high harmonic generation sources has made tremendous progress
recently [112, 113], and laboratory-based XUV imaging of magnetic domains has
recently been demonstrated [114].
1232 R. M. Reeve et al.
CCD
MZP
Sample
OSA
KZP
Fig. 14 Schematic illustration of a transmission x-ray microscope. The incident beam is transmit-
ted through a condenser zone plate (KZP), which is made of alternating opaque and transparent
rings to mimic a Bessel transmission function. The non-diffracted zero-order light, as well as
higher-order diffractions, is blocked using an order selecting aperture (OSA). The sample is placed
close to the focus of the KZP. An image of the transmitted light is generated via an objective zone
plate (MZP) on a CCD camera chip
24 Magnetic Imaging and Microscopy 1233
field of view. The binning allows for low-noise readout in 1 s, and a good quality
image is obtained by accumulating ∼20 images per helicity, yielding a full XMCD
image in approximately 1 min.
The fast acquisition of large-scale images with good resolution is the major
advantage of TXM compared to other magnetic imaging techniques. Furthermore,
some TXM end stations are built such that the OSA and the MZP act as vacuum
windows and the sample is in air, which is helpful for some applications. However,
due to the full-field nature of the technique, fast multi-pixel detection is needed for
dynamic imaging, limiting the repetition rate for dynamic processes.
Photoemission electron microscopy (PEEM) makes use of the fact that an electron
excited by photon absorption can relax by transferring its energy to other electrons
at the Fermi energy [121, 122]. If this release of energy to the Fermi level happens
1234 R. M. Reeve et al.
detector
electrons
X-rays
20kV
Fig. 15 Schematic illustration of PEEM. The incident x-rays hit the sample under grazing
incidence, hence being absorbed in the surface-near region. The larger the absorption cross section,
the more energy is deposited near the surface, where secondary electrons are generated that can
leave the sample into the vacuum. The free electrons are accelerated by a strong electric field of
20 kV toward a detection column, where they are energy filtered and focused to a 2D detector. For
simplicity, the electron optics are not drawn in the schematic
near the surface of the sample, some electrons receive enough energy to leave the
sample into the vacuum. These free electrons can be accelerated by a high voltage
and focused by a series of electromagnetic lenses to a pixel detector (see Fig. 15).
The number of electrons at a specific pixel of the detector is proportional to the
number of electrons emitted at the corresponding position of the sample, which
in turn is proportional to the absorption of photons in the surface-near region.
Making use of the XMCD effect, an image of the magnetization in the direction
of the incident x-rays can be obtained. Due to the low mean free path of secondary
electrons inside the material, the sensitivity is restricted to the first few nm below
the surface. To increase the absorption efficiency in this surface-near region, PEEM
is typically operated with the x-rays hitting the sample at grazing incidence. PEEM
can also be realized in a scanning configuration [116]. Time-resolved measurements
are possible by synchronizing an external excitation of the sample with the x-ray
imaging pulses, thus allowing for pump-probe type measurements. In contrast to
the other x-ray imaging techniques discussed here, PEEM does not require an x-ray
transparent sample. Therefore, bulk substrates of arbitrary thickness can be used,
which makes PEEM very attractive to investigate epitaxial samples. A constraint is
that the sample surface must be conducting. PEEM is also a favorable technique for
imaging the in-plane components of the magnetization due to the grazing incidence
geometry [106], see Fig. 11a.
One example of PEEM imaging is presented in Fig. 16 where pump-probe
techniques have been employed to reveal the dynamic response of a magnetic
domain wall to a displacing field pulse [123]. A transverse domain wall is placed
in the center of a 2 μm wide half-ring by a static external field, as shown in (a).
Repeated pulsed in-plane fields are then generated to displace the domain wall by
24 Magnetic Imaging and Microscopy 1235
Coherent x-ray imaging (CXI) [124] is a common term for lensless imaging
techniques. Generally, the sample is illuminated with a coherent photon beam, and
the far-field scattering pattern, i.e., the squared magnitude of the Fourier transform
1236 R. M. Reeve et al.
Fig. 17 Schematic illustration of x-ray holography. The main image illustrates the principle of
x-ray holography, where a coherent x-ray beam (blue) illuminates a specimen behind a circular
aperture and a close-by reference hole. The scattered beams of these two objects interfere on
a CCD camera chip, forming the hologram. The transmission function of the sample can be
reconstructed from the hologram via an inverse Fourier transform. Within the field of view, the
reconstruction shows two magnetic skyrmions (white) on a black background. Inset: Scanning
electron micrograph of a typical sample. The horizontal wire in the center is a magnetic multilayer.
The large features at the left and right edges of the image are gold contact pads for dynamic
experiments. The bright vertical rectangle is a SiN membrane. On the back side of the membrane
is a 1.5 µm thick gold layer with three holes in it, one 800 nm diameter hole defining the field of
view of the imaging (visible as a black shadow in the center of the image) and two smaller holes
defining the reference beam (visible as two circles below the magnetic wire). The white scale bar
is 5 μm long
pattern to obtain a real-space image. It has been demonstrated that the dynamics of
skyrmions can be tracked with 3 nm precision due to this intrinsic stability [134].
Furthermore, lensless imaging is so far the only viable technique for single shot
imaging at FELs, where the beam intensity is so high that all optical elements would
be destroyed. However, these advantages come at the price of a sophisticated sample
fabrication process and, up to now, a lack of permanent user facility end stations
(with some being under construction at NSLS-II, at PETRA-III, and at MAX-IV).
A nucleus with nonzero spin, such as hydrogen, in an external magnetic field along
the z axis, Bz , will experience a Zeeman splitting of the otherwise degenerate
energy levels corresponding to different z components of the nuclear angular
momentum [144]. This yields a spontaneous polarization of the system; however,
since the energy splitting is very low compared with typical thermal energies, the
resulting polarization is very small. In order to have an appreciable signal, very
strong magnetic fields are required, which tend to be of the order 0.3–2 T in the used
instrumentation, although they can be much higher. Manipulation of the resulting
magnetization is now possible through the application of suitable radio frequency
(RF) field pulses which need to be set around the resonant frequency of the
system for appreciable effects. This frequency is known as the Larmor frequency:
ωL = γ Bz where γ is the gyromagnetic ratio. The large natural abundance of 1 H
in a human body, in combination with its comparatively large gyromagnetic ratio,
make hydrogen an attractive choice for imaging biological systems; however, other
nuclei such as phosphorus or sodium are also sometimes chosen. Since the Larmor
frequency is also dependent on the chemical environment of the proton, a so-called
chemical shift, it is possible to gain contrast based on the unique fingerprint of par-
ticular molecules or on the general environment of the nucleus. In some cases, if no
suitable contrast can be obtained from the naturally occurring differences in tissue
within the body, contrast-enhancing agents may be administered, e.g., intravenously.
These are typically paramagnetic gadolinium compounds or superparamagnetic iron
oxide nanoparticles which modify the magnetic environment of the imaging region.
The NMR experiment is schematically depicted in Fig. 18. In the initialized state,
the magnetization is aligned with the strong external field, Bz . An RF field pulse is
then applied via a coil around the sample, which acts to excite the magnetization and
rotate it away from the +z axis to an extent which is determined by the intensity and
duration of the RF pulse, as shown in Fig. 18a. Following the removal of the pulse,
the magnetization will decay back to the initial state. The relaxation dynamics of
the magnetization back to its equilibrium value, M0 , are described by the Bloch
equations:
dMx Mx
= γ (M × B)x − ∗ , (7)
dt T2
dMy My
= γ (M × B)y − ∗ , (8)
dt T2
dMz Mz − M0
= γ (M × B)z − . (9)
dt T1
The first term in each equation describes the precession of the magnetization
around the Bz field at the characteristic Larmor frequency (ω = ωL ). This
precession of the magnetization leads to a changing magnetic flux which can be
detected as an induced voltage in a series of pickup coils outside of the imaged
1240 R. M. Reeve et al.
Fig. 18 Schematic depiction of the NMR experimental setup. The magnetization vector is
represented in the shown coordinate system and arises due to polarization of the investigated nuclei
in a strong Bz field. (a) RF pulses tuned to the Larmor frequency of the system, ωL , excite the
magnetization, and cause it to rotate away from the z axis to an extent depending on the amplitude
and length of the excitation. (b) When the magnetization is not aligned with the Bz field, it will
precess around the z axis at a frequency ω = ωL . The flux from the magnetization dynamics is
picked up by coils and amplified to generate the signal. (Reprinted by permission of Wiley: (D. P.
Plewes & W. Kucharczyk, Physics of MRI: A Primer, J. Magn. Reson. Imaging 35, 1038, 2012),
Copyright (2012) [142])
object, as shown schematically in Fig. 18b. The same coils can used for detecting
the signal as those employed for the generation of the RF fields that manipulate the
magnetization. The second term in the first two equations describes the relaxation
of the transverse magnetization over a characteristic timescale known as the T2∗
relaxation time. This has contributions due to spin dephasing both as a result of
inhomogeneities in the local effective field that are fixed in time due to the varying
environment of different spins and also dephasing due to slowly time-varying field
variations and spin-spin relaxation processes. These are sometimes referred to as the
T2
and T2 relaxation times, respectively, with T1∗ = T1
+ T12 . The second term in the
2 2
last equation describes the relaxation of the longitudinal magnetization and involves
24 Magnetic Imaging and Microscopy 1241
the dissipation of the excitation energy of the system back to the lattice over a time
characterized by the spin-lattice relaxation time, T1 .
Measurements of the NMR precessional signal decay over time are sensitive
to these various relaxation processes. By changing the measurement scheme, the
relative contribution of the T1 and T2 times to the relaxation can be varied, and
since these values are also influenced by local environments, they provide a flexible
range of contrast conditions for the resulting images, in addition to the basic
proton density contrast. T1 , for example, generally increases with the strength of
the applied field, whereas the T2 values are relatively insensitive to this and hence
field-cycling experiments where the strength of the uniform field is changed allow
one to investigate this dependence. Furthermore, by setting the duration of the
excitation pulse, the initial state can be changed which also yields different dynamic
contributions. For example, with a so-called π/2 pulse, the magnetization is nutated
into the x-y plane and will undergo both precession and relaxation. However, with
a π pulse, the magnetization rotates to the −z axis, and since it is colinear with the
field, no precession occurs and the decay is solely determined by the T1 time. If the
magnetization is subsequently rotated back to the x-y plane to generate a precession
signal, the initial amplitude provides contrast weighted by T1 .
Fig. 19 The spin-echo approach. A 90◦ (π/2) pulse nutates the magnetization into the x-y plane
where it begins to precess. Dephasing occurs over a characteristic T2∗ time. A subsequent 180◦ (π )
pulse at time TE/2 reverses the order of the individual spins, which then begin to come together. At
a time TE, dephasing processes due to static field inhomogeneities characterized by T2
have been
corrected for. However, stochastic field fluctuations still play a role and contribute to the measured
signal. Additional decay of the signal will occur due to longitudinal magnetization relaxation as
characterized by T1 ; however, this is usually over longer timescales. (Reprinted by permission
of Wiley: (B. A. Jung & M. Weigel, Spin Echo Magnetic Resonance Imaging, J. Magn. Reson.
Imaging 37, 805, 2012), Copyright (2013) [145])
which can be more efficient, reducing the time required for data acquisition and
enabling imaging of dynamic processes [142]. Nevertheless, the process of scanning
a given part of the body can take quite a while. A further protocol can be employed
in order to counteract the dephasing caused by non-time-varying spatial gradients in
the global field and thereby separate this contribution to the T2∗ relaxation time. One
approach is known as a spin-echo technique [145], as indicated in Fig. 19. In the
first stage, a π/2 pulse is applied to nutate the magnetization into the x-y plane. The
system is then allowed to precess for a certain time, τ , during which the spins will
dephase due to the spatially inhomogeneous local fields. Next, a π pulse is applied,
after which the phase differences between the spins will have been reversed. Further
precession will gradually bring the spins back to their original in-phase state after
the echo time TE = 2τ . In this manner, the influence of field inhomogeneities and
the spread in fields due to chemical shifts are corrected for, and the measurement is
able to probe the spin-spin interactions from neighboring nuclei.
The spin-echo pulses are applied with a certain repetition time, TR, as the sample
is scanned. The length of TR in relation to the longer T1 relaxation processes, as well
24 Magnetic Imaging and Microscopy 1243
as the choice of TE strongly, affects the weighting of the image contrast with respect
to the T1 and T2 relaxation times, as shown in the example in Fig. 20.
uniform background field to provide the energy splitting of nuclear states, but
rather the splitting is determined by the interaction of nuclear quadrupole electric
moments and the electric field gradients around the nucleus. Such field gradients
are determined by the precise chemical environment of the nucleus, and as such
the energy splitting and associated resonant frequencies can be used for chemical
fingerprinting. NQR is restricted to nuclei with a spin quantum number ≥1 for which
the quadrupole moment is nonzero, making it complementary to NMR, offering
alternative contrast origins when imaging a given system and new possibilities for
contrast agents. As with NMR, the system is excited using RF field pulses, and the
relaxation of the system is detected via the free induction decay signal generated in
pickup coils. Imaging is achieved in a similar manner to MRI by applying spatially
varying RF fields or magnetic fields [147]. Field cycling NQR systems can be
employed to improve the sensitivity of the measurements, for example, in the case
of low abundance of the investigated nuclei, in an approach combining NQR with
NMR. In a typical measurement, the field at the sample is alternated between a high-
field and low- or zero-field condition. This is most readily achieved by physically
moving the sample into and out of a field region. In the high-field environment, the
large nuclear splitting occurs, polarizing the nuclei. The sample is then transferred
to a low-field region and the RF pulse applied at the appropriate NQR frequency
to excite the state. Finally, the sample is transferred back to the strong field, and
an NMR measurement is carried out. In addition to the chemical environment, the
resonance lines are strongly affected by physical parameters of the system, and
hence the technique has also been employed for imaging temperature, stress, and
pressure in a sample [148].
Magnetoencephalography
Summary
As has been presented, a wide variety of techniques are available to image the
magnetic state of a system, and for a given application, it is necessary for the
user to judge the most appropriate option depending on the type of specimen,
the information that one wants to acquire, and the required spatial and temporal
resolution. To conclude this chapter, Table 1 provides a summary of some of the key
attributes of a selection of the most widely employed techniques to enable ease of
comparison. We note that the quoted values are not necessarily the ultimate limits
of the techniques, but rather in most cases represent typical values under standard
operating conditions.
Acknowledgments A large number of students, postdocs, colleagues, and collaborators have also
been involved in the authors’ research efforts on magnetic imaging over the years, only a few
examples of which we have been able to present here. Without these individuals, this work would
not have been possible, and we gratefully acknowledge all their contributions and insights.
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Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1256
Magnetic Neutron Diffraction Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1257
Polarized Neutron Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1260
Polarized Neutron Reflectometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1261
Resonant Magnetic X-ray Diffraction Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1262
Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1265
Inelastic Neutron Scattering Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1265
Resonant Inelastic X-ray Scattering Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1267
Magnetic Diffraction Examples with Neutrons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1268
Magnetic Diffraction Examples with X-rays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1276
Spin Dynamics with Neutrons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1282
Spin Dynamics with RIXS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1287
Facilities and Online Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1289
Summary and Future Directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1291
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1292
Abstract
The present chapter reviews current neutron and X-ray scattering techniques
employed to elucidate the magnetic structures and spin dynamics of mag-
netic materials. Both techniques provide measurements as a function of the
energy and the momentum transferred from the spin system to the probe
particles, in terms of five-dimensional data sets as a function of various ther-
J. W. Lynn ()
NIST Center for Neutron Research, National Institute of Standards and Technology,
Gaithersburg, MD, USA
e-mail: [email protected]
B. Keimer
Max-Planck Institute for Solid State Research, Stuttgart, Germany
e-mail: [email protected]
Introduction
Magnetic neutron scattering originates from the neutron’s magnetic dipole moment.
As a spin-½ fermion, the neutron carries a magnetic dipole moment of −1.913
nuclear magnetons that interacts with the unpaired electrons in the sample, either
through the dipole moment associated with an electron’s spin or via the orbital
motion of the electron. The strength of this magnetic interaction is comparable
to the neutron–nuclear interaction. The magnetic scattering cross section reveals
the magnetic structure and dynamics of materials over wide ranges of length scale
and energy. Magnetic neutron scattering plays a central role in determining and
understanding the microscopic properties of a vast variety of magnetic systems –
from the fundamental nature, symmetry, and dynamics of magnetically ordered
materials to elucidating the magnetic characteristics essential in technological
applications.
One traditional role of magnetic neutron scattering has been the measurement of
magnetic Bragg intensities in the magnetically ordered regime. Such measurements
can be used to determine the spatial arrangement and directions of the atomic
magnetic moments, the atomic magnetization density of the individual atoms in
the material, and the value of the ordered moments as a function of external
parameters such as temperature, pressure, and applied magnetic or electric fields.
These types of measurements can be carried out on single crystals, powders, thin
films, and artificially grown multilayers, and often the information collected can be
obtained by no other experimental technique. For magnetic phenomena that occur
over length scales that are large compared to atomic distances, the technique of
magnetic Small Angle Neutron Scattering (SANS) can be applied. This is an ideal
technique to explore domain structures, long wavelength oscillatory magnetic states,
vortex structures in superconductors, skyrmions, nanomagnets, and other spatial
variations of the magnetization density on length scales from 1 to 1000 nm. Another
specialized technique is neutron reflectometry, which can be used to investigate the
magnetization profile in the near-surface regime of single crystals, as well as the
magnetization density of thin films and multilayers. This particular technique has
enjoyed dramatic growth during the last decade or so due to the rapid advancement
of atomic-layer deposition capabilities.
The cross section for magnetic Bragg scattering can be written as Ref. [10]
2
γ e2
IM (ghkl ) = C Mg A (θB ) |FM (ghkl )|2 (1)
2mc2
where IM is the integrated intensity for the magnetic Bragg reflection located at the
reciprocal lattice vector ghkl , the neutron-electron coupling constant in parentheses
1258 J. W. Lynn and B. Keimer
N
FM (ghkl ) = eig·rj ĝ × M j (g) × ĝ e−Wj (2)
j =1
where ĝ is a unit vector in the direction of the reciprocal lattice vector ghkl , Mj (ghkl )
is the vector form factor of the j-th ion located at rj in the unit cell, Wj is the Debye-
Waller factor that accounts for the thermal vibrations of the j-th ion, and the sum is
over all (magnetic) atoms in the unit cell. The triple cross product originates from
the vector nature of the dipole–dipole interaction of the neutron with the electron.
A quantitative calculation of Mj (g) in the general case involves evaluating matrix
elements of both spin and orbital operators [11, 12]. This can be quite a complicated
angular-momentum computation involving all the electron orbitals in the unit cell,
but has the simple result that only the components of the magnetic moment that
are perpendicular to ghkl (or more generally the wave vector K) contribute to the
scattering. Often the atomic spin density is collinear, by which we mean that at
each point in the spatial extent of the electron’s probability distribution, the atomic
magnetization density points in the same direction. In this case the direction of
Mj (g) does not depend on g, and the form factor is just a scalar function, f (g),
which is simply related to the Fourier transform of the magnetization density. The
free-ion form factors have been tabulated for essentially all the magnetic elements
(see, for example, https://www.ill.eu/sites/ccsl/ffacts/ffachtml.html). Note that for
X-ray scattering the form factor for charge scattering corresponds to the Fourier
transform of the total charge density of all the electrons, while in the magnetic
neutron case it is the transform of the “magnetic” electrons only, which are the
electrons whose spins are unpaired. Recalling that a Fourier transform inverts the
relative size of objects, the magnetic form factor typically decreases much more
rapidly with |ghkl | than for the case of X-ray charge scattering since the unpaired
electrons are usually the outermost ones of the ion. This dependence of the scattering
intensity on f (g) is a convenient way to distinguish magnetic cross sections from
nuclear cross sections, where the equivalent of the form factor is just a constant
since the nucleus (≈10−5 Å) looks like a point particle to a thermal/cold neutron
(see the nuclear coherent scattering amplitude b in Eq. (6)).
If in addition to the magnetization density being collinear, the magnetic moments
in the ordered state point along a unique direction (i.e., the magnetic structure is a
ferromagnet, or a simple + − + − type antiferromagnet), then the square of the
magnetic structure factor simplifies to
2
2 −Wj ig·rj
|FM (g)| = 1 − ĝ · η̂
2 z
ηj μj fj (g) e e , (3)
j
25 Magnetic Scattering 1259
We see from these expressions that neutrons can be used to determine several
important quantities: the location of magnetic atoms in the unit cell and the spatial
distribution of their magnetic electrons; the dependence of <μz > on temperature,
field, pressure, or other thermodynamic variables, which is directly related to the
order parameter for the phase transition (e.g., the sublattice magnetization). Often
the preferred magnetic axis η̂ can also be determined from the relative intensities.
Finally, the scattering can be put on an absolute scale by internal comparison with
the nuclear Bragg intensities IN from the same sample, given by
with
2
2
|FN (g)| = bj e ig·r j −Wj
e (6)
.
j
Here, bj is the coherent nuclear scattering amplitude for the j-th atom in the unit
cell, and the sum is over all atoms in the unit cell. Typically, the nuclear structure
is known accurately and FN can be calculated, whereby the saturated value of the
magnetic moment in Bohr magnetons can be obtained.
There are several ways that magnetic Bragg scattering can be distinguished from
the nuclear scattering from the structure. Above the magnetic ordering temperature
all Bragg peaks are nuclear (structural) in origin, while as the temperature drops
below the ordering temperature the intensities of the magnetic Bragg peaks rapidly
develop, and for unpolarized neutrons the nuclear and magnetic intensities simply
add. If these new Bragg peaks occur at positions that are distinct from the nuclear
reflections, then it is straightforward to distinguish magnetic from nuclear scattering.
In the case of a ferromagnet, however, or for some antiferromagnets which contain
two or more magnetic atoms in the chemical unit cell, these Bragg peaks can occur
at the same position. One standard technique for identifying the magnetic Bragg
scattering is to make one diffraction measurement in the paramagnetic state well
above the ordering temperature, and another in the ordered state at the lowest
temperature possible, and then subtract the two sets of data. In the paramagnetic
1260 J. W. Lynn and B. Keimer
state the (free ion) diffuse magnetic scattering is given by Refs. [1, 10]
2
2 γ e2
IP ara = C 2
peff f (K)2 (7)
3 2mc2
where peff is the effective magnetic moment (= g[J(J + 1)]1/2 for a free ion). This
is a magnetic incoherent cross section, and the only angular dependence is through
the magnetic form factor f (K). Hence this scattering looks like “background.”
There is a sum rule on the magnetic scattering in the system, though, and in the
ordered state this diffuse scattering shifts into the coherent magnetic Bragg peaks
and magnetic excitations. A subtraction of the high temperature data in (7) from
the data obtained at low temperature (1) will then yield the magnetic Bragg peaks,
on top of a deficit (negative) of scattering away from the Bragg peaks due to the
disappearance of the diffuse paramagnetic scattering in the ordered state. On the
other hand, all the nuclear cross sections usually do not change significantly with
temperature (apart from the Debye-Waller factor e−2W ), and hence drop out in the
subtraction. A related subtraction technique is to apply a large magnetic field in
the paramagnetic state, to induce a net (ferromagnetic-like) moment. The zero field
(nuclear) diffraction pattern can then be subtracted from the high-field pattern to
obtain the induced-moment diffraction pattern.
type model the magnetic contribution to the reflection consists of the spin-flip (− +)
and non-spin-flip (+ +) intensities of equal intensity. For the case where P||g, all the
magnetic scattering is spin-flip. Hence for a pure magnetic Bragg reflection where
(Sx ,Sy ,Sz ) are active, the spin-flip scattering should be twice as strong as for the P⊥g
configuration.
The arrangement of having P||g or P⊥g provides an experimental simplification
and hence data that are straightforward to interpret. More generally, however, P and
g can have any relative angle. This more general technique of neutron polarimetry
is more difficult to realize experimentally and can complicate the interpretation of
the data, but can provide additional details about the magnetic structure that cannot
be obtained otherwise [14].
If neutrons are incident on a surface at (very small) grazing angles the scattering
can be cast in the form of a neutron “optical potential,” analogous to photons in
optical fibers. For most materials the wavelength-dependent index of refraction for
neutrons (and x-rays) n is slightly less than unity, so that at sufficiently small angles
of incidence the scattering can be described by the one-dimensional Schrödinger
equation and the neutrons undergo total external reflection – the basis for neutron
guides. For a simple material with a net magnetization, interference between nuclear
and magnetic scattering leads to the following expression for n [10, 15]:
1/2
± λ2 γ e2
n = 1− N b± μ , (8)
π 2mc2
where N is the number density of the material and < μ > is the average moment.
The magnetic form factor is unity since we are scattering at very small angles. Note
that N b is the nuclear scattering length density for the material, and the magnetic
term is the magnetic scattering length density. The critical angle below which we
have mirror reflection is given by
1/2 2 1/2
λ2 γ e2 ∼ λ γ e2
θC = arcsin N b± μ = N b ± μ ,
π 2mc2 π 2mc2
(9)
where ± denotes the two polarization states of the neutron. Above the critical angle
the neutrons penetrate the surface, and Fourier transforming the scattering provides
a quantitative measure of the structural profile and magnetic profile of the material.
For thin films and multilayers the layers, substrate, and front and back surfaces
produce interference effects that provide a standard and very powerful technique for
determining the properties of a wide variety of magnetic materials [16, 17].
1262 J. W. Lynn and B. Keimer
Magnetic X-ray scattering was first demonstrated off resonance, that is, with
photons that were not tuned to any absorption edge of the material under study.
However, the nonresonant magnetic X-ray scattering cross section is so small that
this technique is not useful for magnetic structure determination. Magnetic X-
ray scattering has only risen to prominence when synchrotron radiation enabled
experiments with photons tuned to X-ray absorption edges, where the resonant cross
section can be enhanced by several orders of magnitude [5, 6]. The enhancement is
greatest when the partially occupied valence shell is reached by an electric dipole-
allowed transition, that is, at the L2,3 -absorption edges of transition metals with
valence d-electrons, and at the M4,5 -absorption edges of lanthanides or actinides
with valence f-electrons. Magnetic X-ray scattering is then activated by the strong
core-hole spin-orbit coupling in the intermediate state, prior to reemission of the
photon.
From an instrumental perspective, one can group magnetic X-ray scattering
experiments into three categories, depending on the photon energy E required
to reach the respective absorption edges, namely, soft (E < 1 keV), intermediate
(1 ≤ E ≤ 5 keV), and hard (E > 5 keV). Whereas soft X-ray experiments use
gratings to monochromate the synchrotron radiation, intermediate and hard x-ray
experiments are performed with single-crystal monochromators. Because of air
absorption, soft and intermediate X-ray experiments are carried out under vacuum
conditions. The soft and intermediate X-ray ranges comprise the L-edges of 3d (4d)
metals and the M-edges of 4f- (5f-) electron systems, respectively. Experiments
at the dipole-active L-edges of 5d metals are carried out with hard X-rays, as are
experiments at the K-absorption edges of d-electron systems and L-absorption edges
of f-electron systems where the resonant enhancement of the magnetic cross section
is weaker.
Unlike neutron scattering, resonant magnetic X-ray scattering experiments
require photons with a specific energy, so that only the direction and not the
magnitude of the photon momentum is adjustable. Momentum conservation yields
kinematic constraints that are particularly severe for soft X-ray experiments on
the important class of 3d metal compounds, where simple antiferromagnetic
Bragg reflections characteristic of a doubled crystallographic unit cell cannot be
reached in many cases (Fig. 1 [7]). Magnetic order with larger periodicities (and
correspondingly shorter reciprocal lattice vectors) can be studied by resonant X-ray
diffraction, but dynamical diffraction effects can be important (see the example
below). For resonant X-ray diffraction with intermediate and hard X-rays (Fig. 1),
these constraints do not apply.
In contrast to magnetic neutron scattering which is generally straightforward
to interpret, a complete quantitative calculation of the magnetic X-ray scattering
cross section requires numerical electronic structure calculations that describe the
many-body correlations in the intermediate state. In many cases, however, one is
25 Magnetic Scattering 1263
Fig. 1 (Top)
energy/density-of-states
diagram illustrating RIXS
with photons near the
L-absorption edges of 3d
(green) and 4d (blue) metals.
(Bottom) reciprocal lattice of
orthorhombic perovskite
antiferromagnets, with
structural (black) and
magnetic (red) Bragg
reflections. Circles indicate
the maximal coverage of
RIXS with photons at the Cu
(green) and Ru (blue)
L2,3 -edges. (Top panel
adapted from Ref. [7], ©
American Physical Society
2011)
interested in the magnetic moment orientation, which can be extracted from the
dependence of the scattered intensity on the photon polarization without reference
to such calculations. In spherical symmetry, the scattering tensor can be expressed
in the following way [18]:
where Mj is the magnetization vector of the ion j, εi and εo are the polarization vec-
tors of the incoming and outgoing photons, and σ (0) , σ (1) , and σ (2) are proportional
to the X-ray absorption (XAS), x-ray magnetic circular dichroism (XMCD), and x-
ray magnetic linear dichroism (XMLD) tensors, respectively. Additional terms arise
1264 J. W. Lynn and B. Keimer
from the crystal field, but they tend to be small for collinear spin structures, as long
as M points along a high-symmetry direction of the crystal lattice [18].
To separate magnetic scattering from charge scattering (first term in Eq. 10),
magnetic X-ray scattering experiments can be carried out in crossed linear polariza-
tion. With the caveats mentioned above, the intensity of a magnetic Bragg reflection
of a collinear antiferromagnet at the reciprocal lattice vector g can then be written
as
2
ig·r (1)
I = e j σj (E) εi × εo · M j ,
∗
(11)
j
where the summation runs over the magnetic unit cell. To determine the spin
structure of a given material, one commonly uses the so-called “azimuthal scan”
where the momentum transfer g is kept fixed, and the sample is rotated such that
the orientation of M varies relative to the photon polarization vectors. In this way,
simple spin structures can be determined based on a single Bragg reflection.
Even for simple spin structures, however, it is important to keep in mind that the
spectral functions σ (E) are tensors with properties that may be strongly influenced
by the symmetry of the crystal lattice. If the site symmetry is tetragonal, for instance,
the XAS spectra for light polarized in the xy-plane and along the z-axis, σ (0) xy and
σ (0) z , are generally different – a phenomenon known as “natural linear dichroism”–
σ (1) and σ (2) are also generally anisotropic.
The deviations from spherical symmetry are particularly prominent in situations
where orbital order is present. An elementary example is the Cu2+ ion with electron
configuration 3d9 (i.e., a single hole in the d-electron shell) [18]. Materials based
on Cu2+ usually exhibit Jahn-Teller distortions that lift the degeneracy between
d-orbitals of x2 -y2 and 3z2 -r2 symmetry. The lobes of these orbitals are extended
in the xy-plane and along the z-axis, respectively. For instance, the cuprate high-
temperature superconductors exhibit a tetragonal structure with holes in the x2 -y2
orbital. In this case, the electric dipole selection rules prohibit excitation of a
2p core electron into the valence shell with z-polarized light, so that σ (0) z = 0
whereas σ (0) xy = 0. The selection rule completely changes the azimuthal scans,
as observed in resonant elastic scattering experiments on copper-oxide compounds
[19]. This example illustrates the important influence of orbital order on azimuthal
scans in magnetic X-ray scattering. Proper consideration of the crystal symmetry
is especially important for experiments performed with polarized incident light, but
without polarization analysis of the scattered beam, because magnetic and charge
scattering may then both contribute to the detected signal.
The photon energy dependence of the scattering tensor σ(E) contains a lot of
additional information, some of which can be extracted without extensive model
calculations. In particular, the large enhancement of the scattering intensity at the
absorption edges of magnetic metal atoms gives rise to the element sensitivity of
25 Magnetic Scattering 1265
Dynamics
Neutrons can also scatter inelastically, to reveal the magnetic fluctuation spectrum of
a material over wide ranges of energy (≈10−8 → 1 eV) and over the entire Brillouin
zone. Neutron scattering plays a truly unique role in that it is the only technique
that can directly determine the complete magnetic excitation spectrum, whether it
is in the form of the dispersion relations for spin wave excitations, wave-vector
and energy dependence of critical fluctuations, crystal field excitations, magnetic
excitons, or moment/valence fluctuations. In the present overview we will discuss
some of these possibilities.
As an example, consider identical spins S localized on a simple cubic lattice, with
a coupling given by -JSi ·Sj , where J is the Heisenberg exchange interaction between
neighbors separated by the distance a. The collective excitations are magnons (see
Chap. 6, “Spin Waves”). If we have J > 0 so that the lowest energy configuration
is where the spins are parallel (a ferromagnet), then the magnon dispersion along
the edge of the cube (the [100] direction) is given by
Eq = 8 J S sin2 (qa/2) (12)
At each wave vector q a neutron can either create a magnon at (q, E) with a
concomitant change of momentum and loss of energy of the neutron, or conversely
1266 J. W. Lynn and B. Keimer
destroy a magnon with a gain in energy. The observed change in momentum and
energy for the neutron can then be used to map the magnon dispersion relation.
Neutron scattering is particularly well suited for such inelastic scattering studies
since neutrons typically have energies that are comparable to the energies of
interesting collective excitations in the solid, and therefore the neutron energy
changes are large and easily measured.
Additional information about the nature of the excitations can be obtained by
polarized inelastic neutron scattering techniques, which are finding increasing use.
The cross section for spin wave scattering from a simple Heisenberg ferromagnet is
given by Refs. [1, 9, 13]
± 2
d 2σ γ e2 k ’ S (2π )3
= f 2
(g) nq +1/2∓1/2 δ E∓Eq δ (K∓q−g)
d 2 2mc 2 k 2 V q,g
× 1 + (K · η)2 ∓ 2 (P · K) · (K · η)
(13)
where nq is the Bose thermal population factor and η̂ is a unit vector in the direction
of the spins. Generally spin wave scattering is represented by the familiar raising
and lowering operators S± = Sx ± iSy , which cause a reversal of the neutron spin
when the magnon is created or destroyed. These spin-flip cross sections are denoted
by (+ −) and (− +). If the neutron polarization P is parallel to the momentum
transfer K, P||K, then the spin angular momentum is conserved (as there is no
orbital contribution in this case). In this experimental geometry, Eq. (13) shows
us that we can only create a spin wave in the (− +) configuration, which at the
same time causes the total magnetization of the sample to decrease by one unit
(1 μB for a spin-only system). Alternatively, we can destroy a spin wave only in the
(+ −) configuration, while increasing the magnetization by one unit. This gives us a
unique way to unambiguously identify the spin wave scattering, and polarized beam
techniques in general can be used to distinguish magnetic from nuclear scattering in
a manner similar to the case of Bragg scattering.
Finally, we note that the magnetic Bragg scattering is comparable in strength to
the overall magnetic inelastic scattering. However, all the Bragg scattering is located
at a single point in reciprocal space, while the inelastic scattering is distributed
throughout the three-dimensional Brillouin zone. Hence when actually making
inelastic measurements to determine the dispersion of the excitations one can only
observe a small portion of the dispersion surface at any one time, and thus the
observed inelastic scattering is typically two to three orders of magnitude less
intense than the Bragg peaks. Consequently, these are much more time-consuming
measurements, and larger samples are needed to offset the reduction in intensity.
Of course, a successful determination of the dispersion relations yields a complete
determination of the fundamental magnetic interactions in the solid.
25 Magnetic Scattering 1267
Fig. 2 Magnetic diffraction pattern for Na5/8 MnO2 , obtained by subtracting the crystallographic
diffraction pattern obtained at 100 K, above the antiferromagnetic phase transition, from the data
at 2.5 K in the magnetic ground state. The structural scattering cancels in the subtraction if there
is no significant change when the sample magnetically orders. The inset shows the temperature
dependence of the intensity of the strongest magnetic peak, and reveals a transition temperature of
≈60 K. (Adapted from Ref. [30], © Spinger Nature 2014)
that there is magnetic intensity only for the low angle position, while no intensity
survives for the peak on the right, unambiguously establishing that the one peak is
purely magnetic and the other purely nuclear. These data also demonstrate that all
three components of the angular momentum contribute to the magnetic scattering.
This simple example demonstrates how the technique works; obviously it plays a
more critical role in cases where it is not clear from other means what is the origin
of the peaks, such as in regimes where the magnetic and nuclear peaks overlap, or
in situations where the magnetic transition is accompanied by a structural distortion
where the structural peaks change significantly in intensity.
When investigating the magnetic structures of new materials, it is generally best
to first carry out powder diffraction experiments to establish the basic properties
of the magnetic structure, assuming of course that the ordered moment is large
enough to observe the magnetic Bragg peaks. Once the basics are established,
on the other hand, measurements on a single crystal can provide much higher
1270 J. W. Lynn and B. Keimer
Fig. 3 Polarized neutron diffraction on polycrystalline YBa2 Fe3 O8 . The top portion of the figure
is for P⊥g, where the open circles show the non-spin-flip scattering and the filled circles are in the
spin-flip configuration. The low angle peak has equal intensity for both cross sections, and thus is
identified as a pure magnetic reflection, while the ratio of the (+ +) to (− +) scattering for the high
angle peak is just the instrumental flipping ratio. Hence this is a pure nuclear reflection. The center
portion of the figure is for P||g, and the bottom portion is the subtraction of the spin-flip data for
the P⊥g configuration from the spin-flip data for P||g. Note that in the subtraction procedure all
background and nuclear cross sections cancel, thereby isolating the magnetic scattering. (Reprinted
by permission from Ref. [31], © American Physical Society 1992)
25 Magnetic Scattering 1271
Fig. 4 Neutron diffraction intensity map observed in the (h, k, 0) scattering plane of a single
crystal of the multiferroic Co3 TeO6 . The temperature is 22 K, just below the antiferromagnetic
phase transition at TN = 26 K. The nuclear Bragg peaks at integer positions are accompanied by
four satellite magnetic reflections, indicating the development of incommensurate (ICM) magnetic
order. Note that the ordering wave vector is incommensurate in both h and k. No energy analyzer
was used for these measurements so that the data are energy-integrated, and there is clear diffuse
scattering surrounding the ICM peaks at this temperature originating from magnetic excitations.
(Adapted from Ref. [32], © American Physical Society 2012)
quality and more detailed information about the magnetic properties. Figure 4
shows a map of the scattering intensity in the (h,k,0) scattering plane at 22 K for
a single crystal of the multiferroic Co3 TeO6 , which orders antiferromagnetically at
26 K [32]. The crystal structure is monoclinic, and we see four satellite magnetic
peaks around each (integer) structural peak, indicating that the initial magnetic
structure is incommensurate in both the h and k (and l as well, it turns out [33])
directions. With further decrease of temperature, a series of additional transitions
are observed, details of which would be difficult to determine with a powder. At
lower temperatures, separate commensurate peaks develop, then there is a lock-
in transition along k that includes a ferroelectric order parameter, and then finally
a transition into the ground state with both commensurate magnetic order and
incommensurate order along h, k, and l. [33, 34].
The magnetic superconductor ErNi2 B2 C goes superconducting at TC = 11 K,
and then develops incommensurate antiferromagnetic order below TM = 6 K as
shown in Fig. 5 [35]. The wave vector for the ordering is (h,0,0) with h ≈ 0.55, with
the spin direction transverse, along (0,y,0). Initially, the magnetic order exhibits a
1272 J. W. Lynn and B. Keimer
Fig. 5 (Top) Unpolarized neutron diffraction measurements along the (h,0,0) direction at 1.3 K,
2.4 K, and 4.58 K of a single crystal of ErNi2 B2 C. At 10 K no peaks are observed in this wave
vector range. The data have been offset along the intensity axis for clarity. Above the weak
ferromagnetic transition at 2.3 K the fundamental incommensurate peak is observed at h = 0.55,
along with higher odd-order harmonics. Below the ferromagnetic transition a new set of even-
order harmonics develops, indicated by the arrows. (Bottom) Schematic of the initial transversely
polarized spin-density-wave, and ground state square-wave. (Adapted from Ref. [35], © American
Physical Society 2001)
25 Magnetic Scattering 1273
Fig. 6 Polarized neutron diffraction measurements on a single crystal of ErNi2 B2 C showing both
the odd-order (5th) and even-order (16th) harmonics for the P||g configuration. The solid circles
(−, +) and solid triangles (+, −) are spin-flip scattering, while the open circles (+, +) and open
triangles (−, −) are non-spin-flip scattering. The data demonstrate that both types of reflections
are magnetic in origin, with the moment direction along the b axis. (Adapted from Ref. [35],
© American Physical Society 2001)
occurs in the cubic rare-earth (R) pyrochlore (R2 Ti2 O7 ) systems where the R ions
occupy corner-sharing tetrahedra [39]. For R = Ho, Dy, for example, the single-
ion anisotropy restricts the moments to point along diagonal (111) directions, along
lines that intersect the center of each tetrahedron. The ground state turns out to be
with two of the moments pointing into each tetrahedron and two pointing out. But
you do not know which two are in and which two are out, exactly like the hydrogen
bonding in ice where two H move into the oxygen in the center of the tetrahedron
and bond and two move out, resulting in a macroscopic degeneracy that violates the
third law of thermodynamics. The first measurement of the ground state correlations
was carried out for Ho2 Ti2 O7 , where the observed scattering from the correlated
moments agreed quite well with simulations [40]. An interesting simplification
occurs for a field applied along the (111) direction, which isolates the layers and
forms two-dimensional “kagomé spin-ice.” The scattering for this case is shown
25 Magnetic Scattering 1275
Fig. 7 Radially averaged small angle neutron scattering intensity of the vortex scattering in
ErNi2 B2 C vs wave vector K at 85 mT, above and below the weak ferromagnetic transition.
The shift in the peak position demonstrates that additional vortices spontaneously form as the
macroscopic magnetization develops at low temperatures. The temperature dependence shows that
this spontaneous vortex formation is directly related to the weak ferromagnetic transition. The inset
shows vortex Bragg peaks on the two-dimensional SANS detector; K = 0 is in the center. (Adapted
from Ref. [37])
in Fig. 8 for Dy2 Ti2 O7 , which shows the broad distributions of diffuse magnetic
scattering that are in excellent agreement with Monte Carlo simulations [41].
The ground state properties are not the only remarkable property of spin-ice,
as the magnetic excitations are equally fascinating. Theory showed that these
excitations, which simply consist of flipping one of the spins in a tetrahedron so
that you have three pointing out and one pointing in (and in the adjacent tetrahedron
three point in and one out), correspond to the creation of a magnetic monopole and
anti-monopole [42]. The subsequent motion of these particles is governed by the
Coulomb Hamiltonian for magnetic charges, and this scenario was subsequently
confirmed by neutron scattering measurements [43, 41, 44].
Advances in thin film deposition methods have facilitated the synthesis of com-
plex heterostructures with atomic layer accuracy, which has enabled investigators
1276 J. W. Lynn and B. Keimer
Fig. 8 (a) Neutron measurements of the diffuse magnetic scattering in the kagomé spin-ice
compound Dy2 Ti2 O7 at T = 0.43 K and B = 0.5 T. The sharp structural Bragg peaks, such as
(2,-2,0), are contained within one pixel and have been removed from the plot. (b) Monte Carlo
simulations of the expected scattering in this kagomé spin-ice state. The overall features are in
excellent agreement with the data. (Adapted from Ref. [41], © The Physical Society of Japan
2009)
Fig. 9 (a) Non-spin-flip polarized neutron reflectivity data R++ (red) and R− − (blue) on a
LaMnO3 /SrMnO3 multilayer, measured in a 675 mT field at 120 K. The inset shows a schematic
of the superlattice. (b) Magnetic depth profile determined by the fit to the data. Location of
the LaMnO3 (pink) and SrMnO3 (green) layers are shown. (c) Spin-flip intensity, showing the
antiferromagnetic peak and satellite peak. Inset shows the non-spin-flip scattering in the same
range. (Adapted from Ref. [45], © American Physical Society 2011)
1278 J. W. Lynn and B. Keimer
Fig. 10 Photon energy dependence of the (1, 0, 22) magnetic Bragg reflection at the L3 -(left) and
L2 -edges (right) of Sr2 IrO4 . The black lines show the x-ray absorption spectra for comparison.
(Reprinted with permission from Ref. [46], © American Association for the Advancement of
Science 2009)
25 Magnetic Scattering 1279
Fig. 11 Map of the resonant elastic X-ray scattering intensity at the (0, 0, 1) magnetic Bragg
reflection of La0.96 Sr2.04 Mn2 O7 at the Mn L3 -edge. The data indicate domains where the Mn spins
point in different directions in the MnO2 layers. (Reprinted with permission from Ref. [47], ©
American Physical Society 2013)
tation, allow magnetic X-ray scattering experiments with beam dimensions well
below typical magnetic domain sizes. Figure 11 provides an example of such an
experiment on the layered antiferromagnet La0.96 Sr2.04 Mn2 O7 , which comprises
alternately stacked sheets of ferromagnetically aligned Mn spins [47]. The (001)
1280 J. W. Lynn and B. Keimer
magnetic Bragg reflection of this spin array can be reached with photons tuned to
the Mn L3 -edge. The data shown in Fig. 11 were taken with a beam of 300 nm
diameter. They reveal that the diffracted intensity varies on a characteristic length
scale of several microns. A detailed analysis shows that the intensity variation results
from domains with different spin directions, which diffract photons with different
scattering amplitude due to the photon polarization dependence of the scattering
cross section (Eq. 11). In another study, domains with different helicities in a spiral
magnet were imaged by resonant diffraction with circularly polarized X-rays. The
spatial resolution and imaging capabilities of magnetic X-ray scattering methods
are expected to develop rapidly with the advent of coherent X-ray beams at fourth-
generation synchrotron sources.
In analogy to neutron reflectometry, polarized magnetic X-ray reflectometry has
recently developed into a powerful, element-sensitive probe of complex oxide thin
films, heterostructures, and superlattices. As an example, we discuss resonant X-
ray diffraction data on RNiO3 -based films and superlattices (where R denotes a
lanthanide atom). RNiO3 perovskites exhibit a Mott metal-insulator transition as
a function of the radius of the R cation, which modulates the Ni-O-Ni bond angle.
Recent work has shown that the metal-insulator transition can also be controlled
by epitaxial strain and by spatial confinement of the conduction electron system.
Antiferromagnetism with ordering vector g = (¼, ¼, ¼) develops in the Mott-
insulating phase. Figure 12 (top) shows azimuthal scans at the corresponding
magnetic Bragg reflection taken with photons tuned to the Ni L3 -edge [48]. The
data analysis demonstrates that the magnetic order is noncollinear, with Ni spins
forming a spiral propagating along the (111) direction of the perovskite unit cell.
The polarization plane of the spiral can be controlled by epitaxial strain.
Figure 12 (bottom) shows a contour map of the resonant scattering intensity from
a LaNiO3 -LaAlO3 superlattice as a function of the azimuthal angle and the momen-
tum transfer perpendicular to the superlattice plane [49]. Strong modifications of
the azimuthal-angle dependence of the intensity occur particularly under grazing-
incidence or grazing-exit conditions, where the incident or scattered beams are
strongly refracted at the external and internal interfaces of the superlattice. These
data illustrate the possibly important influence of dynamical effects in resonant
soft X-ray diffraction from thin-film structures, which go beyond the kinematic
approximation usually employed in the analysis of such data.
Very recently, X-ray free-electron lasers have enabled time-resolved resonant
magnetic diffraction experiments capable of imaging the real-time dynamics of
magnetic order under nonequilibrium conditions. As an illustration of this emerging
capability, Fig. 13 shows the time evolution of the g = (¼, ¼, ¼) antiferromagnetic
Bragg peak of a NdNiO3 film following a THz pump pulse exciting an infrared-
active phonon mode of the LaAlO3 substrate [50]. As the phonon propagates from
the substrate through the film, it obliterates the antiferromagnetic order in its wake
on a picosecond timescale. The mechanism underlying this “non-thermal melting”
phenomenon may involve transient distortions of the NiO6 octahedra, which weaken
the magnetic exchange interactions between Ni spins.
25 Magnetic Scattering 1281
Fig. 12 (Top left) Ni L3 -edge scans through the (¼, ¼, ¼) magnetic Bragg reflection of LaNiO3 -
LaAlO3 superlattices with different numbers of consecutive unit cells. The absence of the magnetic
Bragg peak in superlattices with three or more LaNiO3 layers indicates that the magnetic order in
the 2×2 superlattice is induced by spatial confinement of the conduction electrons. (Reprinted
with permission from Ref. [48]). (Top right) azimuthal angle dependence of the (¼, ¼, ¼)
magnetic Bragg peak of nickelate thin films and superlattices with simulations that rule out
collinear (CM) and favor noncollinear (NCM) magnetism. (Bottom) simulated contour map of
the scattering intensity of 2×2 LaNiO3 -LaAlO3 superlattice as functions of azimuthal angle
and momentum transfer perpendicular to the superlattice plane, demonstrating the importance of
dynamical diffraction effects. (Reprinted with permission from Ref. [49], © American Physical
Society 2016)
1282 J. W. Lynn and B. Keimer
Fig. 13 (a) Schematic illustration of the demagnetization process of a NdNiO3 film triggered
by a coherently excited phonon of the LaAlO3 substrate. (b) Depth profile of the (¼, ¼, ¼)
resonant magnetic Bragg peak intensity at different time delays between the phonon pump pulse
and the resonant X-ray diffraction probe measurement. (Reprinted with permission from Ref. [50],
©Springer Nature 2015)
There are many types of magnetic excitations and fluctuations that can be measured
with neutron scattering techniques, such as magnons, spinons, critical fluctuations,
crystal field excitations, magnetic excitons, and moment/valence fluctuations. We
start with classic magnons in an isotropic ferromagnet, where the excitations are
gapless and the dispersion relation is given by Eq. (12). Figure 14 (left) shows a
measurement for La0.67 Ca0.33 MnO3 , which is a colossal magnetoresistive (CMR)
material [51]. The data reveal two magnon peaks at a given wave vector, one in
energy gain where the neutron destroys a magnon and gains energy, and one in
energy loss where a magnon is created. This is a small q (long wavelength) excita-
tion, and in fact this sample is polycrystalline rather than single crystal, and the data
were collected around the (0,0,0) reciprocal lattice position. Such measurements are
restricted in wave vector and energy, and are only viable for isotropic ferromagnets;
otherwise the excitations fall outside the accessible experimental window dictated
by momentum and energy conservation. If there is a question of whether these
excitations are magnons or phonons, the polarized beam technique can be employed
as shown in Fig. 14 (right) for the prototypical isotropic ferromagnet amorphous
Fe86 B14 [52]. These data were taken with the neutron polarization P parallel to the
momentum transfer K (P||K), Eq. (13) with q = K. In this configuration magnons
require the neutron spin direction to reverse (spin-flip), while phonons can only be
observed in the non-spin-flip configuration. For magnons we should be able to create
25 Magnetic Scattering 1283
La0.67Ca0.33MnO3
1400 Horizontal Field Q=0.09 T=500K
–1 200 K
Q = 0.07Å
1200
300
1000 (+–)
(–+)
Counts/7 min.
Counts/30 min
800
200
600
400 100
200
0 0
–1.0 –0.5 0.0 0.5 1.0
–0.8 –0.6 –0.4 –0.2 0 0.2 0.4 0.6 0.8
Energy (meV) Energy (meV)
Fig. 14 Spin waves in isotropic ferromagnets. (Left) energy scan at a wave vector q of 0.07 Å−1
for La0.7 Ca0.3 MnO3 , (Reprinted with permission from Ref. [51], © American Physical Society
1996) showing the spin waves in energy gain (E < 0) and energy loss (E > 0). (Right) polarized
beam energy scan on the Fe86 B14 amorphous ferromagnet at a fixed wave vector of 0.09 Å−1 , with
the neutron polarization parallel to q. In this configuration spin angular momentum is conserved,
and the neutron can only create an excitation (E > 0) if its moment is initially antiparallel to the
magnetization, and can only destroy a spin wave (E < 0) when its moment is parallel. (Reprinted
with permission from Ref. [52], © American Institute of Physics 1996)
a spin wave only in the (− +) configuration where the incident neutron moment is
antiparallel to the magnetization; the scattered neutron moment is then parallel to
the magnetization direction, and the magnetization is decreased by one unit by the
creation of the magnon. On the energy gain side the process is reversed and we
destroy a magnon only in the (+ −) configuration. This is precisely what we see
in the data; for the (− +) configuration the spin waves can only be observed for
neutron energy loss scattering (E > 0), while for the (+ −) configuration spin waves
can only be observed in neutron energy gain (E < 0). This behavior of the scattering
uniquely identifies these excitations as magnons.
Expanding the sine in Eq. (12) we see that the small-q dispersion relation can
be written as Esw = D(T)q2 , where D is the spin wave “stiffness” constant. The
general form of the spin wave dispersion relation is the same for all isotropic
ferromagnets, a requirement of the (assumed) perfect rotational symmetry of the
magnetic system, while the numerical value of D depends on the details of the
magnetic interactions and the nature of the magnetism. The small-q dispersion
relation can be readily measured, as shown in Fig. 15 (left) for a single crystal of
La0.85 Sr0.15 MnO3 , and D(T) obtained [53]. The effect of temperature is to soften
the average exchange interaction as the magnetization decreases, and hence the
magnons renormalize to lower energies with increasing temperature as also shown
Fig. 15. With single crystals the dispersion curves can be determined in different
directions and throughout the Brillouin zone, as shown in Fig. 15 (right) for a
1284 J. W. Lynn and B. Keimer
La0.85Sr 0.15MnO 3
5
4 T = 10 K
Energy [meV]
T = 220 K
3
(a)
0
0 0.50 0.1 0.15 0.2 0.25 0.3 0.35
q (0, 0, ζ)
100
(b)
80
D010
D [meV Å2]
60 D 001
40
_ k T 5/2
20 Fit to D0{1 - ct. l2 ( ____
B
) ζ(5/2) }
4πD 0
Fit to a power law
0
0 50 100 150 200 250
Temperature [K]
Fig. 15 (Left) (a) Low energy spin wave dispersion relations at two different temperatures. The
dispersion relation follows a quadratic dependence expected for a ferromagnet, which defines the
spin stiffness D, and no significant gap in the excitation spectrum is observed indicating an isotropic
system. D(T) is shown in (b), which follows a power law behavior as the Curie temperature
is approached. (Reprinted with permission from Ref. [53], © American Physical Society 1998).
(Right) spin wave dispersion relations for a series of colossal magnetoresistive perovskite oxides.
(Reprinted with permission from Ref. [54], © American Physical Society 2006)
Fig. 16 (Left) intrinsic spin wave linewidths for the ground state magnetic excitations in
La0.85 Sr0.15 MnO3 . The linewidths are quite anisotropic, and are small at small wave vectors but
become very large at large q (Reprinted with permission from Ref. [53], © American Physical
Society 1998). (Right) magnon linewidths as a function of temperature for a series of q’s in the
insulating antiferromagnet Rb2 MnF4 , measured using the high resolution spin-echo triple-axis
technique. (Reprinted with permission from Ref. [55], © American Physical Society 2006). The
solid curves are calculations using spin wave theory
(right) shows the measured linewidths for the prototype insulating antiferromagnet
Rb2 MnF4 [55]. Here the spin-echo triple-axis technique has been employed, which
has extraordinarily good (μeV) resolution. The theoretically calculated linewidths
from spin-wave theory are shown by the solid curves at a series of temperatures, and
are in quantitative agreement with the data.
One area where neutron scattering has played an essential role is elucidating
the spin dynamics of the high temperature superconductors, first for the copper
oxide systems [56] and more recently for the iron-based superconductors [57]. The
magnetic excitations in these classes of materials extend to quite high energies –
as high as ≈0.5 eV – making the measurements particularly challenging since the
magnetic form factor requires that the magnitude of K must be kept small, neces-
sitating quite high incident energy neutrons. These requirements are well matched
to the time-of-flight capabilities of spallation neutron facilities where high energy
neutrons are plentiful. To illustrate the basic technique, consider the excitations from
BaFe2 As2 , which is one of the antiferromagnetic “parent” materials of the iron-
based superconductors. The antiferromagnetic ordering temperature TN = 138 K,
which corresponds to a thermal energy of just ≈12 meV (1 meV ➔ 11.605 K). Yet
we see from Fig. 17 that the magnons extend up to 200 meV, an order-of-magnitude
higher energies than the ordering temperature represents, indicating that the system
has a low-dimensional character [58]. The in-plane dispersion relations are also
quite anisotropic, even though the orthorhombic distortion away from tetragonal
symmetry (that accompanies the magnetic order) is small. Another very interesting
aspect of the magnetic excitations is that they have quite large linewidths at high
energies, indicating that the magnetic electrons are itinerant in nature. Indeed, the
1286 J. W. Lynn and B. Keimer
Fig. 17 (Left) constant-energy cuts of the magnetic excitations in BaFe2 As2 at a series of
energies. The solid curves are the fits to a spin wave model. (Right) spin wave dispersion along the
(1, K) direction as determined by energy and Q cuts of the raw data. The solid curve is a Heisenberg
model calculation using anisotropic exchange couplings. The dotted line is a Heisenberg model
calculation assuming isotropic exchange coupling. (Adapted from Ref. [58], © American Physical
Society 2011)
iron d-bands where the magnetism originates cross the Fermi energy – the definition
of itineracy.
Our final neutron example concerns the spin dynamics of one-dimensional (1D)
magnets, which (together with 2D magnets) have played a special role in developing
a fundamental understanding of quantum magnetic systems. This is because they
are more tractable theoretically and therefore enable a deeper comparison with
experiment. They also entail the emergence of new types of cooperative states and
their associated excitations. A classical case is the spin one-half antiferromagnet
chain, where quantum effects are maximal, represented by materials such as KCuF3
[59] and CuSO4 ·5D2 O [60], which have enjoyed a long and interesting history of
investigations. The ground state turns out to be an entangled macroscopic singlet,
but where the two-spin correlation function decays only algebraically, rendering
long lengths of the chain to be correlated antiferromagnetically. The fundamental
excitations of such a 1D system are spinons in these (isolated) spin chains, which
can be considered to a first approximation as moving domain walls. Measurements
of the dynamic structure factor for CuSO4 ·5D2 O are shown in Fig. 18 [60].
Spinons carry fractional spin, and hence these fractionalized excitations can only
be created in pairs in the scattering process. Thus the lower energy part of the
spectrum corresponds to two-spinon excitations and has the appearance of a simple
antiferromagnetic spin wave dispersion relation. However, only 71% of the spectral
weight is contained in this two-spinon component, with essentially all the remainder
being accounted for by the four-spinon contribution. Precise calculations of the
25 Magnetic Scattering 1287
0.1
w
0.0 0.0
Fig. 18 Intensity color maps of the experimental inelastic neutron scattering spectrum measured
along the Cu chain in CuSO4 ·5D2 O are shown in the left, compared with the theoretical two-
and four-spinon dynamic structure factor. (Reprinted with permission from Ref. [60], © Springer
Nature 2013)
dynamic structure factor for two-spinon and four-spinon scattering are also shown
in Fig. 18, which account for essentially the entire measured spectral weight, and
are in excellent agreement with the measurements [60].
The set of materials investigated by high-resolution RIXS is thus far mostly limited
to magnets with characteristic exchange interactions of the order of 100 meV.
A milestone was set by early experiments on La2 CuO4 , the antiferromagnetic,
Mott-insulating end member of a family of high-temperature superconductors,
which exhibits an exceptionally large magnon bandwidth of ≈300 meV. A RIXS
spectrometer with energy resolution of E ≈ 100 meV proved to be capable of
separating these excitations from the elastic line over a substantial fraction of the
Brillouin zone (Fig. 19) [22, 23]. Comparison with prior inelastic neutron scattering
data on the same materials demonstrated that the RIXS excitation features indeed
originate from single antiferromagnetic magnons.
RIXS experiments have also revealed the persistence of high-energy paramagnon
excitations in highly doped, superconducting cuprates. Based on the polarization
dependence of the scattering cross section at specific scattering geometries, they can
be separated from charge excitations, as shown in Fig. 20 for YBa2 Cu3 O6 + x [29].
The measurements are complementary to inelastic neutron scattering experiments,
which have much higher energy resolution and can therefore access spin excitations
with energies from 1 to 100 meV, comparable to the superconducting energy
gap. The RIXS measurements, on the other hand, are more sensitive to high-
energy excitations, which can also be investigated with high energy neutrons from
spallation sources. The photon energy dependence of the RIXS intensity yields
1288 J. W. Lynn and B. Keimer
20 Cu L3 T = 15 k 300
Energy (meV)
q = +1.885 RIXS
//
B 200
930 932
Photon energy (eV)
10
D LCO 100
C A T = 15 k
0
0
1.0 0.5 0.0 –3 –2 –1 0 1 2 3
Energy loss (eV) q
//
Fig. 19 (Left) RIXS profile of La2 CuO4 taken at the Cu L3 edge with ≈100 meV energy
resolution. The spectrum can be decomposed into elastic (A), single magnon (B), multiple magnon
(C), and optical phonon (D) components. The inset shows the X-ray absorption spectrum near
the Cu L3 edge, the arrow marks the energy of the incident photons. (Right) single magnon
dispersion determined by RIXS (blue dots), compared to inelastic neutron scattering data (dashed
line). (Reprinted with permission from Ref. [23], © American Physical Society 2010)
additional insight into the nature of these excitations. Whereas the spin excitation
energy is independent of photon energy, as expected for collective modes, the
spectral weight of the charge excitations shifts upon detuning the photon energy
away from the L-edge resonance, signaling a broad excitation continuum. This
supports models that treat collective spin excitations as mediators of unconventional
superconductivity.
Hard X-ray RIXS experiments on the layered iridates have revealed magnon
dispersions remarkably similar to those of the cuprates – a finding that has fueled
predictions of unconventional superconductivity in the iridates. In addition to the
usual low-energy magnon branches emanating from the antiferromagnetic Bragg
reflections, these experiments have also revealed weakly dispersive “spin-orbit
exciton” modes corresponding to spin excitations from the Jeff = ½ ground state
into the Jeff = 3/2 excited state (Fig. 21) [27]. Since the dispersion of these modes is
controlled by the combination of the intra-atomic spin-orbit coupling, the crystalline
electric field, and the inter-atomic exchange interactions, RIXS experiments are an
incisive probe of the low-energy electronic structure of these materials.
Finally, to illustrate the diversity of inelastic X-ray scattering methods applied
to magnetism, we highlight results of an X-ray emission spectroscopy study of iron
arsenide superconductors of composition Ca1-x Rx Fe2 As2 (where R = rare earth)
[61]. The goal of this experiment was to elucidate the origin of a pressure-induced
structural phase transition from an antiferromagnetic to a nonmagnetic state that is
associated with a large volume reduction [62, 63]. To measure the local magnetic
moment of the Fe ions independent of any inter-atomic correlations, X-ray photons
were tuned to the Fe K-absorption edge (1 s-3d), and the spectrum of emitted X-rays
was monitored around the dipole-active Kβ emission line (2p-1 s). A local moment
on the Fe site induces a splitting of this line (inset of Fig. 22) whose size depends
25 Magnetic Scattering 1289
Fig. 20 Photon energy dependence of the RIXS intensity (a, b) for undoped antiferromagnetic
YBa2 Cu3 O6.1 and (c, d) superconducting Ca-substituted YBa2 Cu3 O7 in polarization geometries
that predominantly select spin (a, c) and charge (b, d) excitations. The horizontal dashed lines
highlight the energy independence of the magnetic peak position, while the dashed green line is a
guide to the eye underlining the fluorescence behavior of the continuum of charge excitations from
the doped holes. (Reprinted with permission from Ref. [29], © American Physical Society 2015)
A list of current neutron scattering facilities around the world can be found at
(http://en.wikipedia.org/wiki/Neutron_research_facility). Numerical values of the
free-ion magnetic form factors for neutrons can be obtained at https://www.ill.eu/
sites/ccsl/ffacts/ffachtml.html. Values of the coherent nuclear scattering amplitudes
and other nuclear cross sections can be found at http://www.ncnr.nist.gov/resources/
n-lengths/.
1290 J. W. Lynn and B. Keimer
Fig. 21 (Top) the spin-orbital level scheme of Sr2 IrO4 . The spin-orbit coupling λ splits the
d-electron manifold into Jeff = 1/2 and 3/2 multiplets. The crystal field lifts the degeneracy
of the Jeff = 3/2 multiplet. Orange (blue) colors in the images of the orbitals represent spin up
(down) projections. (Bottom) dispersion of magnons and spin-orbit excitons (marked with QP for
“quasiparticle”) extracted from RIXS data at the Ir L-edge. (Reprinted with permission from Ref.
[27], © Springer Nature 2014)
Fig. 22 Fe Kβ emission spectra of Ca1-x Rx Fe2 As2 with R = Nd, and difference spectrum with
FeCrAs where Fe is in a nonmagnetic spin-0 state. The difference spectrum indicates a splitting of
the emission line due to a local magnetic moment on the Fe site (inset). (Reprinted with permission
from Ref. [61], © American Physical Society 2013)
Energy Units: Traditionally magnetic excitations are quoted in units of meV but
sometimes authors use THz, particularly for phonons in older literature. Raman
and IR experimenters often use cm−1 . 1 meV ➔ 0.24180 THz ➔ 8.0655 cm−1
➔ 11.605 K.
For a wavelength λ = 1.54 Å the photon energy is 8.05 keV, the electron energy
is 63.4 eV, and for a neutron the energy is 34.5 meV.
In this review we have discussed the basic characteristics of magnetic neutron and
X-ray scattering and provided a number of experimental examples of how these
techniques can be employed. Neutron scattering is a rather mature technique which
has the advantage of being a weakly interacting probe that does not affect the
properties of the sample. The source of neutrons has traditionally been steady-state
reactor-based facilities, but this has now been complemented by the newer, pulsed
spallation neutron source facilities which can offer higher peak flux than steady-
state reactors. Both types of sources have many different types of spectrometers that
enable magnetic investigations over many orders-of-magnitude in both spatial and
1292 J. W. Lynn and B. Keimer
time domains. In addition to new sources and new types of sources, many of the
advancements in neutron techniques over the years have come from developments
in how to tailor and manipulate neutrons, vast arrays of detectors, and the software
to analyze and visualize the data, and this progress continues unabated. New sources
and new instrumentation currently are being planned and developed, with the
anticipation that measurement capabilities will be greatly increased together with
an increased quantity and scale of data acquired.
Resonant X-ray scattering is a much newer technique, with high brightness that
allows measurements of small bulk samples, thin films, and multilayers. It also has
the advantage of being element-specific as the resonance is tuned to an absorption
edge. Tremendous progress in measurement capabilities has been realized in the
last few years, both with magnetic diffraction and magnetic inelastic scattering.
In contrast to neutron scattering which is on a solid theoretical foundation,
the theoretical understanding and interpretation of magnetic X-ray scattering is
undergoing considerable development, which should lead to improved interpretation
of experimental data and exciting new capabilities.
The future of both techniques is brilliant, pun intended.
Acknowledgments We thank our many colleagues who have collaborated with us on our own
projects, where we have taken a number of the examples for our own convenience and familiarity
with the systems.
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024525 (2012)
Jeffrey Lynn received his Ph.D. in 1974 from Georgia Tech while
conducting his thesis research at Oak Ridge National Laboratory.
He was a postdoctoral Fellow at Brookhaven National Laboratory,
before becoming Professor of Physics, University of Maryland
and consultant at the National Bureau of Standards (now NIST).
Currently he is a NIST Fellow and Adjunct Professor in the
Quantum Materials Center at the University of Maryland.
1296 J. W. Lynn and B. Keimer
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1298
Magnetic Resonance of Electrons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1299
Microscopic Equation of Motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1299
Macroscopic Equation of Motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1301
On the Difference Between EPR and FMR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1302
Electron Paramagnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1303
Bloch Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1303
Effective Spin Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1304
Anisotropic Zeeman Interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1306
Fine Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1308
Hyperfine Interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1310
Ferromagnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1312
Effective Magnetic Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1312
Shape Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1314
Magnetocrystalline Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1316
Exchange Energy and Spin Wave Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1317
FMR in Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1319
Experimental Observation of Electron Magnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . . . 1321
Frequency Domain Cavity EPR/FMR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1321
Survey of Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1324
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1329
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1329
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1331
D. Menard ()
Department of Engineering Physics, Polytechnique Montreal, Montréal, QC, Canada
e-mail: [email protected]
R. Barklie
School of Physics, Trinity College, Dublin, Ireland
Abstract
This chapter presents the principles and practice of electron paramagnetic reso-
nance (EPR) and of ferromagnetic resonance (FMR). In spite of their common
physical origin and experimental methods, EPR and FMR are rarely presented
together. The combined treatment emphasizes their similarities and differences.
EPR is treated quantum mechanically in terms of transitions between energy
levels, exploiting the concepts of effective spin Hamiltonian and a rotating frame
of reference. FMR uses a macroscopic method to describe quasi-rigid macro-
scopic magnetization with precessional motion around an effective magnetic
field. Both approaches involve phenomenological parameters in a mathematical
form consistent with the symmetry of the interactions. The parameters, which
can be calculated theoretically in principle, are often determined experimentally
by fitting the angle-dependent data to the calculated phenomenological response.
The classical methods of observing EPR and FMR are presented, along with a
survey of alternative complementary techniques.
Abbreviations
AFC Automatic frequency control
AWG Arbitrary waveform generator
CPW Coplanar waveguide
CW Continuous wave
EDMR Electrically detected magnetic resonance
ENDOR Electron nuclear double resonance
EPR Electron paramagnetic resonance
FMR Ferromagnetic resonance
GMI Giant magnetoimpedance
HF Hyperfine
LLG Landau-Lifshitz-Gilbert
LNA Low-noise amplifier
NMR Nuclear magnetic resonance
ODMR Optically detected magnetic resonance
PIMM Pulsed inductive microwave magnetometry
PSD Phase-sensitive detection
SHE Spin Hall effect
SHF Super hyperfine
TR-MOKE Time-resolved magneto-optical Kerr effect
TWTA Traveling-wave tube amplifier
VNA Vector network analyzer
Introduction
The observation of nuclear magnetic resonance (NMR) [1, 2], electron paramagnetic
resonance (EPR) [3, 4], and ferromagnetic resonance (FMR) [5] was reported in the
mid-1940s, following declassification of radar and microwave research that took
place during World War II. By 1950, most of the underlying physical principles
of the three resonance phenomena were well understood, except for the detailed
26 Electron Paramagnetic and Ferromagnetic Resonance 1299
relaxation mechanisms leading to resonance line broadening. From there on, the
three domains have evolved into distinct communities, gradually developing their
own languages, formalisms, and powerful characterization techniques associated
with various areas of physics, chemistry, and materials sciences.
This chapter gives a brief, simplified account of the principles and practice
of EPR and FMR spectroscopy. Comprehensive accounts are provided in several
excellent EPR [6–10] and FMR [11–13] textbooks. Our aim is to explain the
occurrence of electron magnetic resonance in paramagnetic and ordered materials,
highlighting the common physical origin and the distinct formalism of the two
methods. We do not cover the relaxation mechanisms responsible for the resonance
linewidth, for reasons of conciseness. References are kept at a minimum, mostly
focusing on textbooks and review chapters.
which can be rewritten using the commutation relations for angular momentum [8]:
d μ̂
= − |γ | μ̂ × B 0 . (3)
dt
The absolute value for the gyromagnetic ratio has been chosen to remove any
ambiguity on the sign of γ , as both signs are used in the literature. Solutions of (3)
describe a classical precession of the moment μ around B0 at an angular frequency:
ω0 = |γ | B0 , (4)
also called the Larmor frequency. Alternatively, (3) may be obtained by combining
the classical equation of motion (with J in units of ) dJ/dt = μ × B0 with the
relation μ = γ J leading to the same equation of motion, provided one replaces the
expectation value by a proper statistical average.
It is common practice in EPR and NMR to employ an alternative coordinate sys-
tem, rotating
at an angular frequency
around the z axis, such that (3) transforms
into d μ̂ /dt = (|γ | B 0 − ) × μ̂ [8]. As a result, in the rotating frame, the
magnetic moment precesses around the effective field B e = (B0 − / |γ |) ẑ and
remains fixed for = ω0 . By including a microwave field B1 alongside B0 in the
Hamiltonian, where B1 is circularly polarized at right angles to B0 and oscillating at
a frequency of ω0 , so that B1 is fixed in the frame of reference rotating at = ω0 ,
the solution of (2) or (3) yields a periodic oscillation of μ around B1 , called Rabi
oscillations, at a frequency of ω1 = |γ |B1 in the rotating frame of reference.
Quantum mechanics shows that the effect of the B0 field is to split the degenerate
ground state of the system into 2MJ + 1 equally spaced energy levels, separated by
1
N
M= μi , (6)
V
i=1
dM
= − |γ | M × B eff − R, (7)
dt
(Mz − M0 ) ẑ Mx x̂ + My ŷ
RB = + , (8)
T1 T2
usually associated with NMR and EPR studies, and the Gilbert relaxation term,
α dM
RG = M× , (9)
Ms dt
mostly used for FMR. We discuss them further in Sects. “Electron Paramagnetic
Resonance” and “Ferromagnetic Resonance”.
EPR and FMR are both related to electron resonance: in paramagnetic substances
for EPR and in materials with magnetic order for FMR. Both are based on the same
physics, as described by (7), and can be observed with the same experimental setup.
What differentiates EPR and FMR is the nature and magnitude of the interactions
experienced by the elementary moments, as phenomenologically included in the
effective fields in (7). Historically, their practitioners adopted their own theoretical
formalisms to treat these interactions: for EPR microscopically in terms of an
effective spin Hamiltonian (Sect. “Electron Paramagnetic Resonance”) and for
FMR by exploiting a macroscopic micromagnetic free energy (Sect. “Ferromagnetic
Resonance”).
The usual aim of an EPR experiment is to obtain information about the nature
and population of paramagnetic centres by inducing magnetic dipole transitions
between the energy levels. These are associated with the local environment of the
magnetic moment, including the presence of nearby nuclear spins or interaction
with the crystal field. A resonant centre may be an impurity atom, a free radical, or
a defect such as a vacancy; these are often referred to as point defects since they have
zero dimension. The local environment provides small perturbations of the energy
levels with respect to that of the isolated moment. The information about the centres
is extracted from the number and positions of the resonance lines, as well as their
shapes and linewidths.
In FMR studies, the specimen may be viewed as an ensemble of magnetic
moments locked together by the strong, short-range, exchange coupling. As such,
they tend to precess together as a large macrospin in an effective mean field.
The interactions of the moments with their environment are no longer small
perturbations, as they often result in effective fields far greater than the applied
fields. Exchange and dipolar interactions also give rise to a rich spectrum of spin
wave excitations. The resonance positions and linewidths enable us to probe spin
wave excitations and magnetization dynamics, and they may serve as chemical and
structural characterization parameters.
26 Electron Paramagnetic and Ferromagnetic Resonance 1303
Bloch Equations
The combination of (7) and (8), which was used by Bloch [14] to discuss early
NMR experiments, will be referred to as the Bloch equations. In (8), M0 represents
the thermal equilibrium value of the magnetization. The spin-lattice relaxation time,
T1 , is therefore associated with the relaxation of the longitudinal component of the
magnetization toward thermal equilibrium, whereas the spin-spin relaxation time,
T2 , describes the loss of coherence of the transverse components. As noted by Pake
and Estle [8], these equations give the simplest description for magnetic resonance
when relaxation is included, although, as they point out, many paramagnetic
samples will not obey these equations. They are useful because their solutions
provide a guide to understanding what often happens and they introduce the
important concepts of dispersion and absorption.
As a quick primer to EPR, let us consider the time dependence of the magneti-
zation in a continuous wave (CW) experiment as described by the Bloch equations.
Solving (7) combined with (8), when the effective field reduces to the applied field,
B(t) = B0 ẑ + B1 e−iωt x̂, yields [8]
μ0 M⊥ = χ − iχ B1 , (10)
where
(ω0 − ω) ωM T22
χ = , (11)
1 + (ω0 − ω)2 T22 + ω12 T1 T2
ωM T 2
χ = , (12)
1 + (ω0 − ω)2 T22 + ω12 T1 T2
Applied field
ωχ B12
P = . (14)
μ0
Equation (12) shows that χ , and hence P, has a Lorentzian shape with a
maximum at ω = ω0 , given by
ωM T2
χmax = , (15)
1 + ω12 T1 T2
This shows that P initially increases as B1 increases but that saturation occurs
when ω12 T1 T2 1. In the absence of saturation, for small values of B1 , such that ω1
is small compared to relaxation rates , that is, ω12 T1 T2 1, we see that Mz M0 ,
the linewidth simplifies to ΔB1/2 = 2/|γ |T2 , and the maximum of value of χ at ω0
= ω T . Another important result, as noted elsewhere [9], is that,
is given by χmax M 2
in the absence of saturation, the area under the χ curve is independent of T1 and T2
and is proportional to M0 and, hence, to the number of spins per unit volume, N/V.
The EPR spectrum of a single isotropic line with the free electron g-value of
2.002319 is rarely observed. Instead EPR spectra frequently display one or more
lines whose field positions depend on the direction of the applied magnetic field
26 Electron Paramagnetic and Ferromagnetic Resonance 1305
relative to the sample. The aim of this section is to describe several interactions
which give rise to these effects, to show how the relevant parameters may be
extracted from the spectra, and to explain what these reveal about the nature of
the centres.
The field positions of the lines in the spectra come from the resonance condition
ω = ΔE, where ΔE is the energy difference between each pair of levels between
which an electron magnetic dipole transition can occur and ω is the microwave
angular frequency of B1 . To find ΔE, it is necessary to determine the expressions
for the appropriate energy levels. We are primarily interested in energy levels close
to the ground state, since the photon energies used for achieving EPR are usually
only a few cm−1 (on the order of μeV), whereas the ground states are separated
from other excited states by energies much greater than this.
We often refer to this group of states as the ground manifold. As they transform
like spin angular eigenfunctions, we associate an effective spin S̃ to the ground
manifold to represent the behavior of this group of states when a magnetic field is
applied. This is a fictitious spin angular momentum such that the degeneracy of this
group of levels is set equal to (2S̃ + 1). The Hamiltonian operator associated with
this effective spin is called the effective spin Hamiltonian. S̃ may sometimes be the
true spin S, and in what follows we shall continue the usual practice of omitting the
difference between S̃ and S and refer only to the spin Hamiltonian, even though an
orbital component may contribute to it.
Hence, the energy levels appropriate to EPR are the eigenvalues of the eigen-
functions of the relevant spin Hamiltonian. A general and practical form for the spin
Hamiltonian is given by [8]
ĤZ = μB S · g · B 0 , (19)
ĤFS = S · D · S (20)
is associated with the fine structure interaction, where D is the fine structure tensor,
and the other terms, which contain the nuclear spin operator I,
characterize the hyperfine structure, where the A tensor is associated with the
magnetic hyperfine interaction; the second term accounts for the Zeeman splitting
of the nuclear spin and the last one for the nuclear electric quadrupole interaction.
1306 D. Menard and R. Barklie
The appropriate form of the spin Hamiltonian (18–21) is specific for each system.
It is possible in principle to calculate its mathematical form, using perturbation
theory or other means, but it is often more convenient and quicker to work with
the phenomenological expression, which covers a majority of the cases encountered
in practice. Simplifications arise by choosing parameters compatible with the
symmetry of the system under study, and the actual values of those parameters
are then deduced from the EPR spectra. In what follows, we discuss how the
characteristics of the EPR spectra are determined by the Zeeman, fine structure, and
hyperfine structure interactions; the description of the nuclear electric quadrupole
interaction and its effect on the EPR spectrum can be found elsewhere [6–9].
Unlike the electron Zeeman interaction of a free electron treated in Sect. “Bloch
Equations”, for most paramagnetic centres, the interaction depends also on the
direction of the field with respect to certain axes defined by the local symmetry
of the centre. In these cases, the Hamiltonian is given by (19), and the g tensor,
represented by a 3 × 3 matrix, reflects the local symmetry of the centre. In most
practical cases, by choosing suitable axes x, y, z, known as the principal axes, the
tensor becomes diagonal, yielding
ĤZ = μB gxx Sx Bx + gyy Sy By + gzz Sz Bz . (22)
E = gμB B0 MS (23)
where
g= 2 α2 + g2 α2 + g2 α2.
gxx x yy y zz z (24)
ω
B0 αx , αy , αz = . (25)
2 α + g2 α + g2 α
μB gxx x yy y zz z
26 Electron Paramagnetic and Ferromagnetic Resonance 1307
J (J + 1) + S (S + 1) − L (L + 1)
gJ = 1 + (26)
2J (J + 1)
that differs significantly from ge . For instance , an atom with a single unpaired
electron in the p shell with L = 1, S = 1/2 would have g = 2/3 and g = 4/3 for
the 2 P1/2 and 2 P3/2 states, respectively. However, when such an atom is within a
solid, the orbital contribution to the magnetic moment is often largely removed,
and the moment arises almost entirely from the electron spin. This quenching of the
angular momentum arises because it is energetically favorable for the electrons to be
in states where they avoid any negatively charged ions or ligands as far as possible.
As an example, Spaeth, Niklas, and Bartram [9] considered an atom with one
unpaired outer p electron (an L = 1, S = 1/2 state) at a site of orthorhombic
symmetry, in which the appropriate atomic states are |px , |py , |pz states with
energies changed by −, 0, + , respectively, as a result of the electrostatic
interaction with the ions. The ground state, relevant for EPR, is |px , and as this
has no orbital angular momentum, the g-value might be expected to be equal to ge .
However, this ignores the admixture of the excited states into the ground state as a
Fig. 3 (a) Zeeman split energy levels as a function of applied magnetic field and (b) angular
dependence of the resonance line position as a function of field angle θ for an S = 1/2 centre with
axial g tensor
1308 D. Menard and R. Barklie
result of the spin-orbit interaction operator λL · S. The admixture is such that there
remains a small orbital contribution to the magnetic moment. Using perturbation
theory, they showed that [9]
λ 2λ
gxx = ge , gyy = ge − , gzz = ge − , (27)
where terms in (λ/Δ)2 are neglected (it is assumed that λ Δ). In general, as
shown elsewhere [7],
G| Li |n n| Li |G
gij = ge δij − 2λ . (28)
En − EG
n=G
Fine Structure
When a paramagnetic centre has S > 1/2, there may be an interaction called the fine
structure (FS) interaction which leads to additional zero-field splitting of the energy
levels (no applied magnetic field). This can lead to extra lines in the EPR spectrum.
Since for S > 1/2 there is more than one unpaired electron, it is to be expected that
magnetic dipole-dipole interactions between them will occur. However, the situation
can be complicated as the electrical crystal field and spin-orbit interaction may play
a role too; a comprehensive treatment is given by Abragam and Bleaney [6]. An
excellent introduction to this topic is given by Spaeth, Niklas, and Bartram [9].
To illustrate the effect of the FS interaction, let us consider the case where the
paramagnetic centre has S > 1/2 and is in a site of less than cubic symmetry. We
assume a spin Hamiltonian of the form
ĤS = μB S · g · B + S · D · S. (29)
26 Electron Paramagnetic and Ferromagnetic Resonance 1309
With respect to the principal axes x, y, z of the tensor D , the FS term becomes
ĤFS = Dxx Sx2 + Dyy Sy2 + Dzz Sz2 . The trace of D is usually set to 0 since this does
not affect the EPR spectrum. This gives
1
ĤFS = D Sz2 − S (S + 1) + E Sx2 − Sy2 , (30)
3
where D = 32 Dzz is the axially symmetric part and E = 12 Dxx − Dyy represents
the deviation from axial symmetry.
If, to further simplify , the symmetry is axial
(axis//z), g is isotropic, and ĤZ ĤFS , then to first order in perturbation theory,
the energy levels are given by
1 1
E = gμB B0 MS + D 3cos2 θ − 1 MS2 − S (S + 1) , (31)
2 3
where θ is the angle between B0 and z. In this strong field limit, the eigenfunctions
are |MS . Considering S = 1, MS = −1, 0, 1, and the strongly allowed transitions
for ΔMS = ± 1, an EPR spectrum at a constant frequency yields two lines at field
values given by
ω D
B0 = ± 3cos2 θ − 1 , (32)
gμB 2gμB
Fig. 4 (a) Energy levels for an S = 1 system as a function of applied field at θ = 0, with zero-
field splitting of D. The two transitions at fixed frequency correspond to the two resonance fields.
(b) Angular dependence of the two resonances which coincide at θ c = 54.74◦
1310 D. Menard and R. Barklie
Hyperfine Interaction
The interaction between the magnetic moment of the unpaired electron (or hole)
of a paramagnetic centre and that of its central nucleus is called the magnetic
hyperfine (HF) interaction. When the interaction is with the magnetic moment of
a neighboring nucleus, it is known as the superhyperfine (SHF) interaction. The
nuclear Zeeman interaction must also be included. Referring to (21), without the
quadrupole term, and assuming an isotropic nuclear Zeeman effect, which is the
most frequently encountered, the spin Hamiltonian including HF interaction is given
by
ĤS = μB S · g · B 0 + S · A · I − gn μn I · B 0 . (33)
E = gμB B0 MS + KM S MI , (34)
where the nuclear quantum numbers are MI = {−I, . . . , I − 1, I}, the angle-
dependent g factor is given by (24), and
2 α 2 + A2 g 2 α 2 + A2 g 2 α 2
A2xx gxx x yy yy y zz zz z
K= . (35)
2 α2 + g2 α2 + g2 α2
gxx x yy y zz z
ω K
B0 = − MI . (36)
gμB gμB
Therefore, the presence of an HF interaction is revealed by the fact that there are
2I + 1 lines with equal spacing to first order in K/gμB B0 . Inclusion of second-
order terms makes the spacing depend slightly on MI . The generalization to axial
1/2
symmetry is straightforward by using as previously g = g
2 cos2 θ + g⊥ 2 sin2 θ
26 Electron Paramagnetic and Ferromagnetic Resonance 1311
1/2
and K = g −1 A2
g
2 cos2 θ + A2⊥ g⊥ 2 sin2 θ . In the isotropic case, g and K = A
become scalars.
A further characteristic of such spectra, for interaction with a single nucleus, is
that all the lines have very nearly the same intensity. This occurs because, under
normal conditions of applied field and temperature, the populations of the 2I + 1
different nuclear spin states are almost equal. However, if there are N equivalent
nuclei, each of spin I, there will be 2NI + 1 lines with intensity ratios reflecting the
probability of occurrence of each value of magnetic field produced by the nuclear
moments and experienced by the unpaired electron. For example, for N = 2 and
I = 1/2, there will be three lines reflecting the three field values associated with the
nuclear spin states |↑↑, |↑↓, |↓↑, |↓↓ with relative intensities 1:2:1; the field
produced by both states |↑↓ and |↓↑ is zero.
Let us treat the nuclear Zeeman interaction by adding the third term in (33),
which was neglected before. Assuming orthorhombic symmetry, we can write to
first order, if the nuclear Zeeman effect is small compared to the HF term [8]
Axx gxx αx2 + Ayy gyy αy2 + Azz gzz αz2
E = gμB B0 MS + KM S MI − gn μn B0 MI ,
Kg
(37)
where K is given by (35) and g by (24). Likewise, if the Zeeman effect is larger than
the HF splitting, we obtain
Axx gxx αx2 + Ayy gyy αy2 + Azz gzz αz2
E = gμB B0 MS − gn μn B0 MI + MS MI .
g
(38)
Ferromagnetic Resonance
FMR spectra typically look like a broad and high-intensity EPR single peak, with
comparatively strong anisotropy. In his initial experimental observation of FMR
absorption, Griffiths [5] reported resonance conditions significantly far from those
expected from the Larmor frequency. Kittel [15] is usually credited with the proper
explanation, highlighting the important role of the dipolar interaction leading to
strong shape anisotropy and demagnetizing effects. Kittel’s macroscopic approach
also includes effective fields associated with magnetocrystalline anisotropy.
As shown by Van Vleck, the microscopic quantum mechanical approach is,
within a reasonable approximation, equivalent to Kittel’s macroscopic phenomeno-
logical picture [16]. In his own words: “It is both an element of strength and
weakness in Kittel’s macroscopic method of handling the phenomenological energy
of anisotropy by means of an effective field that it frees one from the necessity of
specializing the model.” Also, the relaxation times involved in FMR are usually too
short to expect any significant Rabi oscillations of the longitudinal component of
the magnetization between the up and down states at a frequency of ω1 = |γ |B1 , as
discussed in Sect. “Microscopic Equation of Motion”. A small-response linearized
solution of (7) is usually fully justified.
It is common practice nowadays, in FMR studies, to use the Landau-Lifshitz-
Gilbert (LLG) equation, which is a combination of (9) and (7). Assuming that
the Gilbert parameter α is a constant (9) implies that the magnetization remains
constant in amplitude (but not in direction), so it describes the relaxation of a rigid
magnetization. This macrospin-like behavior is to be expected in ferro- and ferri-
magnetic materials due to strong exchange coupling, which tends to lock the relative
orientation of the moments together. It is also consistent with a viscous damping
proportional to the resonance frequency, another feature generally observed in
FMR experiments. Quenching of orbital angular momentum, as described in Sect.
“Anisotropic Zeeman Interaction”, is also quite effective in 3D ferromagnets,
leading to g-factor value of approximately 2 or equivalently to a gyromagnetic
ratio of approximately 28 GHz/T. Due to small spin-orbit corrections, the g-factor
value is in fact typically between 2.1 and 2.2 for most 3d-based materials, and it is
considered isotropic.
The macroscopic method is similar to the use of the spin Hamiltonian, previously
described for EPR. The macroscopic ground state is first calculated by minimizing
the magnetic part of the macroscopic free energy of the spin system, in the presence
of a static magnetic field, followed by calculating the linear response of (7) to a
microwave field excitation. The magnetic free energy, assuming, for the moment, a
single ferromagnetic domain with average uniform magnetization M, is
UZ = −M · B 0 , (40)
analogous to (19), where B0 is the applied static field. The second term,
μ0
UMS = M · N · M, (41)
2
is the magnetostatic energy arising from the dipolar interaction between the spins, in
which N is the demagnetizing tensor. In contrast with EPR, the dipolar interaction
between the spins leads to a much stronger and sample-shape-dependent magnetic
anisotropy.
The other terms in (39), which are not associated with Maxwellian fields like
the first two, are due to other spin-spin or spin-orbit interactions and lead to
effective magnetic anisotropy fields, discussed further below. Here we separate the
magnetoelastic anisotropy term, UME , arising from external stress from the intrinsic
magnetocrystalline anisotropy term, UA .
Minimizing Utot (ϕ , θ ) with respect to the rigid magnetization orientation leads
to its equilibrium position, from which an effective field
∂U
B eff = − , (42)
∂M
can be calculated and used in (7), which is then solved assuming that the dynamic
parts of M and Beff are much smaller than their static parts (the linear approxima-
tion).
As a simplified example, consider an isotropic sample, magnetically saturated
along the z axis. Assuming B = B0 ẑ + μ0 he−iωt and M = M0 ẑ + me−iωt , where b
and m are small dynamic components of the fields perpendicular to z, (7) combined
with (9) leads to first order to a transverse susceptibility
mx χ −iκ hx
= , (43)
my iκ χ hy
where
ωM ω̃H ωM ω
χ= , κ= 2 , (44)
ω̃B − ω
2 2 ω̃B − ω2
and
ωM = |γ | μ0 M0 , (45)
are in units of angular frequency. Equation (43) describes the response of the
dynamic magnetization to an internal dynamic field, exhibiting the characteristic
resonant response shown in Fig. 1, at the Larmor frequency ω0 . The main difference
with the isotropic EPR response of Sect. “Bloch Equations” is the use of a Gilbert
damping term rather than the Bloch term and the implicit condition mz = 0, arising
from the small signal approximation almost always justified in FMR. The use of
Gilbert damping term is formally equivalent to using a complex field as defined
by (46). Similarly, the use of the Bloch term would have resulted in a complex
frequency ω̃ = ω − i/T in (44).
The effect of magnetic anisotropy on the resonance condition, which is neglected
in (43–46), can be calculated using the Smith-Suhl formula [17]:
2 2 1/2
|γ | ∂ 2 Utot ∂ 2 Utot ∂ Utot
ωres = − , (47)
2 2
M0 sin θ ∂θ ∂ϕ ∂θ ∂ϕ θ = θ0
ϕ = ϕ0
∂U ∂U
= = 0. (48)
∂θ θ=θ0 ∂ϕ ϕ=ϕ0
Shape Anisotropy
The dipolar interaction between spins is accounted for using (41), in which N is the
demagnetizing tensor with a unitary trace N xx + N yy + N zz = 1. It is a widespread
practice to consider a specimen of ellipsoidal shape, for which the demagnetizing
field, Bd = −μ0 N M, is uniform within the sample volume [18]. For fields applied
along one of the principal axes of the ellipsoid, N is diagonal. If the magnetically
saturating DC field is applied parallel to the z axis, the solution of (47) with energy
terms (40) and (41) yields the celebrated Kittel formula:
26 Electron Paramagnetic and Ferromagnetic Resonance 1315
1/2
ωres = ω0 + Nyy − Nzz ωM [ω0 + (Nxx − Nzz ) ωM ] . (49)
Equation (49) shows that the resonance condition depends on the sample shape
and on the direction of the applied DC field relative to it. In ferromagnets, shape
anisotropy is quite significant, producing anisotropy fields on the order of μ0 M0 ,
which may be comparable to the applied fields. In paramagnets however, the shape
anisotropy fields are several orders of magnitude smaller because the magnetic
susceptibility is on the order of 10−5 .
Sample shapes, such as spheres, wires, and thin films, most usually encountered
in FMR experiments, can be considered as limiting cases of ellipsoids. Figure 5
illustrates the resonance condition as given by (49) for limited cases of ellipsoidal
samples, assuming their response is dominated by shape anisotropy. The values of
the demagnetizing factors for these cases are summarized in Table 1. Spherical sam-
ples exhibit no shape anisotropy, whereas thin films show large differences between
the responses to in-plane and out-of-plane applied fields. For non-ellipsoidal shapes,
the demagnetizing field is nonuniform, leading to line broadening and, sometimes,
to the excitation of nonuniform spin wave modes.
(5)
Applied field
Magnetocrystalline Anisotropy
UA = Kc1 αx2 αy2 + αy2 αz2 + αz2 αx2 + Kc2 αx2 αy2 αz2 , (50)
where Kc1 and Kc2 are first- and second-order anisotropy constants and α x , α y , α z
are the direction cosines of the magnetization with respect to the principal axes.
Similarly, uniaxial anisotropy leads to a term of the form [12, 13]
where Ku1 and Ku2 are first- and second-order uniaxial anisotropy constants and θ
is the angle between the magnetization and the anisotropy axis. Formulae such as
(50) and (51) have been developed for all crystalline systems [19]. The anisotropy
field can also be expressed in terms of an effective demagnetizing tensor, analogous
to the demagnetizing tensor used in Sect. “Shape Anisotropy” [12, 13].
As the simplest example, let us consider a sphere with first-order uniaxial
anisotropy along the z axis, with a static field applied at an angle θ B from the z
axis, for which (47) predicts a resonance frequency [13]
1/2
ωres = [ω0 cos (θ0 − θB ) + ωA cos 2θ0 ] ω0 cos (θ0 − θB ) + ωA cos2 θ0 ,
(52)
where ωA = |γ |2Ku1 /M0 is the effective uniaxial anisotropy field in units of angular
frequency. Further assuming that the applied field is sufficiently strong to align the
magnetization parallel to it, that is, θ 0 ∼
= θ B , which also implies ω0 ωA and an
equivalently high resonance frequency, (52) can be simplified into the following
expression for the angle-dependent resonance field:
∼ 1 1
B0 = ω + ωA 1 − 3cos θ .
2
(53)
|γ | 2
3
UME = λs σ sin2 θ (54)
2
is used to account for the extremely small anisotropy. In (54), σ is either a tensile
(σ > 0) or compressive (σ < 0) stress, defining the anisotropy axis, λs is the
magnetostriction constant (also positive or negative), and θ is the angle between the
magnetization and anisotropy axis. In these circumstances, (52) applies, in which
ωA = |γ |3λs σ /M0 , and FMR spectra enable the probing of mechanical stress or
magnetostriction if the other is known.
Finally, in FMR studies of ultrathin films and magnetic multilayers, a phe-
nomenological surface anisotropy is often included in the equations. This con-
tribution is usually highlighted in thin films of variable thicknesses, where the
surface anisotropy contribution appears inversely proportional to the thickness. A
comprehensive treatment of anisotropy in thin films is presented in Ref. [19].
So far the exchange energy has been excluded from (47). Assuming isotropic
exchange, this term takes the form
μ0 nW 2 ∇M 2
Uex =− M +A , (55)
2 M0
where nW is the dimensionless Weiss molecular field constant and A is the exchange
stiffness (typically on the order of 10−11 J/m). Substituting the first term of
(55) into (42) leads to the Weiss effective field BW = μ0 nW M, which locks
the relative orientation of individual moments together into an average uniform
magnetization. While Bw can amount to several hundreds of Tesla, dominating
all other effective fields, it does not contribute to the torque in (7), as it is always
parallel to the magnetization. In addition, any expected anisotropy in the Weiss field
is effectively included in the magnetocrystalline anisotropy treated in the previous
section. The second term of (55), however, reflects the additional cost in energy due
to nonuniform magnetic excitations. Assuming a spin wave of the form m = m0 exp
(i k · r − iωt), (42) yields an effective field
where
2A
ex = (57)
μ0 M02
1318 D. Menard and R. Barklie
In this expression, the k2 terms are due to the short-range exchange interaction,
whereas the sin2 θ k arises from dynamic demagnetizing effects due to the
long-range dipolar interactions. Figure 6 illustrates this spin wave manifold for
unbounded isotropic materials. The shaded area between the two curves represents
the continuum of dipole-exchange spin waves that can be excited. For thin films or
slabs with finite dimension, the low k (long wavelength) spin waves are governed
by dipolar interactions and are influenced by the presence of surfaces. In these
circumstances, proper solutions of the electromagnetic problem, including boundary
conditions, yield a rich spectrum of magnetic excitations, including surface waves,
often called magnetostatic waves. Depending on the direction of the saturating field
relative to the surfaces, they are designated as backward volume waves, forward
volume waves, and Damon and Eshbach surface waves. A detailed treatment of the
subject can be found in Ref. [13].
Spin waves in magnetically ordered materials are usually excited by a nonuni-
form driving field, or they can arise due to pinned spin boundary conditions. They
occur naturally in bulk ferromagnetic metals, in which the skin effect results in a
driving field with gradually decreasing amplitude and phase shift as it penetrates the
material. They can be launched on purpose using localized microstrip antennae or
result accidentally from nonuniform demagnetizing fields or from the presence of
wave vector k
26 Electron Paramagnetic and Ferromagnetic Resonance 1319
inhomogeneities in the material. A uniform driving field can also excite odd mode-
number standing spin waves in thin films with significant surface anisotropy. The
presence of spin waves in FMR spectra provides a mean to experimentally determine
the exchange length dex and exchange interaction A.
FMR in Metals
∇ 2 H − ∇ (∇ · M) + k02 (H + M) = 0, (60)
where k0 = (1 − i)/δ 0 , δ0 = 2/μ0 ωσ eff , and σ eff = σ + iωε is the an
effective conductivity including both ohmic and displacement currents. For good
conductors, k0 is complex and δ 0 is the nonmagnetic skin depth, whereas for
√
nonconductors, k0 = εμ0 ω is real. Assuming dynamic fields of the form m, h ∝
exp (i k · r − iωt), (60) can be written as
k02 I − kk
h= m, (61)
k 2 − k02
where k02 I − kk ij = k02 δij − ki kj is a second-order tensor. Equation (60) is the
dynamic part of the dipolar field. In addition, the linearized LLG equation leads to
a relation of the form h = X · m [13], which in the absence of anisotropy simplifies
to
1 ω0 + ωM 2ex k 2 + iαω iω
h= m. (62)
ωM − iω ω0 + ωM 2ex k 2 + iαω
The simultaneous solution (61) and (62) results in complex dispersion relations.
In the magnetostatic approximation, which is equivalent to setting k0 = 0 in (61),
one recovers the spin wave manifold (59) (provided damping is neglected setting
α = 0). Further setting k = 0 leads to the resonance conditions for uniform modes,
as treated above. However, these approximations are no longer justified in problems
involving conductive materials where the skin depth is smaller than their shorter
dimensions.
Admitting that k is perpendicular to the surface, due to skin effect in metals, the
local approximation, which consists of neglecting the k2 terms in (62), yields an
effective transverse permeability:
1320 D. Menard and R. Barklie
in which the effective scalar permeability is given by (63). The FMR response is no
longer described in terms of complex magnetic susceptibility but rather in terms of
complex impedance [24]. Recognizing that the impedance in metals, in conditions
of strong skin effect, is inversely proportional to δ eff , (65) is indeed the source of
the giant magnetoimpedance effect (GMI) [20]. In the other limit of the weak skin
effect regime, for which δ eff is much larger than the thickness of the sample, one
may use the same formalism as for nonmetallic ferromagnets but with an additional
contribution to the damping due to eddy currents.
If we now relax the local approximation, putting the exchange term back into
(62), the dispersion relation becomes a fourth-order equation in k2 [21]. The four
pairs of roots correspond to two pairs of electromagnetic dispersion branches
and two pairs of spin waves, with strong hybridization around resonance. A
linear combination of the waves is necessary to satisfy the electromagnetic and
magnetization boundary conditions, such as free spin, pinned spin, or a mix of the
two [22]. The solution for the impedance finally appears as a 4 × 4 determinant
equation , which is relatively complicated, especially when anisotropy terms are
included in (62). Fortunately, approximations can be justified to simplify the result
considerably, with only small impact on the accuracy. A comprehensive analysis has
been presented [11, 23, 24].
26 Electron Paramagnetic and Ferromagnetic Resonance 1321
Historically, EPR and FMR experiments have been performed with the same type
of spectrometer, using microwave cavities in which the frequency ω of a relatively
small B1 field is kept constant, while B0 is swept through the resonance at a rate slow
enough that relaxation maintains a constant magnetization in the rotating coordinate
system. In these conditions, the frequency ω1 is far less than the relaxation rate so
that the magnetization remains close to thermal equilibrium and exhibits a small
precession with approximately constant Mz around the average static effective
field. This classical setup has changed little in half a century, apart from some
improvement in the components for producing the microwave fields and digitally
acquiring the signals.
The basic instrumentation is presented in Sect. “Frequency Domain Cavity
EPR/FMR”. Alternative methods are then surveyed in Sect. “Survey of Other
Methods”. This second part is far from exhaustive as the wealth of EPR and FMR
methods would need another chapter, if not a book. The interested reader will find
an alternative complementary treatment in Ref. [25].
fields within the cavity build up to values greatly exceeding those of the incident
microwaves.
The coupling to the cavity can be adjusted with a metal-tipped screw just in
front of the cavity iris. When power is absorbed in the sample during resonance, the
cavity is no longer critically coupled, and some microwave power is reflected back
via the circulator, or transmitted, to a detector diode. In order to be most sensitive
to this reflected power, the diode must be appropriately biased. This is achieved by
passing some of the source output to the diode via the reference arm. Adjustment of
the phase allows either the absorption or dispersion mode of the EPR signal to be
detected.
As the external DC field is swept through resonance, the Q factor of the cavity
changes, and its resonance frequency is shifted, associated with the absorption and
the dispersion of the magnetic susceptibility, respectively. The frequency of the
source is usually locked onto that of the cavity so that only absorption is observed
and the reflected signal monitors changes in the Q factor of the cavity. In absorption
mode, Q exhibits a dip as a function of the sweeping field with the minimum at
the resonance field. The automatic frequency control (AFC) can be achieved using
frequency modulation of the source. This results in an amplitude modulation at the
diode, yielding the correction signal to adjust the source frequency to that of the
cavity.
It is also customary to superimpose a small field modulation on the static field.
This modulation is typically at 100 kHz, and its amplitude should be chosen to be
less than the signal linewidth. The diode output then contains an AC component at
100 kHz with an amplitude proportional to the slope of the bell-shaped resonance
curve. This AC component becomes the signal input to the phase-sensitive detector
(PSD) whose reference input comes from the oscillator driving the modulation coils.
The DC output of the PSD is a measure of the amplitude of its AC input so that the
EPR signal represents the derivative with respect to field of the absorption curve.
There are two advantages of this technique: at 100 kHz, the 1/f noise of the detector
is greatly reduced compared with its value at the sweep frequency, and the noise is
reduced because the PSD acts as a narrow band-pass filter centred on the modulation
frequency.
The signal amplitude S, which is inversely proportional to the minimum
detectable number Nmin of paramagnetic centres, depends on several parameters:
1 B0
S∝ PMW × Bmod × Q × η × √ × , (66)
kB TD ν B1/2
where PMW is the microwave power incident on the cavity; Bmod is the amplitude of
the modulation field; Q has its value for the cavity loaded with the sample; η is the
filling factor, which is a measure of the fraction of microwave energy that interacts
with the sample; TD is the temperature of the detector; Δν is the bandwidth of the
detection system; ΔB1/2 is the half-width at half-height of the single absorption line;
and B0 is the resonance field.
1324 D. Menard and R. Barklie
The signal can be increased both by increasing the modulation amplitude and
microwave power, but if the former is too high, distortion will occur and for the
latter saturation can set in. Increasing the sample size will also boost the signal, but
there is little point in extending the sample beyond the region in the cavity where the
microwave field is concentrated. Working at higher frequencies, in smaller cavities,
helps to increase the sensitivity as it means a larger B0 and, if the sample volume
is constant, also a larger η. Finally, the noise can be reduced by signal averaging
over several sweeps or by taking longer measurements. It is frequently the value of
ΔB1/2 that limits the signal amplitude. For typical operating values, Nmin is in the
range 1011 –1012 .
There are several variants of the setup shown in Fig. 7, such as using microwave
amplitude modulation instead of field modulation, using a transmission cavity rather
than reflection, using mixers for up-conversion and down-conversion of the signals
instead of diodes, sampling the signal with a digitizer rather than conditioning it with
a lock-in detector, and so on. Classical setups are reviewed in detail by Poole [26].
Fig. 9 (a) Illustration (not to scale) of the CoFeB nanowire array built into a microwave
transmission line, sitting on a ground plane with a stripline on top, (b) measured hysteresis loop,
and (c) real and imaginary parts of the effective permeability at several applied fields corresponding
to different saturated or remanent states of the wire system. Details in [29] (Reprinted figure with
permission from [29]. Copyright (2009) by the American Physical Society)
studies, but in which the soft amorphous ferromagnetic metallic wire is part of the
conductive line the transmission line, which is very convenient to carry on FMR or
GMI from a few MHz up to several GHz [28].
Figure 9 shows an example of FMR data collected using a broadband VNA-based
method. The sample consisted in an array of ferromagnetic nanowires electroplated
in nanoporous alumina templates.The resonator was a stripline circuit fabricated
around the magnetic sample, the latter being part of the effective dielectric of
the device under test, in between the conductive lines. Both the dispersive and
absorptive parts of the complex susceptibility could be extracted as a function of
frequency, for different applied fields [29].
1326 D. Menard and R. Barklie
Time-Domain Techniques
Progress in high-speed electronics has also permitted time-domain pulsed EPR
experiments, such as free induction decay or spin echoes, gradually catching up
with extremely well-developed pulsed NMR techniques carried out at much lower
(radio) frequencies [10]. The method is to keep B0 fixed, while a sequence of short
high-power pulses of B1 field is applied, such that the Rabi frequency ω1 is higher
than the relaxation rate. The aim is to prepare the magnetization in a state out of
equilibrium and then measure its evolution by monitoring its recovery to the thermal
equilibrium state. Since T1 and T2 are nearly always much shorter for the electronic
than for the nuclear moments, the pulses used for EPR must be much shorter (ns)
and stronger (kW) than those used in NMR.
Compared to a CW spectrometer, a pulsed EPR spectrometer requires a pulse
shaping stage followed by high-power traveling-wave tube amplifier (TWTA) in
the excitation arm, providing the pulse sequence to a broadband low Q resonator.
A precise control over the timing and synchronization of the pulse shaping,
amplification, and data collection is critical. Figure 10 shows the main components
of a pulsed EPR spectrometer with a transmission resonator. Various components,
such as isolators, attenuators, and filters, are not shown for simplicity. The arbitrary
waveform generator (AWG) allows for pulse shaping, frequency up-conversion
(optional), and synchronization of the different components, including the PIN
diodes (mw switches) for protection of the receiver. Down-conversion of the signal
using a mixer enables the probing of the evolution of the magnetization in the
rotating frame so that the Fourier transform of the time response can display the
resonance peaks around a central frequency. Modern equipment permit fast digital
sampling or subsampling of the signal.
f
Attenuator Phase
Power
divider shifter
Resonator with
Pulse shaping magnetic sample
and frequency
upshift (AWG)
Electromagnets
Fig. 10 Simplified block diagram of a pulsed EPR spectrometer. The AWG control the timing
and synchronization of the components as well as the pulse shaping of the CW signal. Various
components, such as attenuators, isolators, and filters, are not shown for simplicity.
26 Electron Paramagnetic and Ferromagnetic Resonance 1327
Conclusion
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Bibliography
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Oxford (1970)
Weil, J.A., Bolton, J.R., Wertz, J.E.: Electron Paramagnetic Resonance: Elementary Theory and
Practical Applications. Wiley, New York (1994)
Pake, G.E., Estle, T.L.: The Physical Principles of Electron Paramagnetic Resonance. Benjamin,
New York (1973)
Spaeth, J.-M., Niklas, J.R., Bartram, R.H.: Structural Analysis of Point Defects in Solids: An
Introduction to Multiple Magnetic Resonance Spectroscopy. Springer-Verlag, Berlin, Heidelberg
(1992)
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Vonsovskii, S.V.: Ferromagnetic Resonance: The Phenomenon of Resonant Absorption of a High-
Frequency Magnetic Field in Ferromagnetic Substances. Pergamon Press Ltd., Oxford (1966)
Gurevich, A.G., Melkov, G.A.: Magnetization Oscillations and Waves. CRC Press (1996)
Stancil, D.D., Prabhakar, A.: Spin Waves: Theory and Applications. Springer (2009)
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1334
Spin-Transfer Torque, Magnetic Switching, and Oscillations . . . . . . . . . . . . . . . . . . . . . . . . 1337
Spin-Transfer Torque in Phenomenological Form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1337
Spin-Torque-Driven Anti-damping Magnetic Switching . . . . . . . . . . . . . . . . . . . . . . . . . . 1339
Orthogonal Spin-Torque-Driven Magnetic Switching . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1342
Spin-Torque Oscillators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1344
Spin-Transfer-Induced Excitation of Spin Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1344
Spin-Transfer Vortex Oscillators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1346
Synchrotron and Femtosecond Laser-Based Time-Resolved Spin Dynamics . . . . . . . . . . . . 1347
Switching Schemes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1348
Microscopy Using Visible Light or X-Rays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1349
Ultrafast Spin-Transfer Torques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1351
Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1354
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1355
A. D. Kent
Center for Quantum Phenomena, Department of Physics, New York University, New York,
NY, USA
e-mail: [email protected]
H. Ohldag
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
Department of Physics, University of California Santa Cruz, Santa Cruz, CA, USA
Department of Materials Science, Stanford University, Stanford, CA, USA
e-mail: [email protected]
H. A. Dürr
Department of Physics and Astronomy, Uppsala University, Uppsala, Sweden
e-mail: [email protected]
J. Z. Sun ()
IBM T. J. Watson Research Center, Yorktown Heights, NY, USA
e-mail: [email protected]
Abstract
Introduction
dM α dM
= −γ μ0 M × Heff + M× (1)
dt |M| dt
where γ = |g| μB /h̄ is the magnitude of the gyromagnetic ratio, g −2, M is the
magnetization, and Heff is the effective magnetic field, including applied and dipolar
fields, and includes derivatives of M if dimensions approach that of the exchange
length, as discussed in Eq. 2. Here α is a dimensionless phenomenological quantity
describing damping – analogous to mechanical friction or the inverse of a Q-factor
used in describing a classical resonator.
√ In the limit of magnet size small compared to the exchange length [3] λex
A/Ku where A is the exchange constant and Ku is the anisotropy energy density,
the system can be approximately viewed as having a single macrospin moment
described by two degrees of freedoms – i.e., its rotation angles.
Micromagnetics based on the LLG equation remains the most practical method-
ology for understanding dynamics in applications today – applications such as
for thin films in magnetic storage (hard disk and tapes) as well as in solid-state
integrated magnetic random access memories (MRAMs).
For time scales on the order of picoseconds or shorter, with energies above
tens of millivolts per unit cell, the atomic nature of the electronic spin becomes
a significant factor. This is the regime where the electronic band structure and
its spin-space degrees of freedom entangle. These interactions lie at the heart of
ferromagnetism. The two most important interactions are (1) Heisenberg exchange,
originating from the fermionic nature of the electrons that dictates the occupancy
of its atomic orbital states and related band structures, and (2) a usually smaller
spin-orbit interaction, which also plays a role, particularly in materials with heavy
elements. This is the regime where electronic transport processes gets coupled to
that of electron spin degrees of freedom. It gives rise to such properties as the
magnetoresistance and anomalous Hall effect in ferromagnetic conductors, where
the magnetic configuration affects the electrical transport.
Over the last two decades, we began to understand that there also exists an
inverse process – namely, that a transport electronic current carried by itinerant
electrons with spins can affect the magnetic state of the conductor as well. For
magnetodynamics, this interaction with transport current adds new terms to the
LLG equation which describe the so-called spin-torque effects. Such effects couple
magnetodynamics and electronic transport current beyond the dipolar-inductive
interaction. These understandings highlight the importance of angular momentum
conservation in the detailed balance of spin-polarized electronic transport.
The recent ability to control magnetization on ultrafast time scales (pico- or
femtoseconds) and short length scales (nanometers) have attracted interest as such
processes may play an important role for information storage and processing
technologies in the future. For these, classical approaches to describe such systems
are often insufficient, and it is necessary to describe and characterize the magnetic
properties of these physical systems on an atomic scale.
For time scales much shorter than a picosecond, most of the time, one would
need a quantum-mechanical picture of electronic excitation. The combined electron
1336 A. D. Kent et al.
spin system can often be modeled by an atomistic approach [4], which uses an
LLG equation as a semi-classical approximation on an atomic scale, with spins of
fixed length that are exchange coupled via a Heisenberg term. Such models can
numerically describe fast dynamics such as ultrafast laser-induced demagnetization.
An intuitive way to understand excitations involving magnetism is to view the
system as composed of a few “energy reservoirs” with characteristic coupling
strengths (i.e., time scales), as illustrated in Fig. 1. While this as often is an
oversimplification, it highlights the important factors at play and the approximate
time and energy for the various leading order factors. In principle, it is possible
to excite any of these reservoirs through pulsed or periodic optic, magnetic, or
electric fields. For example, the spin-orbit coupling energy is typically a few tens of
meV. If one applies a very strong and short field pulse that is able to overcome this
energy barrier on an atomic scale, it will only take about 100 fs for spin and orbital
momentum to realign, the spin-orbit relaxation time. Effect on these time scales
becomes relevant when the magnetization is excited using, for example, ultrafast
laser pulses that are able to perturb the electron system. However, in cases where
external magnetic fields or current pulses are applied, the typical electron-phonon
relaxation time of 1–10 ps and spin-lattice relaxation time of typically ≈100 ps play
a more important role since such excitations are limited to frequencies of a few tens
of GHz compared to optical laser excitations.
In what follows, we discuss several recent topics in magnetodynamics that
become important, thanks both to the advances of fundamental understanding and
to the significant development of modern metrology in X-ray and laser pump-
probe measurement technologies. We start with a discussion on the phenomena of
spin angular momentum transfer and the basic nonlinear dynamics involved, which
affects ferromagnetic systems in the form of a new term in the LLG equation.
The presence of spin-torque brings us a new, spin current-induced switching
mechanism for nanostructured magnets. It also brings a rich variety of nonlinear
27 Magnetization Dynamics 1337
magnetodynamics that have been most directly probed by the recently developed
X-ray spin-resolved microscopy. These new discoveries highlight the importance of
spin angular momentum current. We will also briefly review the dynamics occurring
on shorter time scales, often investigated by using femtosecond laser excitations. A
more extensive review on the femtosecond-level magnetic excitation can be found
in a separate chapter by Theo Rasing et al. in this volume.
Spin-transfer torque (STT) is a term that describes the dephasing effect of a spin-
polarized current upon entering a magnetically ordered material at a well-defined
interface. The dephasing of the spin component transverse to the magnetization
under the usually strong s-d exchange-like interaction results in a net torque being
exerted on the ferromagnetic moment. The effect was first proposed in spin-valve-
like structures [5, 6] as a manifestation for a type of energy-nonconserving torque
discussed in a ferromagnetic tunnel junction [7]. Such an energy-nonconserving
torque acts along the same vector axis as the damping torque. With the right
orientation of the spin polarization and the spin current direction, the STT can
overcome the damping torque in a nanomagnet and result in a magnetic reversal
if the nanomagnet is situated in an uniaxial anisotropy potential [5, 8, 9, 10]. The
same torque can also, under more general energy landscapes for the magnetic
moment, promote magnetic instability that results in persistent magnetic precession
or emission of spin waves [6, 11, 12].
H
damping
I < Ic
I > Ic
q spin-torque I >> Ic
(a) M (b)
ns the spin polarization unit vector direction (Fig. 2). γ = |g| μB /h̄ is the magnitude
of the gyromagnetic ratio constant. μB here is the Bohr magneton, and g −2 for
simple ferromagnetic metals is the Landé g-factor. For a charge current Icg with spin
polarization factor of 0 < η < 1, for example, Is = (μB /e) Icg η.
When the magnetic body in volume Ω is larger than the relevant magnetic length
and the system is not in its macrospin limit, the quantities in Eq. 2 take on a position
dependence in addition to the time dependence. Then Eq. 2 becomes a constitutive
equation that, with appropriate boundary conditions, determines the micromagnetic
dynamics of the system, with the usual non-local dipolar field interactions described
by Hd r, r . The location dependence of the magnetic moment also introduces an
exchange energy-related term into Eq. 2 [13]. These result in a modification of the
field term as
A 2
H eff → H eff (r) + Hd r, r d 3 r + nm (r) , (3)
Ω μ0 Ms
to-plane (CPP) spin-valve structures, either diffusive or ballistic [14, 15]. It may
originate from spin filtering through a barrier in magnetic tunnel junctions (MTJs)
[16, 17]. The spin current could also be generated by transport processes involving
a strong spin-orbit interaction [18, 19, 20, 21, 22, 23]. Large spin-torques have also
been reported at interfaces between topological insulators and ferromagnets; see
Refs. [24,25,26], for example, for a review on the subject. The spin current can also
be induced by heat flow involving a magnon thermal gradient [27, 28, 29]. For these
non-spin-filtering mechanisms, the electron to spin current conversion is in principle
not limited to one h̄/2 per electron charge current, whereas for the spin-filtering
processes, one electron can only transfer one h̄/2 of spin angular momentum, that
is, one Bohr magneton μB of magnetic moment, which sets a limit to the charge-spin
conversion efficiency.
Two factors make STT dynamics rich and often complex. They are (1) the
effect of finite temperature, which makes thermal fluctuations and thus related
stochastic distribution issues important for STT-driven dynamics, and (2), in most
realistic samples, various internal degrees of magnetic freedom that participate in
the STT dynamics, making the whole process more complex than a macrospin.
Both are significant scientific challenges to one’s ability to quantitatively understand
and control the STT-related behavior. Both are critically important for technology
development.
The primary effect of spin-torque on a magnetic nanostructure is to change its
effective magnetic damping. When a sufficient amount of spin-torque is applied in
the right direction, the net damping of the nanomagnet can become negative for a
certain region on the macrospin coordinate unit sphere, which can amplify magnetic
precession (see Fig. 2). For a nanomagnet with uniaxial magnetic anisotropy, this
can result in its moment reversing from the easy-axis direction anti-aligned to the
spin polarization to the direction aligned with it [5, 8, 10]. In other geometries, it
is possible to send the moment into persistent oscillation mode, which becomes an
STT-driven oscillator [30].
2e α
Ic0 = μ0 mHeff , (4)
h̄ η
where η is the effective spin polarization of the charge current, whose exact
functional form depends on the structure of the nanomagnet’s spin current transport
environment [5, 31, 17, 32, 33]. Heff = Hk + Ha in the case of a simple uniaxial
anisotropy with its anisotropy field as Hk and the applied field Ha in the same
direction.
In the low-temperature T → 0 K limit, a current larger than Ic0 is required to
initiate the anti-damping switching. The time it takes to switch a nanomagnet in the
macrospin limit is inversely proportional to I − Ic0 in the form of
τ0 π
τ≈ ln , (5)
I /Ic0 − 1 2θ0
with θ0 being the initial angle the moment makes with its easy axis upon the
m/μB 1
switching on of the spin-torque and τ0 = = [10, 34, 33].
ηIc0 /e αγ μ0 (Hk + Ha )
At finite temperature, there is a thermal distribution of initial angles θ0 about
the easy axis. The precessional reversal process would also be thermally scattered.
Of these two processes, in the short-time, high STT drive limit (strictly speaking
in the asymptotic limit of I /Ic0 10 [34]) where τ 1/(αγ μ0 Hk ), the initial
condition’s thermal distribution usually dominates the consideration [34,35]. Taking
this distribution into account, one arrives at the probability for switching at time
t for I Ic0 as P (t), which has the high-barrier Eb kB T and long-time
t τ0 / (I /Ic0 − 1) asymptote [36, 37, 34, 38]
π 2 Eb − τ2t (I /Ic0 −1) π 2 Eb
P (t) ≈ exp − e 0 + O exp − , (6)
4kB T 4kB T
Eb H ν1 I ν2
P (t) ≈ 1 − exp −f0 t exp − 1− 1− , (7)
kB T Hk Ic0
for 0 P (t) 1 with I Ic0 and H Hk , with f0 being the attempt frequency
for escape from the metastable magnetic state. ν1 2 if H is nearly collinear
with the anisotropy axis; otherwise ν1 < 2 [39], and 1 ≤ ν2 ≤ 2 depending on
the details of the anisotropy potential shape [40, 41], with ν2 → 2 for a perfectly
collinear, uniaxial anisotropy-only configuration. The exact values of the exponents
27 Magnetization Dynamics 1341
Eb Q0
Iw ≈ + , (8)
κ τw
for a write pulse width in the range of τw ∼ τ0 or smaller. Here, Iw is the write
current amplitude. κ = Eb /Ic0 ≈ (h̄/4e) (η/α) is the so-called STT “switching
efficiency” here expressed in the macrospin limit [44, 45]. From Eq. 6 and Ref. [44]
e m π 2 Eb
Q0 ≈ ln , (9)
2η μB 4kB T r
Spin-Torque Oscillators
Spin-torque can cause persistent magnetic oscillations under many situations and
excite spin waves. This can either be of the form of coherent precession of a near
macrospin [10,30,91] or spatially non-uniform magnetization patterns [6,11,92,93,
94, 95, 96] of various wavelengths and amplitudes. In both cases, the magnetization
dynamics can be highly nonlinear.
A point contact to an otherwise extended ferromagnetic thin film stack is a
prototypical configuration that can be used to excite spin waves. The STT is
concentrated in the contact region and thus will generate a non-uniform magnetic
excitation (i.e., because regions outside the contact do not experience a significant
STT). A typical structure consists of a thin film stack in the form FM | NM | FM
(free) surface, and the point contact can be either via a metallic tip [92] or by
lithographic patterning [93] to create a “nanocontact,” an aperture with a diameter
200 nm in a dielectric that is filled with a non-magnetic metal (Fig. 4).
The magnetization excitations can be localized or extended. In the former case,
spin excitations are near the contact and decay rapidly outside the nanocontact
region, while in the latter case, propagating spin-wave modes can be excited. The
nature of the excited modes (extended or localized) depends on many characteristics
of the contacts, ferromagnetic layers, and applied current and field. The basic issue
is whether spins excited by STT in the contact region can couple to the propagating
spin waves in the free layer.
In a linear response region (limit of low currents, currents just above the
threshold for current-induced excitations), it was shown theoretically that the
wavelength of the spin waves would be approximately the nanocontact diameter
and propagating spin waves would be excited, with spin-wave amplitudes that decay
algebraically with distance from the nanocontact [97]. However, this situation is not
generic. At higher current amplitudes, spin waves can be localized in the contact
region [98, 99, 100], and the nature of the excitations depends on the applied
field (i.e., there can be transitions between localized and extended spin waves as
27 Magnetization Dynamics 1345
a function of the applied field [101]). Both extended and localized excitations have
been observed experimentally using optical and X-ray imaging methods, such as
Brillouin light scattering [102, 103], Kerr effect [104], and scanning transmission
X-ray microscopy [105, 106].
In the case in which the free layer has perpendicular magnetic anisotropy and
the field is perpendicular to the layer plane, the excitations are localized, and
spin waves can “condense” in the contact region forming a magnetic droplet
soliton [107], a state that was predicted theoretically in the 1970s for a ferromagnetic
layer with axial anisotropy and no dissipation or damping [108, 109]. This has
recently been observed experimentally [110, 111, 112], including directly using
scanning transmission X-ray microscopy (STXM) [105]. In the latter experiment,
the profile of the excitation in the contact region was directly measured, and the
spin-wave amplitude was seen to decay rapidly outside the contact, i.e., the spin
excitation was shown to be localized in the contact region. Modeling has shown
that STT in nanocontacts to thin films with perpendicular magnetic anisotropy
can also stabilize topological magnetic structures, including dynamical magnetic
skyrmions [113, 114]. Solitons were also directly observed in in-plane magnetized
free layers in which the Oersted field from the current leads to a more complex
potential for spin waves [106], for example, the potential favors propagation of spin
waves in particular directions away from the contact. In this case, STXM was used
to create movies of the magnetic excitations, using a heterodyne method of locking
the frequency of the spin excitations to an external microwave source. Further,
this directional propagation of spin waves has been used to phase-lock multiple
nanocontact oscillators [115].
1346 A. D. Kent et al.
Spin transfer can also be used to nucleate, excite, and study magnetic vortices and
can be applied to the study of other types of topological magnetic structures (e.g.,
skyrmions). Vortices can form in thin ferromagnetic layers and disks composed
of soft magnetic materials, such as permalloy. In a nanodisk, they minimize
magnetostatic energy at the cost of exchange and anisotropy energy, forming a
circular spin structure shown in Fig. 5. They can thus be favored by the geometry
of the magnetic layer; typically thicker disks will have a tendency to have vortex
ground-state magnetic configurations (see, for example, [126]). In a thin extended
layer, such as in a spin-transfer nanocontact (Fig. 5), vortices can be nucleated by
applying a current pulse, as the Oersted field from the pulse favors a circular spin
configuration [127]. The center of the vortex has a singular region, a core, in which
the moments point out of the film plane [128]. There are thus two physical quantities
that characterize a magnetic vortex, the sense of spin circulation in the plane (a
winding number) and the direction of core magnetization (a polarity). Both these
quantities play an important role in the dynamics of vortices – as described by
27 Magnetization Dynamics 1347
West East
SiO2
Free layer
Metal
Fixed layer
Current Bottom Current
electrode
Fig. 5 Schematic of a nanocontact with the free layer in a magnetic vortex configuration. A pulse
current can nucleate a vortex, the planar spin configuration shown above the contact, and currents
used to excite gyrotropic vortex motion. This motion can be studied by measuring the contact
resistance as a function of time or spectral measurements. (Figure adapted from Ref. [127])
the Thiele equation, an equation derived from the LLG equation that describes a
vortex’s “center of mass” motion as well as that of other types of magnetic objects
(e.g., domain walls) [129].
Part of the interest in vortex oscillators is that they can have high-quality
factors [130]. Their oscillation frequency is typically 0.1 to a few GHz, about
one order of magnitude less than spin-wave frequencies (i.e., the FMR frequency).
However, the oscillator’s output power can be large, particularly when the magnetic
layer in which the vortex forms is one of the electrodes of a magnetic tunnel junction
nanopillar [131]. Spin-torques also enabling exciting nonlinear dynamics and vortex
oscillators are a physics playground for exploring such dynamics, including chaotic
magnetization dynamics [132]. A variety of experimental studies have examined the
interactions between magnetic vortices, including in nanopillars with two magnetic
layers that each contains a vortex [133] and in proximal nanopillars [134].
Further, as with other types of spin-torque oscillators [135], injection locking of
vortex oscillators has been demonstrated [136]. Time-resolved imaging studies of
magnetic vortex dynamics have been conducted using MOKE [137] as well as X-ray
microscopy [138].
Switching Schemes
In the following, we are concerned with the manipulation and ultimately the
reversal of magnetization on fast time scales. Naively one would expect that
the magnetization of a sample reverses upon application of a magnetic field of
the opposite direction. However, this is not the case, since the origin of the
magnetization is the spin angular momentum of the atoms, and to change angular
momentum, one has to supply angular momentum to the sample. The most common
way to do this is it to apply a torque with an external field. That means that the
external field has to be applied at an angle to the magnetization. This is in general
described in the Landau-Lifshitz-Gilbert equation shown in Eq. 1, which includes
the gyromagnetic ratio γ , the effective field (sum of external field, demagnetization
field, and anisotropy fields), as well as the damping constant α, which is necessary
to include dissipative processes in a realistic medium.
Figure 6 shows three different possibilities to affect the magnetization by
supplying angular momentum or by applying a torque to the current magnetization
in an experiment. The panel on the left hand side shows the simple case of applying
Fig. 6 Illustration of different switching schemes, via application of a local magnetic field (left),
optical excitation (center), or spin-polarized current (right)
27 Magnetization Dynamics 1349
a magnetic field. While this approach is rather straightforward to realize and can be
described using Eq. 1, it has practical limitation given by the maximum field that
one can achieve and the fact that it is non-trivial to localize magnetic fields to the
area of interest. The fact that field-induced dynamics on larger length scales are
rather complex limits the speed with which the magnetization can be reversed using
external fields. Interestingly, one finds that even when using the extremely strong
fields of several Teslas generated by a relativistic electron bunch for a picosecond
or less, the magnetization far away from the excitation is still precessing for about
100 picosecond [141], essentially limiting the speed with which information stored
in such a system can be processed by only using conventional magnetic fields.
To speed up the reversal and to control the magnetization in a more confined
manner, other excitation mechanisms are considered. For example, the surprising
possibility to manipulate magnetization using short and powerful laser pulses has
evolved over the past decade [142, 143, 144, 145, 146]. Here a magnetic sample
is irradiated with an ultrashort laser pulse without the application of an external
field or current. The exact nature of the reversal mechanism and the role of the
angular momentum supplied by the photons are still debated. We will give a
short overview over this field in section “Ultrafast Spin-Transfer Torques”. A more
thorough overview will be given by T. Rasing et al. in another chapter.
One of the most efficient ways to detect magnetization dynamics on these
time scales is via electrical transport. This approach uses standard radiofrequency
analysis and lock-in equipment that is commercially available, which is why it is
widely used. For this detection method, one makes use of magnetoresistance effects
like giant magnetoresistance (GMR) or anisotropic magnetoresistance (AMR). Any
time one investigates a layered magnetic system, it is usually possible to use the
GMR effect, which manifests itself as a change in magnetization when a current
flows between two magnetic layers separated by a non-magnetic layer. This is
in particular useful for studies of spin-torque oscillators where the current flows
through a small nanocontact from a fixed polarizing layer to a free oscillating
layer. In this case, one can make use of the already existing electrical contacts and
directly determine the magnetization dynamics using a spectrum analyzer and lock-
in detection. If there is only one magnetic layer or the devices are simply planar,
one can use the AMR effect, which manifests itself in a change in resistance if the
magnetization is parallel or perpendicular to the current direction. This effect is at
least an order of magnitude smaller than the GMR, but it is compatible with most
experimental geometries. However, none of these approaches provide microscopic
or spatially resolved information. Typically, one can obtain indirect information
about the microscopic behavior of the sample by comparing the macroscopic
transport results to model calculations.
Fig. 7 Two different approaches to image spin-wave dynamics excited by a nanocontact. The
image on the left is acquired using Brillouin light scattering from [102], while the image on the
right shows a localized spin wave acquired using scanning transmission X-ray microscopy [105]
using visible light based on the magneto-optical Kerr effect has the advantage that
the setup can be fairly simple and requires few components. Also using standard
pump-probe approaches, one can achieve very good time resolution of the order of
100 fs. However, the spatial resolution is limited, and the fact that the Kerr rotation is
generally small means that it is not generally possible to use time-resolved MOKE
microscopy. Nevertheless, using sophisticated lock-in approaches, one can today
use TR-MOKE to image different spin-wave modes on materials like YIG [147]
or permalloy [148]. Improved sensitivity to spin-wave dynamics in particular using
optical microscopy has been demonstrated more recently by using Brillouin light
scattering (BLS). In BLS, one images not the directly reflected light from the surface
of the magnetic sample but light scattered at a certain angle. The angle is determined
by the interaction of the incoming photon with magnons in the sample related to
the existence of magnetic excitations, like, e.g., spin waves. This approach provides
excellent sensitivity to magnetization dynamics, since there is very little background
at the observation angle, and in theory, all scattered light is related to the presence
of magnons. The left panel in Fig. 7 shows an image of the envelope of a spin wave
propagating from a nanocontact located underneath the triangular-shaped electrical
contact. Due to the limited penetration of the light, no information can be obtained
underneath the electrical contact.
One way to improve the spatial resolution and to gain the ability to study
buried magnetic layers is X-ray microscopy [149, 150], either in scanning or
full-field manner. These studies are usually conducted using a synchrotron X-ray
source, which provides short tunable and polarized X-ray pulses between 50 and
100 ps duration. The absorption of circular polarized X-rays at the L-absorption
resonances of the 3d transition metals like Fe, Co, and Ni between 500 and 1000 eV
depends strongly on the relative alignment of X-ray propagation and magneti-
zation (X-ray magnetic circular dichroism or XMCD), providing a suitable and
27 Magnetization Dynamics 1351
element-specific contrast mechanism for magnetic imaging. Due to the short wave-
length of such X-rays (1–10 nm), one is also able to obtain magnetic information on
the nanoscale [139]. If one combines X-ray microscopy with pump-probe schemes
and dedicated detection electronics [151, 152, 153], it is then possible to follow
magnetization dynamics with 10 nm spatial and 10 ps temporal resolution. One
example is shown on the right hand side of Fig. 7, where the presence of a magnetic
soliton generated by a spin-torque nano-oscillator is shown [105].
We note that another way to image magnetization dynamics is to use scan-
ning electron microscopy with polarization analysis (SEMPA); see, for example,
[154,155]. In SEMPA, a standard SEM instrument is combined with a Mott detector
to identify the spin of the emitted electrons. By using an orthogonal set of Mott
analyzers, it is then even possible to obtain a full three-dimensional map of the
magnetic behavior after excitation. However, due to the rather low efficiency of
the Mott detector, the very high surface sensitivity of the detector, and the vacuum
requirements, there are practical limitations on the types of samples that can be
studied.
Fig. 9 Schematic illustration of how superdiffusive spin currents generated by fs laser excitation
of a ferromagnetic layer (red bottom layer) can be utilized to manipulate spins in a (blue)
ferromagnetic layer separated by a non-magnetic spacer (yellow). (left) and (right) panels indicate
how superdiffusive spin currents can affect the magnetic moments of collinear spins and can lead
to a precessional spin motion, respectively. (From Hellman et al. [188])
precession angles are still small due to the limited amount of observed spin angular
momentum transfer of several percent between the orthogonally magnetized layers,
such experiments represent a unique tool to actually quantify and consequently
optimize angular momentum transfer through interfaces.
A key ingredient in all-optical switching presented in more detail in the chapter
by Rasing et al. in this book is the dramatic reduction of the sample magne-
tization via ultrafast demagnetization. This allows angular momentum exchange
between magnetic subsystems to take over as clearly demonstrated by ultrafast
element-specific X-ray magnetometry in GdFeCo films [185]. The emergence of
a ferromagnetic transient state out of the antiferromagnetically aligned transition
metal and rare-earth magnetic subsystems bears this fingerprint of non-local angular
momentum exchange [185]. The question arises whether demagnetization accom-
panied by superdiffusive spin currents can also enable magnetic switching. Graves
et al. [186] found such a mechanism for GdFeCo using ultrafast X-ray scattering at
novel X-ray free-electron laser facilities. The basis of this study was the chemical
segregation observed in GdFeCo films into Gd-rich and Fe-rich nanoregions on a
10 nm length scale. Following ultrafast demagnetization of both the Gd 4f and Fe
3d magnetic sublattice, a reversal of the Gd 4f moments in Gd-rich nanoregions was
observed. This led to a local ferromagnetic state with parallel alignment of Fe 3d and
Gd 4f moments. The authors also measured the net spin angular momentum transfer
across ∼10 nm distances and showed that it is compatible with spins arising from
Fe 3d states. They must become delocalized from Fe-rich regions being transported
laterally into Gd-rich areas to accumulate there until the originally antiparallel Gd
4d magnetization is reversed [186]. These measurements lead the way to study the
effects of ultrafast spin transport over nanoscale dimensions. Although currently
only the action on local magnetic moments can be probed [186], future advances in
X-ray nano-spectroscopy offer the unique opportunity to also determine the effects
of non-local transport currents on local valence-level populations [187].
Modern magnetism and magnetodynamics have seen significant progress in the last
two decades. The theoretical discovery and experimental observation of spin-torque
opened up new frontiers for fully localized control of nanomagnetic objects. This
provided a useful means of writing a magnetic bit in high-density arrangement such
as silicon-integrated STT-MRAM. Spin-torque also brought about a new type of
dynamics involving negative damping, opening up the world of spin current-driven
nonlinear magnetic oscillators, new ways of propagating and manipulating spin
waves, and new nonlinear magnetic condensates. Much of the nonlinear properties
of such magnetodynamics are still being explored at the time of this writing. For
such exploration, the new metrologies developed during the last two decades have
become very important; those of XMCD-based spin-resolved and time-resolved
microscopy with sub-20 nm resolution have enabled direct observation of many
such dynamic states, accelerating in many cases our understanding of such complex
27 Magnetization Dynamics 1355
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27 Magnetization Dynamics 1365
Contents
Permanent Magnets and Physics Behind Them . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374
Stray Fields and Demagnetizing Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1376
On the Thermodynamics of Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379
Hysteresis Curves and Magnetization Processes of Permanent Magnets . . . . . . . . . . . . . . 1384
Permanent Magnet Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1387
Hard Magnetic Steels and Alnico . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
Hard Ferrite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1392
Rare-Earth Magnets Based on SmCo5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1394
Sm2 Co17 -Based Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1395
Nd2 Fe14 B-Based Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1397
Other Permanent Magnet Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1401
Resource Constraints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1405
Future Permanent Magnet Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1409
Permanent Magnet Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1412
Permanent Magnet Assemblies and Their Dynamic Application with
Mechanical Recoil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1413
Dynamic Applications with Active Recoil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1421
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1425
K.-H. Müller
IFW Dresden, Institute for Metallic Materials, Dresden, Germany
S. Sawatzki
Technische Universität Darmstadt, Materialwissenschaft, Darmstadt, Germany
Vacuumschmelze GmbH & Co.KG, Hanau, Germany
e-mail: [email protected]
R. Gauß
EIT RawMaterials GmbH, Berlin, Germany
e-mail: [email protected]
O. Gutfleisch ()
Technische Universität Darmstadt, Materialwissenschaft, Darmstadt, Germany
e-mail: [email protected]
© Springer Nature Switzerland AG 2021 1369
J. M. D. Coey, S. S. P. Parkin (eds.), Handbook of Magnetism and Magnetic
Materials, https://doi.org/10.1007/978-3-030-63210-6_29
1370 K.-H. Müller et al.
Abstract
A Exchange constant
Ag Cross-sectional areas of a cavity
Am Cross-sectional areas of a magnet
AC Alternating current
B Vector of the flux density (or induction)
B(r) Flux density (or induction) depending on the position
r
B Magnitude of the flux density (or induction)
(BH )max “Energy product,” i.e., the maximum value of (−BH )
of a homogeneously magnetized body measured on its
major hysteresis loop, sometimes called energy density
(BH )u “Recoil product,” i.e., the maximum energy product in
a dynamic application with mechanical recoil
C Torque constant of a motor
d-HDDR Dynamic hydrogenation-disproportionation-
desorption-recombination
d Distance of a small air gap
Dc Critical single-domain particle diameter
28 Permanent Magnet Materials and Applications 1371
A permanent magnet (PM), also called hard magnet, is a piece of material that cre-
ates a magnetic field outside that material without the need for any external source of
power. In this section, we will briefly summarize the physics of phenomena typically
found for the PM. More details can be found in Chapters “ATO,” “EXC,” “ANI,”
“MPT,” “MIC,” “DOM,” “ELE,” “MMA,” and “MOX.”
An important class of PMs are bodies that carry a persistent magnetization vector
M(r, T , {H }) depending on the position r in the body, the temperature T , and the
history, {H }, of the externally applied magnetic field H . This influence of the
history {H } will be discussed in section “On the Thermodynamics of Magnets”.
The vector M(r, T , {H }) is an ingredient of the continuum theory of mag-
netism called micromagnetism or micromagnetics [1, 2, 3]. For a typical PM
material based on a uniaxial (tetragonal, rhombohedral, or hexagonal) magnetic
phase, the simplest version of micromagnetism contains three material properties:
the magnitude of the spontaneous magnetization, Ms ; the so-called second-order
anisotropy constant K1 > 0; and the exchange constant A. These properties
are not constants but functions of temperature and are assumed to be independent
of H . It is known that Ms is based on microscopic magnetic moments that are
closely related to the orbital and spin momentum of valence electrons and are
strongly coupled by exchange interaction, resulting in cooperative phenomena such
as ferromagnetism (as in Fe or Nd2 Fe14 B) or ferrimagnetism (as in (Ba,Sr)Fe12 O19
or in lodestone composed of Fe3 O4 , which is the main source of rock magnetism)
or canted antiferromagnets which show weak ferromagnetism (as in hematite,
α-Fe2 O3 , that has a very small value of Ms but if present in large amounts
contributes to natural magnetic remanence of rocks and, consequently, plays an
important role in paleomagnetism).
A finite magnetization Ms can only exist at room temperature because the
exchange interaction between the concerned spins is very strong. It arises from the
electrostatic (Coulomb) interaction between electrons under the rules of quantum
mechanics, in particular the Pauli exclusion principle [4]. In micromagnetism,
the exchange interaction between neighboring parts of a material is represented
by the exchange parameter A. The persistence of the magnetization of a PM
material in a particular direction is due to magnetic anisotropy represented by
K1 . If in a uniaxial material K1 > 0, such preferred directions are parallel to
the crystallographic c-axis, which is then called the easy axis of magnetization.
The magnetic anisotropy can be based on different microscopic mechanisms. In
modern PM materials, its dominant mechanism has two components. The first
component is the electron orbitals and with them the orbital magnetic moments,
which are coupled to the crystal axes by electrostatic forces (again governed by
quantum mechanics). This was first described by Hans Bethe who investigated
this effect for certain materials, and he related these forces to crystalline electric
fields (Kristallfeld – in German) [5]. The second component is the spin-orbit
interaction that mediates this anisotropy to the spins, which mainly contributes to
28 Permanent Magnet Materials and Applications 1375
the magnetization Ms . The crystalline electric fields obviously do not have rotational
symmetry, and, consequently, the orbital magnetic moments observed in free atoms
or ions are quenched in the solid (at least partially). Hence, magnetic and electric
phenomena are not only closely connected according to the electrodynamics of
Maxwell or Einstein’s theory of relativity but also in terms of exchange interaction
and magnetic anisotropy, which are magnetic phenomena but result from the
electrostatic Coulomb interaction. A different type of magnetic anisotropy, shape
anisotropy, will be discussed in section “Hard Magnetic Steels and Alnico”.
In ferrite magnets based on BaFe12 O19 and SrFe12 O19 , which represent the lion’s
share by mass of the PM shipped worldwide each year [6], the magnetization is
exclusively a superposition of the spin magnetic moments of Fe3+ ions (from 5 of
their 23 electrons). In Nd2 Fe14 B-based materials, which dominate the PM world
market by value [7], besides the contribution of spin magnetic moments, a few
percent of the magnetization is contributed by Nd 4f orbital magnetic moments,
because they are not quenched due to the strong spin-orbit interaction resisting the
crystalline electric fields in the rare earths [8].
The intrinsic properties Ms , A, and K1 of a material lead to the anisotropy-related
exchange length
A
lκ = (1)
K1
and further intrinsic magnetic lengths li of the system that are generally given by
K1
li = lκ Fi (κ) with κ 2 = (2)
μ0 Ms2
where Fi (κ) is a function of the hardness parameter κ [9], relating the anisotropy
energy to the magnetostatic energy, and μ0 is the permeability of free space.
Micromagnetism is a mesoscopic theory, and limits of its validity arise if it predicts
phenomena on length scales li which are not considerably larger than the lattice
constant of the considered magnetic phase.
Alternatively, a piece of superconducting material can also be magnetized and
can be used as a permanent magnet [10,11]. Much higher fields can be realized using
superconducting permanent magnets compared to that of their ferromagnetic
counterparts. Trapped fields as high as 16 T could be achieved at 24 K in the gap
between two YBa2 Cu3 O7−δ superconducting bulk samples (25 mm in diameter)
which were doped with Zr and Ag and placed inside of a reinforcing stainless steel
tube [12]. An even higher trapped field of 17.6 T at 26 K was reported for a stack
of two Ag-doped GdBa2 Cu3 O7−δ superconducting bulk samples, each 25 mm in
diameter, reinforced with shrink-fit stainless steel [13]. However, superconducting
permanent magnets only exist at cryogenic temperatures, and they will not be further
considered in this chapter.
1376 K.-H. Müller et al.
∇ × H (r) = 0 (3)
∇ ◦ M(r) + H (r) = 0 (4)
where the spatial dependence of M(r) describes the transition from the uniformly
magnetized body to its nonmagnetic environment. To solve (3) and (4) is straightfor-
ward but laborious [14]. As an example, Fig. 1 schematically shows the field H (r)
and the induction or flux density
B(r) = μ0 M(r) + H (r) (5)
The volume average of the field within a uniformly magnetized body of arbitrary
shape is given by
H V = −N M (6)
N1 + N2 + N3 = 1. (7)
Fig. 3 Uniformly
magnetized spheroidal shell
based on two ellipsoids with
the demagnetization factors
Na and Ni and values of H at
the indicated positions. N is
the (unknown)
demagnetization factor of the
shell
Fig. 4 (Left) Uniformly magnetized long hollow cylinder; (right) long Halbach cylinder; at the
position ∗, the field in the material has the same value as in the bore, H . Thick arrows indicate the
local direction of the magnetization M
where r1 and r2 are the radii of the inner and the outer cylinder, respectively. Hence,
for (r2 /r1 ) > 2.72, the field in the bore, H , will be larger than M. However,
such field concentration has its price as can be seen in Fig. 4: because the field is
irrotational, its value at the position ∗ in the material is also H , i.e., it is antiparallel
to M. Consequently, H can only increase with increasing r2 /r1 as long as the
coercivity of the material is larger than H given by (8). For comparison, Fig. 4 also
shows that inside a homogeneously magnetized hollow cylinder, the field is zero, as
in the hole of the shell of Fig. 2.
√
AK1
Ds ≈ 3 Dc with Dc = 72 lκ κ = 72 2
. (9)
μ0 Ms2
1380 K.-H. Müller et al.
W.F. Brown has shown that, in thermal equilibrium, there is a certain critical
diameter Dc above which spherical samples consisting of easy-axis material are not
in a homogeneous state but are nonuniformly magnetized [23], and the value of
the critical single-domain particle diameter Dc in (9) had been estimated by Kittel
[24]. According to Coey (9), the value of Dc can be easily obtained from pictures
of domains on grains in, for example, as-cast material such as in Fig. 5.
Non-homogeneous equilibrium states of chemically homogeneous systems such
as the domain structure at zero external field, H = 0, in Fig. 5 are not uncommon
in thermodynamics and are examples of spontaneously broken symmetry, like the
coexistence of water and vapor of H2 O at fixed values of volume and temperature
[25]. In an approximation neglecting the interface energy and the stray field energy,
the two types of magnetic domains, that is, the brighter and darker areas in Fig. 5
with magnetizations antiparallel to each other and parallel to the easy axis (i.e.,
the crystallographic c-axis), can be considered as different thermodynamic phases
coexisting at H = 0 [26]. The detailed shape of the equilibrium domain structure
results from taking into account interface energy and stray field energy. At H = 0,
in thermodynamic equilibrium, the net magnetization of a PM is zero, and the field
created by it is very small. If the grain size of the easy-axis magnetic main phase in
the material is considerably larger than Dc , such demagnetized states are realized
by magnetic domains within the grains as can be seen in Fig. 5. The width of the
interface between those domains, the Bloch wall width, is given by
A
δw = π l κ = π (10)
K1
states will develop as, for example, interaction domains shown in Fig. 6. The width
of these domain-like patterns is considerably larger than the grain size, and they are
not limited by regions, such as Bloch walls, which are smooth and can be easily
mathematically described [28].
PM materials are developed to create stray fields H at zero applied fields H and
even for finite H antiparallel to H . Thus, as a matter of principle, magnetized
PM are in relatively stable non-equilibrium metastable states. These states and,
in particular, their volume average of magnetization MV depend not only on
the actual applied field H but also on the time dependence of H in the past.
This phenomenon is known as magnetic hysteresis. Usually only the component
of MV ≡ M parallel to H is considered. As can be seen in Fig. 7, in a typical
PM, the hysteretic behavior disappears for sufficiently large fields |H | where a
unique dependence M(H ) corresponding to thermal equilibrium is observed. For
values of (M, H ) within the major hysteresis loop which is obtained by starting
the measurements at large positive or negative H , an infinite number of different
M(H ) curves can be measured belonging to different magnetic histories {H } of
the magnet. In Fig. 7, besides the major hysteresis loop, the initial magnetization
curve is shown, which is just one of this infinite number of curves.
Due to their non-equilibrium character, the hysteretic states show small effects
of relaxation called magnetic viscosity or magnetic aftereffect or time lag in
magnetization as discovered by J.A. Ewing [29]. The result of a typical viscosity
experiment is shown in Fig. 8. For a large class of experiments, a logarithmic time
law
has been found where S is the magnetic viscosity and t0 is some reference time
depending on the investigated sample as well as on the measuring procedure. The
first theoretical analysis of magnetic viscosity was done by F. Preisach [30], who
1382 K.-H. Müller et al.
Fig. 7 Magnetization curves of a typical permanent magnet; thick blue, measured major hysteresis
loop with Mr as the remanence and Hc the coercivity; thin blue, initial magnetization curve (or
virgin curve) starting at the thermally demagnetized state; arrows indicate the direction of field
changes; dashed dark blue, states of thermal equilibrium
suggested that it is based on thermal fluctuations and pointed out that the logarithmic
time dependence can be understood as a superposition of exponential relaxation
processes with a broad range of participating relaxation times. Later it was found
that the magnetic viscosity S does not go to zero but approaches a finite constant
value at low temperatures, and the reason for this observation is that quantum
tunneling of magnetization also results in magnetic viscosity, that is, in addition to
thermal fluctuations [31]. Preisach introduced a simple model connecting hysteresis
with viscosity. In this model, ferromagnetic materials are considered as collections
of bistable units each of them characterized by its individual rectangular non-
symmetric hysteresis loop (see Fig. 9). If the state of such an individual unit is on
its upper branch (js ) or its lower branch (−js ) and the applied field H is near the
critical value b − a or b + a, respectively, very small changes of H will result in
switching of that unit and, consequently, will contribute to an irreversible change of
the total magnetization M along macroscopic hysteresis curves of the material. In
such a critical state of the bistable unit, switching would also be caused by small
thermal fluctuations, thus contributing to the aftereffect, that is, to a spontaneous
28 Permanent Magnet Materials and Applications 1383
change of M at constant H . In recent years, Preisach-type models had a great
renaissance [32] and have been widely used to describe hysteresis as well as
relaxation phenomena.
In a thermodynamic description of uniformly magnetized materials, thermal
equilibrium is described by the Gibbs free energy G(p, T , H ), which is the
thermodynamic potential for given values of pressure, temperature, and external
field, p, T, and H , respectively, and equilibrium states as those represented by the
dashed dark-blue curve in Fig. 7 should be given by
1 ∂G
M(H ) = − (12)
μ0 V ∂H p,T
where V is the volume of the magnet. The Gibbs free energy G of a system in
the absence of an internal constraint is the minimum of the Gibbs free energy of a
manifold of constrained equilibrium states, G̃, [33]. This can be expressed by
G(p, T , H ) ≤ G̃(p, T , H ; λ) (13)
Ĝ(A, K, H ; [M(r )]) → min with |M(r )| = Ms (14)
The data characterizing the hysteretic behavior of a PM material are called extrinsic
properties because they are governed not only by the intrinsic magnetic properties
of the main phase in the material, which are in the simplest cases the quantities Ms ,
K1 , A, and Tc , but also by details of the microstructure of the material. One of the
important extrinsic properties is the remanent magnetization or simply remanence
Mr (see Figs. 7 and 10). Obviously an upper limit for the remanence of a material
is the spontaneous magnetization of its magnetic main phase, Mr ≤ Ms . The
difference between Mr and Ms is mainly caused by incomplete magnetic alignment
and by the presence of additional phases in the material.
and consequently
dV BH = − dV BH = −μ0 dV H 2 = −2 Eout (16)
body out out
or
Eout
B(−H )body = 2 . (17)
V
Hence, the volume average of −BH within the magnetized body is twice the value
of the magnetostatic energy Eout created by that body outside of it, divided by its
volume. If M, B, and H are uniform in the body, averaging is not needed, and
the negative value of BH of the magnet is often slightly incorrectly termed its
energy product (or energy density). The second quadrant of a major hysteresis
loop like that in Fig. 7 can be realized by using the magnets’ own demagnetizing
field H instead of the external field H , for example, by using ellipsoids with one
of their principal axes parallel to the magnetization M. If now the corresponding
demagnetization factor N varies between 0 and 1 (long cigar to flat disc), the value
of B runs from Br = μ0 Mr to 0, representing the second quadrant of the major
B − H demagnetization curve (see Fig. 10). Obviously, on that path on the B − H
curve, (−BH ) starts and ends at the value 0 and achieves somewhere in between
its maximum value, which is the so-called maximum energy product (BH )max ,
one of the most important extrinsic magnetic properties of a PM material. In our
gedanken experiment with the varying ellipsoids, in case of the PM material of
Fig. 10, the demagnetization factor needed to achieve the (BH )max is N = 1/2, and
we have (−BH )max = μ0 Mr2 /4. If Hc in Fig. 10 were smaller than Mr /2, the value
of (−BH )max would be smaller than μ0 Mr2 /4 and would be limited by Hc as will
be discussed later (see (22)). It is obvious that these results can be generalized to the
case of an arbitrary major demagnetization curve:
Hc Mr . (19)
K1
Hc > 2 − NMs (20)
μ0 M s
as a lower bound for the coercivity (in terms of the external field as specified
in Fig. 7) of an ellipsoid with one of its principal axes, as characterized by the
demagnetization factor N, being parallel to the external field H ; and the ellipsoid
is assumed to consist of a homogeneous material characterized by a spontaneous
magnetization Ms , an exchange constant A, and the second-order anisotropy
constant K1 , and the presence of nonvanishing higher-order anisotropy constants
is not excluded [36]. It should be noted that (20) is independent of the sample
size! Although this inequality is a rigorous result of micromagnetism, the Hc values
measured on real specimens are orders of magnitudes smaller than the right-hand
side of (20) in most cases. Only in some rare cases of magnets obtained by great
efforts in industry and laboratories a coercivity could be achieved that exceeds
20 to 30 percent of the right-hand side of (20) [37]. These discrepancies, known
as “Brown’s paradox,” can only be explained by the fact that the assumptions
made by Brown are never met in real situations. Thus the samples are never fully
aligned ellipsoids, and, consequently, there are always components of the stray field
H perpendicular to H . Also, as discussed above, at corners or other irregularities
of the microstructure, the magnitude of H can be rather large. Furthermore, there
will always be local deviations from the regular chemical composition that result in
local magnetic softening. It is not yet well investigated how far these and further
irregularities may result in destabilization of the metastable magnetized states. At
this point, the well-known observation by J. C. Barbier [38] is helpful, who showed
that for a large class of magnetic materials, the coercivity Hc is strongly correlated
to the viscosity coefficient Sv (Fig. 11), which is connected to the viscosity in (11)
by S = χirr Sv , with χirr as the irreversible part of the susceptibility.
Furthermore Sv is related to the activation volume va in which the thermally
activated elementary processes of viscosity experiments are thought to take place
[39, 10]:
kB T
va = (21)
μ0 Sv Ms
grained magnets with weakly interacting magnetic grains that are larger than Dc
from (9) have been successfully considered as nucleation-controlled magnets or
pinning-controlled magnets with large or small initial susceptibilities, respectively
(see Fig. 7) [42]. Prime examples for nucleation-controlled magnets are sintered
magnets based on SmCo5 and Nd2 Fe14 B, whereas magnets based on Sm2 Co17 are
usually considered as typical pinning-controlled magnets [42]. In both scenarios,
nucleation of reverse domains as well as pinning of domain walls, the elementary
processes are also assumed to take place in small spatial regions. Interestingly, it
has been found that the 2:17-type magnets could be also (and even better) described
as being controlled by interaction domains (similar as those in Fig. 6) where the
Sm2 Co17 cells of 50 to 100 nm in size have to be considered as weakly interacting
“grains” [43]. Generally the large class of fine-grained materials obtained, for
instance, by rapid quenching, mechanical milling, and HDDR processing, with
typical grain sizes smaller than Dc (often termed as nanocrystalline materials),
cannot be described as being nucleation controlled or pinning controlled but have to
be treated separately [44].
The first permanent magnet known to man was lodestone based on the common
mineral magnetite, Fe3 O4 . The ancient civilizations in Sumer, China, Europe, and
America were familiar with the natural magic of this magnet. It has not only
been a subject of curiosity, but already in ancient China, it has also been used
to manufacture a precursor of the modern compass [45]. At room temperature,
magnetite is cubic, and [111] are the easy axes of magnetization. Its spontaneous
1388 K.-H. Müller et al.
Mr ≈ Hc /N. (23)
It should be noted that the expression for Mr in (23) does not depend on Ms
and is usually below 0.1 T in lodestones and (BH )max < 1 kJ/m3 . In modern times,
lodestones have been replaced by artificial man-made magnets, and in particular,
in the twentieth century, (BH )max was improved enormously as can be seen in
Fig. 12.
In order to obtain a PM, the PM material has finally to be magnetized. For
the natural lodestones, the leading theory suggests that they were magnetized by
strong lightning strikes [48]. In the middle ages, in China as well as in Europe,
compass needles were made of steel and have been magnetized by touching them
with a lodestone or by quenching them from red heat in the Earth’s magnetic
field [9]. Since the nineteenth century, the steel magnets have been magnetized by
electromagnets, whereas since the twentieth century, magnetizing is mainly done
by using pulsed magnetic fields in the range of 1 to 10 Teslas with pulse lengths
of typically 0.5 to 1000 milliseconds, where capacitive discharge magnetizers are
mostly used. Because there are many technical difficulties in assembling devices like
motors, using magnetized magnets, post-assembly magnetizing has been developed,
where the magnets become magnetized in the final step of the device manufacturing
process. For this purpose, sophisticated magnetizing fixtures may have to be
designed [49]. A further special feature of modern magnetizers is that, if needed,
they can generate multipole magnetizations. Figure 13 shows a six-pole ring magnet
made by backward extrusion (at 750 ◦ C) of rapidly quenched Nd-Fe-B powder,
prepared to construct a brushless servomotor [50]. The hot deformation results in
a radial texture, where the local magnetically easy axis of the Nd2 Fe14 B phase in
the hollow cylinder is radially oriented, in contrast to the cases of hollow cylinders
28 Permanent Magnet Materials and Applications 1389
Fig. 12 Development of the “energy product” (BH )max in the twentieth century. Illustrating
the results, the different cylinders have a relative volume needed to store the same amount of
magnetostatic energy in the corresponding material. (Modified after [7])
in Fig. 4. The cylinder of Fig. 13 has a length of 25 mm, an outer diameter of about
33 mm, and an inner diameter of 27 mm. To obtain the six-pole field configuration
shown in the figure, a corresponding magnetizing coil for a pulse magnetizer needs
to be constructed.
In the following, we will discuss the properties of the most relevant materials
in the development shown in Fig. 12 – steel and alnico, hard ferrites, and rare-
earth material based on SmCo5 , Sm2 Co17 , and Nd2 Fe14 B. We will also consider
some further materials with remarkable properties and, in particular, those that are
considered as candidates for future PM materials.
1390 K.-H. Müller et al.
The abovementioned compass needles made of steel are the first artificial permanent
magnets. Until the beginning of the twentieth century, the strongest magnets were
martensitic carbon steels, mainly consisting of the metastable martensite phase α -
Fe(C), stable phase ferrite α-Fe(C), residual austenite γ-Fe(C), and precipitations
of cementite Fe3 C. Their (BH )max was typically 3 kJ/m3 . Later, (BH )max was
increased by adding W, Cr, Mo, and/or Co. The strongest steel magnets have been
developed around 1920 in Japan. They contained the four elements Fe, C, Cr, and Co
and had a (BH )max of about 8 kJ/m3 [48]. Interestingly, the term “hard magnetic”
was originally used because the martensite steels are mechanically hard. Obviously,
the coercivity of steels not exceeding 10 mT is based on pinning of domain walls,
but the details of the pinning mechanism have not yet really been investigated. In
particular, the effect of the mentioned alloying elements and of the tetragonality of
a α -Fe(C) martensite (space group I4/mmm) are not yet understood.
In the 1930s, the research on hard magnetic steels led to the development of
a new iron-based series of compounds that were later named Alnico and had its
commercial success in the 1950s. This subject has been comprehensively reviewed
by several authors [51,52]. Besides the main components Fe, Co, Al, and Ni, Alnico
contains various further additives. The crucial difference between Alnico and hard
magnetic steels is that in Alnico, magnetic shape anisotropy is formed in addition
to the magnetocrystalline anisotropy where the latter is relatively weak in both types
of materials. Shape anisotropy stands for the fact that the magnetostatic energy of
an arbitrarily shaped uniformly magnetized body depends on the direction of its
magnetization M by
1
Em = μ0 V M N M (24)
2
where V is the body’s volume and N is its demagnetization tensor (6) [1]. In case
of axial symmetry, that is, if one of the principal axes of N has an eigenvalue
(demagnetization factor) of N and the other eigenvalues are 1/2 (1 − N ), one
can conclude from (24) that an effective anisotropy constant
(m) 1
K1 = μ0 (1 − 3N )M 2 (25)
4
of the needles. Obviously, the shape anisotropy is strong if the needles are thin and
long, and, consequently, N is small.
With the introduction of Alnico, it became possible, for the first time, to
replace electromagnets with permanent magnets in many devices such as generators,
motors, and microphones, which was a revolution in the use of permanent magnets.
The main advantage of Alnico is its structural as well as magnetic temperature
stability (its Curie temperature is 700 to 850 ◦ C [52]). Its biggest disadvantage is the
poor resistance to self-demagnetization due to its small coercivity Hc as compared
to remanent magnetization Mr (Table 1). The answer to this problem is the use
of horseshoe magnets that are known since the eighteenth century [9]. A typical
Alnico horseshoe magnet is shown in Fig. 14. The effect of its shape can be made
plausible as follows. Compact bodies have a demagnetization factor of typically
N ≈ 1/3, that is, if they are uniformly magnetized by a magnetization M, their
average demagnetizing field is about −M/3, which, according to Table 1, is much
too strong to maintain the magnetization M ≈ Mr of magnetic steel or Alnico.
Even in the case of a long rod with N 1, the demagnetizing field in the rod
close to its face side (position ∗ in Fig. 1) is −M/2, so even a long rod of Alnico
cannot be completely magnetized. If now the rod is imagined to be bent around
into a torus with a narrow gap (see Fig. 14, left), the demagnetizing field at the
position ∗ becomes very small, and the field within the gap will be H ≈ Mr . In
some approximation, a horseshoe magnet can be considered as a gapped ring as
shown in Fig. 14. Systems composed of magnets, air gaps of finite width, and soft-
magnetic segments are called magnetic circuits and are well described in many
publications [56,54,9]. Although Alnicos are still used in many special applications,
they have been gradually priced out of the market with the availability of hard
1392 K.-H. Müller et al.
ferrites and rare-earth magnets that can be made in any desired shape, without
having to resort to horseshoes to avoid self-demagnetization. Thus, Alnico magnets
saw no significant advancement in composition or processing since the 1970s,
until quite recently, stimulated by the rare-earth supply crisis and much advanced
characterization techniques [55, 57], new research started to better understand the
microstructure of Alnico and to improve its permanent magnet properties [55].
Hard Ferrite
The term ferrite is used for a wide class of iron-based oxides and, in metallurgy,
also for bcc α-Fe(C), whereas the term hard ferrite is usually confined to permanent
magnets based on the hexagonal compounds strontium ferrite, SrFe12 O19 (or
SrO·6Fe2 O3 ), and barium ferrite, BaFe12 O19 (or BaO·6Fe2 O3 ), discovered in 1951
in the Netherlands [58]. The dashed line in Fig. 12 represents Co-ferrite magnets
based on CoFe2 O4 that show (BH )max values of typically 1 kJ/m3 [59, 60].
CoFe2 O4 has the same spinel structure as Fe3 O4 . Intrinsic magnetic properties of
the hexagonal ferrites are shown in Table 2. As can be seen there, the anisotropy field
Ha of these compounds is considerably larger than their spontaneous magnetization
Ms . Thus, it was possible, for the first time, to prepare permanent magnets in any
desired shape without having to fear self-demagnetization. This is the main reason
why hard ferrites are much more common than Alnico although the energy density
(BH )max of the latter is considerably larger (see Fig. 12). The ferrite magnets based
on SrFe12 O19 are the most common, and according to [9], the following extrinsic
properties have been achieved for them: remanent magnetization μ0 Mr = 0.42 T,
coercivity (as defined in Fig. 7) μ0 Hc = 0.3 to 0.4 T, and maximum energy product
(BH )max = 34 kJ/m3 . Usually powders with particle sizes around 1 micron are
aligned in an external field and then sintered. A further advantage of the hard ferrites
in addition to their relatively large coercivity is their very low price as well as their
chemical stability and good corrosion resistance. The anisotropy field in Table 2 is
given by
K1
Ha = 2 . (26)
μ0 M s
Table 2 Curie temperature Tc and room-temperature values of other intrinsic magnetic properties
of some hexagonal ferrites. The data are taken from [9], with A, exchange constant; K1 , second-
order anisotropy constant; Ha , anisotropy field (26); Ms , spontaneous magnetization; κ, hardness
parameter (2); δw , Bloch wall width (10); and Dc , critical single-domain particle diameter (9)
Phase Tc A K1 μ0 Ha μ0 M s κ δw Dc
(K) (pJm−1 ) (MJm−3 ) (T) (T) (nm) (μm)
BaFe12 O19 742 6 0.33 1.7 0.48 1.3 13.6 0.56
SrFe12 O19 746 0.35 1.8 0.48
PbFe12 O19 725 0.25 1.5 0.41
28 Permanent Magnet Materials and Applications 1393
Fig. 15 Temperature
dependence of the anisotropy
fields of BaFe12 O19 and
SrFe12 O19 . (Reproduced
from [62], with the
permission of AIP
Publishing)
Hc = α Ha − Neff Ms (27)
Table 3 Curie temperature Tc and room-temperature values of further intrinsic magnetic proper-
ties of uniaxial ferromagnetic and ferrimagnetic phases commercially used for permanent magnets.
The data are taken from [9] with the exception of (1) , which is taken from [71], with A, exchange
constant; K1 , second-order anisotropy constant; Ha , anisotropy field (26); Ms , spontaneous
magnetization; κ, hardness parameter (2); δw , Bloch wall width (10); and Dc , critical single-
domain particle diameter (9)
Phase Crystal Tc A K1 μ0 Ha μ0 M s κ δw Dc
system (K) (pJm−1 ) (MJm−3 ) (T) (T) (nm) (μm)
BaFe12 O19 Hexagonal 740 6 0.33 1.7 0.48 1.3 13 0.6
SmCo5 Hexagonal 1020 12 17 40 1.07 4.3 2.6 1.2
Sm2 Co17 Trigonal 1190 16 4.2 6.5 1.3 1.8 5.7 0.5 (1)
Nd2 Fe14 B Tetragonal 585 8 4.9 6.7 1.61 2.5 4 0.2
significantly smaller than the Curie temperature; it also depends on how fast the
coercivity decreases with increasing temperature and up to which temperature the
microstructure of the material remains stable. Commercial SmCo5 magnets can be
used at temperatures up to 250 ◦ C or even higher because their intrinsic properties as
well as their microstructure are sufficiently stable. The values of remanence μ0 Mr ,
coercivity μ0 Hc , and energy product (BH )max achieved in them are 0.95 T, 2.5 T,
and 200 kJ/m3 , respectively. More detailed information on SmCo5 magnets can be
found in [75, 76] and [52].
but its structure and chemistry are still somewhat controversial [43]. These lamellae
are considered to stabilize the cellular microstructure and, more importantly, to
modify the phase-ordering kinetics needed to obtain high-performance materials
[77]. The Z-phase has reported to be ferromagnetic with a Curie temperature of 473
K [79].
It has been proposed [80] that the coercivity of well-prepared 2:17-type magnets
is controlled by pinning of domain walls at the 1:5 cell boundaries. This is generally
accepted in literature and is in accordance with the magnetization behavior of these
magnets [81]. It should be noted that microstructures similar as that shown in
Fig. 16 and, consequently, high magnetic hardness of SmCo 2:17-type magnets are
achievable for various processing routes, namely, not only in sintered magnets but
also in ingot materials [78] and in melt-spun ribbons [82, 83]. In other words, the
actual grain size itself, pivotal for the magnetization reversal in many other PM
materials, plays only a minor role in 2:17 SmCo magnets. A crucial step in magnetic
hardening of this material is a final slow cooling from 850 ◦ C to 400 ◦ C (0.7 K/min),
which does not significantly change the cellular and lamellar microstructure but
results in a diffusion of copper from the 2:17 cell interior into the 1:5 cell boundary
phase (see Fig. 16) [84]. Furthermore, it has been shown that after the slow cooling,
the copper shows a strong maximum of its concentration in the middle of the cell
boundaries, probably much reducing the exchange interaction between neighboring
2:17 cells [82]. Consequently this material should behave like a well-textured fine-
grained material. This concept is supported by the domain patterns shown in Fig. 17
that are notably similar to those of Fig. 6 and can be considered as interaction
domains [43]. In Fig. 17, it can be seen that magnetic hardening of the 2:17 magnets
by chemical modification of the 1:5 cell boundaries not only changes domain
Fig. 17 Magnetic domain structure observed by magnetic force microscopy of a thermally demag-
netized Sm(Co0.784 Fe0.100 Cu0.088 Zr0.028 )7.19 magnet, with the nominal c-axis of the rhombohedral
Sm2 Co17 phase perpendicular to the imaging plane; (left), slowly cooled from 850 ◦ C to 400 ◦ C
(i.e., in the high coercivity state); (right), quenched from 850 ◦ C (low coercivity state). (Modified
after [43])
28 Permanent Magnet Materials and Applications 1397
wall pinning forces but changes the domain patterns themselves drastically. More
detailed information on Sm2 Co17 -type magnets and their history can be found in
[75, 76, 85, 86] and [52].
Fig. 18 Dependence of
(BH )max on temperature for
sintered PM materials.
(Modified after [95])
1398 K.-H. Müller et al.
Nd-rich GBs are few nanometers thick and separate the 2:14:1 grains with respect to
exchange interaction, making the coercivity in sintered Nd-Fe-B magnets controlled
by nucleation of reverse magnetic domains [89, 96, 97]. Sagawa et al. found that the
coercivity of sintered Nd-Fe-B magnets can be considerably improved by a post-
sinter heat treatment at a temperature somewhere between 500 and 600 ◦ C, and they
explained this effect by a modification of the solidified liquid eutectic Nd-rich phase
[89]. If the magnets are doped by further elements like Cu and Al, the increase
of coercivity caused by such post-sinter annealing (PSA) can be remarkably large
[98]. Meanwhile, many investigations of this important effect have been published,
but it is not well understood. Certainly, solidification of thin layers of the liquid
eutectic phase will not result in the relatively coarse two-phase heterostructures
known for bulk eutectic systems. Nevertheless, the formation of non-homogeneous
concentration profiles, comparable to those observed in the cell boundaries of
heat-treated Sm2 Co17 -based magnets, as discussed in section “Sm2 Co17 -Based
Magnets”, cannot be excluded. Examples of mechanisms proposed in literature are
during PSA, the liquid eutectic phase dissolves surface irregularities at the 2:14:1
grains, consequently smoothing them [99]; PSA improves wetting of the 2:14:1
grains by the liquid eutectic phase [100]; PSA results in a beneficial redistribution
of Nd-rich material between the triple junctions and the GBs [101]; and even the
presence of a ferromagnetic phase in the GBs, caused by PSA, has been reported
[102, 103], what is in contrast to the commonly accepted paramagnetic GB model.
The extrinsic properties (BH )max , Hc , and Mr of sintered 2:14:1-based magnets
cannot be further improved much. However, in view of the expected increasing
demand in strong sintered Nd-Fe-B magnets, the process for producing them has
to be improved to get high-performance magnets at lower cost [104]. Two recent
developments are particularly interesting, the so-called pressless process (PLP) and
grain boundary diffusion (GBD) of Dy and Tb. In the case of PLP, the Nd-Fe-B alloy
powder is aligned in a pulsed field, but no heavy press machine and no dc electric
magnet are needed. Therefore, extremely fine and reactive powders with particle
sizes down to 1 μm, which requires milling in He, can be used and sintered without
serious oxidation, and, therefore, sufficiently large coercivity can be achieved for
magnets with reduced or even zero Dy content [105]. The Dy additions in Nd-
Fe-B magnets increase their anisotropy field Ha and, consequently, increase their
coercivity and their operating temperature. On the other hand, the Dy as well as
the Tb additions decrease the remanence Mr because the magnetic moments of
these heavy rare earths couple antiferromagnetically to the Fe moments, and, as
a further drawback, Dy and Tb are considerably more expensive than Nd. GBD is
successfully used to reduce the content of Dy needed in Nd-Fe-B magnets [106].
Thereby, small Dy-free magnets [107] or melt-spun ribbons [108] are coated with
a Dy-rich material, and in a subsequent heat treatment or during hot compaction, it
diffuses along grain boundaries into the interior of the magnet. There the Dy will
be mainly located in the intergranular regions and in regions of the 2:14:1 grains
that are close to the GBs, that is, at positions where nucleation of reverse magnetic
domains takes place. High-coercivity Nd-Fe-B without heavy rare-earth additions
could also be obtained by thick-film technology [109].
28 Permanent Magnet Materials and Applications 1399
Fig. 19 Flowchart illustrating the principal processing routes of Nd-Fe-B permanent magnets
based on coarse-grained and nanocrystalline powders. (Modified after [44])
1400 K.-H. Müller et al.
Table 5 Ferromagnetic and ferrimagnetic phases used to develop permanent magnet materials
[71, 117]
Phase Symmetry Tc μ0 M s μ0 Ha K1 δw Dc
(K) (T) (T) (MJ/m3 ) (nm) (nm)
α-Fe Cubic 1043 2.16
Fe65 Co35 Cubic 1170 2.43
Co Hexagonal 1390 1.81 0.76 0.43 14 68
Nd2 Fe14 B Tetragonal 585 1.61 6.7 4.9 3.9 ∼300
Pr2 Fe14 B Tetragonal 567 1.56 8.7 5 ∼4 ∼300
Dy2 Fe14 B Tetragonal 598 0.71 15.0 4.2 ∼4
Tb2 Fe14 B Tetragonal 620 0.70 22.0 6.4 ∼4
Nd2 Fe14 C Tetragonal 532 1.41 9.5 5.4 ∼4 ∼300
Y2 Fe14 B Tetragonal 575 1.32 1.05
Sm2 Fe17 N3 Rhombohedral 749 1.54 14 8.6 3.6 380
Sm2 Fe17 C3 Rhombohedral 668 1.45 16 7.4 ∼300
Sm2 Co17 Rhombohedral 1100 1.3 6.5 3.3 8.6 500
SmCo5 Hexagonal 993 1.05 40 17 3.7 1700
FePt Tetragonal 750 1.45 11.5 6.6 6.3 560
FePd Tetragonal 760 1.39 3.5 1.8 11.5 330
CoPt Tetragonal 720 1.0 12.3 4.9 7.4 1000
BaFe12 O19 Hexagonal 742 0.48 1.8 0.33 14 660
(Sm0.75 Zr0.25 )(Fe0.7 Co0.3 )10 Nx Hexagonal 877 1.7 7.7 ∼300
NdFe10 V2 Ny Tetragonal 743 1.11 10 ∼300
SmFe11 Ti Tetragonal 584 1.14 10.5 4.8 4 440
YFe11 Ti Tetragonal 525 1.07 0.85
Fe3 B Tetragonal 786 1.62 ∼0.4 -0.32 20
(Fe0.7 Co0.3 )2 B Tetragonal 937 1.31 1.0 0.42
YCo5 Hexagonal 987 1.07 6.5
La2 Co7 Hexagonal 479 0.7 6.7 1.4
MnAl Tetragonal 650 0.75 1.7
MnBi Hexagonal 633 0.73 0.9
Mn2 Ga Tetragonal >770 0.59 2.35
α -Fe16 N2 Tetragonal 810 2.41 1.0
its demagnetization curve does not contain any dip or step in the second quadrant
of the M-H’ plane and that the value of Mr is larger than expected (remanence
enhancement). Furthermore, the recoil curves are very steep, and the change in
magnetization along them is nearly reversible [134] as can be seen in Fig. 20.
These properties have been explained by exchange coupling of the different types of
small grains, and the materials showing such behavior have been called exchange
spring magnets [136]. This effect is closely related to the exchange coupling
between ferromagnetic and antiferromagnetic regions in a material, resulting in
exchange anisotropy [137]. Now many exchange spring-type materials are known
obtained by different preparation routes (see Fig. 19) and combining different types
of low-anisotropy and high-anisotropy phases. Usually, such materials are non-
textured, that is, the magnetically easy axes are randomly oriented [138, 139].
Among them, those based on melt-spun Fe/Nd2 Fe14 B are still most promising.
The typically achieved (BH )max is 180 kJ/m3 [139]. The weak point of spring
magnets is their low coercivity, μ0 Hc , usually not exceeding 0.5 T. A remarkable
increase of coercivity up to more than 1 Tesla could be achieved by doping melt-
spun Nd2 Fe14 B/α-Fe spring magnets with titanium [140]. An obvious idea is to
align the easy axes of the high-anisotropy grains in the fine-grained mixture. In a
much noted paper, Skomski and Coey showed, by micromagnetic calculations, that
in such a material, (BH )max values as high as 1 MJ/m3 should be achievable if the
grain size is a few nanometers [141]. To implement this practically has proved very
challenging and is still subject of ongoing studies [142]. One of the reasons for this
difficulty is the fact that it is very challenging to orient the nanostructured high-
anisotropy phase. Furthermore, the micromagnetic approach used in [141] may be
not sensitive enough to the details of the microstructure that govern the coercivity
mechanism in real nanostructured materials. A similar situation results in Brown’s
paradox (see section “Hysteresis Curves and Magnetization Processes of Permanent
Fig. 20 Demagnetization
curve and minor loops of the
spring magnet Nd4 Fe77 B19 .
(Modified after [134])
1404 K.-H. Müller et al.
Fig. 21 Interstitially
modified rhombohedral
Th2 Zn17 -type unit cell with
three formula units of
Sm2 Fe17 N3 or Sm2 Fe17 C3
28 Permanent Magnet Materials and Applications 1405
these materials, it has to be taken into account that the Sm2 Fe17 particles are never
fully nitrided which supports nucleation of reverse magnetic domains [155]. More
about the interstitially modified R2 Fe17 compounds and magnets made of them can
be found in [156, 153, 157, 158, 52, 150, 54, 9].
Resource Constraints
The search for new permanent magnet materials goes beyond modeling and
investigating the chemical and physical properties of a given candidate material.
A truly innovative, mass-market permanent magnet material (i) will have to be
produced at low cost on an industrial scale, using non-toxic raw materials and
processing routes; (ii) is expected to have an overall small ecological footprint;
and (iii) is based on low-cost raw materials with a stable supply worldwide. A
systematic study of these kinds of material properties would involve a resource
criticality assessment. It is a tool to identify and specify potentials and risks in
the use and processing of certain strategic raw materials [159, 160, 161]. A basic
approach to resource criticality is to specify two factors, the supply risk and
the economic importance of a strategic material [162, 163]. Beyond this two-
dimensional perspective, resource criticality can be described by factors such as
geological availability, geopolitical situation, economic development, substitution
potential, recycling potential, ecological footprint, and competing technologies in
the use of specific strategic materials [161].
Indeed, history shows that crucial technological breakthroughs in the devel-
opment of permanent magnets were driven by specific technological demands,
most importantly the compass, electric motors, aerospace engineering, magnetic
recording, and automation. Likewise, the success of certain material developments
was also influenced by resource constraints. As an example, the production and
use of ferrite magnets surpassed those of Alnicos in the 1960s, although ferrites
offer much lower energy densities (see Fig. 12). In fact, the low raw material and
production costs of ferrites were a key reason for their market breakthrough. Nd-Fe-
B permanent magnets were the answer to costly Sm-Co magnets developed in the
1960s and 1970s: in 1978/1979, the cobalt price exploded sixfold, due to increasing
global demands and the civil war in the Democratic Republic of the Congo, then
and now by far the main cobalt-producing country [164, 162]. In fact, for many
years, Nd-Fe-B was considered the perfect permanent magnet material. Apart
from its unsurpassed magnetic properties, the material is composed of elements
that are abundant in the Earth’s crust and that are comparatively inexpensive.
However, despite their abundancy, prices of rare-earth metals multiplied by an
order of magnitude within few months in 2010 and 2011 (Fig. 22). The diagram
shows that the world has become dependent on Chinese rare-earth production and
market policies: the price explosion correlates with a period of absolute Chinese
market dominance. A systematic criticality assessment provides a key perspective
to evaluate (i) why this price increase happened, (ii) if the global market will
experience a similar situation again within the next years to come, and (iii) if
1406 K.-H. Müller et al.
Fig. 22 Rare-earth crisis. World mine production of rare-earth oxides (according to [165]) versus
price development of Nd, Dy, Tb, and Pr (metal prices FOB China, according to [166]). Note:
There is a considerable uncertainty in estimating REO production outputs, at least in the order of
20 %
resource and material constraints might hinder the development of key future
technologies.
Geological availability: Rare earths occur in several places worldwide. They
are currently extracted, however, almost exclusively in China, apart from minor
production volumes in countries like Thailand, Russia, India, Australia, and the
USA (Fig. 22). US production was closed in 2015 and resumed in 2018. The
relative abundance of rare earths varies in relation to their atomic number: heavy
rare earths (Gd-Lu) are much less abundant than light rare earths (La-Sm). In
addition, rare earths with odd atomic numbers are less abundant than their adjacent
elements (Oddo-Harkins rule). Rare earths co-occur in natural deposits, due to their
chemical similarity. Thus, the mining and production of one rare-earth oxide will
always deliver a number of others. This phenomenon is called rare-earth balance
[167, 168, 169, 170]: today, the rare-earth market is mainly driven by the demand
for Nd, Pr, Dy, Tb, Y, and Eu for magnets and luminescent materials (Fig. 23).
However, producing 1 kg of Nd, the main deposits in China will also, on average,
produce about 2.5 kg of Ce and 1.5 kg of La, which are currently available in
excess [162, 161]. Taking a rare-earth balance perspective on the search for new
magnet materials clearly shows that a mass-market rare-earth permanent magnet
may only be based on La, Ce, Pr, and/or Nd as the main rare-earth metal component.
Furthermore, rare-earth minerals are mostly associated with other ore minerals, such
as those containing U and Th and/or Fe as it is the case of the Bayan Obo mine
(China). Economic and environmental issues in the extraction and handling of these
materials will ultimately also influence the economic success of the rare-earth metal
production.
28 Permanent Magnet Materials and Applications 1407
Fig. 23 Rare-earth balance – the oxides co-occur in nature. The diagram shows the average
distribution of the individual REE across 51 deposits worldwide, excluding Chinese deposits as
data is not accessible. (According to P. Christmann BRGM; see [162])
robust and show a high energy efficiency, there are currently no alternatives to
motors containing Nd-Fe-B.
Critical competing technologies: It is meaningful to consider whether there are
other technologies that might compete with the magnet industry in the access and
long-term use of strategic metals. In the case of Nd and Pr, these are the glass, steel,
ceramic, and automobile (catalysts) industries. The absolute amounts used for these
fields of applications are, however, negligible. This is different for Tb: currently,
more than 70 percent of its global production is used in phosphors. However, this
is most likely to change, since LED lighting is now revolutionizing the market,
substituting traditional fluorescent lamps in many applications, which will result in
a lower demand for Tb in this application [175]. From a rare-earth balance point
of view, a growing availability of Tb would be welcomed by the magnet and motor
industry in order to make use of this heavy rare earth as an alloying agent in Nd-Fe-
B to increase magnetocrystalline anisotropy. Finally, Dy is almost exclusively used
in magnets.
Ecological factors: The mining and processing of rare-earth materials does
not necessarily come with a high environmental footprint. However, according to
literature, several mine operations, and particularly those in China, fail to apply
state-of-the-art environmental technology and management practices [173, 176].
This is, for example, related to insufficient control over filtering of acidic off-gases,
liquid discharges, mining waste management, and post-operational cleanup [173].
In addition, there are illegal mining practices with high impact. These malpractices
are of particular concern regarding the fact that rare earths often co-occur with Th
and U, and radioactivity should be carefully managed in mining, processing, and
waste management. Thus, today, rare-earth permanent magnets mostly come with
significant environmental footprints. This is challenging, particularly in the light of
their growing importance for e-mobility, wind power, air-conditioning, consumer
electronics, as well as robotics and industrial machinery. There is a rising awareness
for the environmental aspects of rare earth, and the Chinese government seems to
tighten rules and regulation for its rare-earth-producing companies [173].
Recycling potential: Industrial Nd-Fe-B recycling of end-of-life products is
still in its infancy. This is alarming considering the value of the material and
the environmental issues associated with its production. There are two major
approaches: first, to regain the metals or oxides using chemical extraction routes
(e.g., solvent extraction, selective precipitation) and, second, to pursue advanced
functional recycling routes that aim at re-processing the Nd-Fe-B alloys by casting
or powder metallurgical treatment, thus re-processing the material and thereby
preserving its functionality [181, 173, 182, 71]. The second kind of route is very
promising in terms of total energy and process costs. Nevertheless, particularly the
functional recycling approaches very much depend on well-defined feedstocks. This
is a major problem, since the extraction of scrap magnets from waste streams and
their characterization and classification are challenging.
Conclusions: The analysis shows that, today, Nd-Fe-B is a highly critical mate-
rial, although prices have not reached those levels of 2010/2011 again. We observe
a high supplier country concentration in raw materials production as well as in the
28 Permanent Magnet Materials and Applications 1409
magnet industry itself; the material cannot be substituted in many key applications;
it has a significant ecological footprint; and the industrial-scale recycling of Nd-
Fe-B from end-of-life appliances is still in its infancy. The rare-earth and magnet
materials’ prices are not governed by a flexible, sustainable supply-demand balance
but by prices set by a Chinese planned economy and speculation. A way out of
the dilemma would be the development of equivalent substitute materials as well
as a diversification of the magnet supply chain (including recycling) by reviving
a magnet industry in several different places worldwide. Resource constraints
might once again turn out to be the catalyst for the development of new, stronger,
permanent magnet materials. At the same time, overcoming these constraints will
be crucial for the breakthrough of a number of emerging technologies, most
importantly e-mobility, large-scale wind power applications, robotics, and energy-
efficient industrial production machines (Fig. 24).
The energy product (BH )max = 474 kJ/m3 achieved for PM materials at room
temperature (Fig. 12) cannot be greatly improved for Nd-Fe-B materials because
1410 K.-H. Müller et al.
its value is close to its upper limit ≈ 510 kJ/m3 given by the relation (18). It is
unpredictable whether or not phases will be discovered that exhibit a spontaneous
magnetization exceeding that of Nd2 Fe14 B (1.61 T) and, at the same time, show
a sufficiently strong magnetic anisotropy and are sufficiently stable at processing
temperatures and operation temperatures at which magnets will be produced and
used, respectively. A possible candidate for this is the tetragonal compound α -
Fe16 N2 from Table 5. It was discovered by K.H. Jack who prepared it by a
quench-aging route starting with N-austenite γ-(Fe, N). The maximum N content
of γ and of N-martensite α that forms from it by quenching is considerably less
than 12.5 at%. Subsequent heat treatment promotes clustering of the interstitial
nitrogen in α and results in the two-phase system α -Fe8 N + α-Fe, and, at the same
time, α transforms into α where the N atoms occupy 2 of the 48 octahedral
interstices in a perfectly ordered manner: γ(Fe,N)→ α -(Fe, N)→ α -Fe8 N + α-
Fe → α -Fe16 N2 + α-Fe [183, 184]. Therefore, this conventional preparative route
will never produce more than 50 % α -Fe16 N2 . Further difficulties arise if the
processes are not fully completed, and, consequently, residual content of γ and
α further reduce the average magnetization of the material. However, in recent
years, α -Fe16 N2 nanoparticles were produced in gram amounts by a completely
different preparation route starting from iron oxides [185]. A new process for
the reduction of iron oxides at elevated pressures and high hydrogen pressure
and subsequent nitrogenation in an ammonia flow yielded fine, 99 % phase-pure
α -Fe16 N2 nanoparticles [186, 187, 188]. A serious problem is the fact that the
metastable phase α -Fe16 N2 decomposes at temperatures of at least ≈ 100 ◦ C [189],
and, therefore, an important goal is to stabilize it.
A more exotic compound is L10 -FeNi (tetrataenite) that is found in meteorites.
However, so far, thermodynamic and kinetic conditions for producing it are not well
known and may be difficult to implement [190]. The L10 -type lattice structure also
adopted by the equilibrium phases FePt, CoPt, and FePd is shown in Fig. 25. These
latter compounds can be obtained by annealing the quenched disordered cubic high-
temperature γ phases of A1-type structure, which is represented by the left part of
the figure if ac = c and both sublattices are statistically equally occupied. The L10 -
type structure (with a = c in the right-hand part of the figure) can also be obtained
by a tetragonal distortion of the cubic B1-type structure (with a = c). The following
intrinsic magnetic properties of L10 -FeNi, measured on meteoritic material, are
texture Mr /Ms as high as 0.85 has been achieved for hot-extruded MnAl(C)
[204]. Hot extrusion also results in an increase of coercivity due to grain refin-
ing. Extrinsic magnetic properties obtained for those magnets are μ0 Mr = 0.61 T,
μ0 Hc = 0.32 T, and (BH )max = 56 kJ/m3 [205, 206]. Later reported values for hot-
extruded gas-atomized MnAl(C) powders are μ0 Mr = 0.54 T, μ0 Hc = 0.25 T, and
(BH )max = 42 kJ/m3 [207]. A larger coercivity, μ0 Hc = 0.52 T, has been achieved
for annealed, mechanically milled Mn-Al-C powders [208, 209].
Among the Mn compounds, the tetragonal Heusler alloys Mn3 Ga and Mn2 Ga
as well as the L10 -phase MnGa are also under investigation [194, 210, 211, 212,
213]. However, this approach does not seem to be promising because the magnetic
properties of these materials are moderate and gallium is expensive.
The strategy for plugging the gap between high-performance rare-earth magnets
and hard ferrites should also include downgrading rare-earth magnets by substi-
tuting the expensive elements Dy, Tb, Nd, Sm by cheaper ones such as Ce and
La [214, 215]. Also, it should be emphasized that Alnico has a respectable energy
product (see Fig. 12) and a high Curie temperature. Drawbacks are its low coercivity
and the fact that Co is a strategic material. Recent investigations show that – now
that the microstructure of Alnico and its influence on Hc are better understood –
Hc can be possibly further improved [55]. An interesting question is whether PM
materials can be developed that are governed by shape anisotropy, comparable to
Alnico and FeCrCo, but contain only small or even zero amounts of cobalt. It cannot
be excluded that such low Hc magnets with moderate (BH )max will be used in the
future for energy-related applications.
Fig. 26 Demagnetizing curves showing the working points P1 and P2 for (a) a static application,
(b) a dynamic application with mechanical recoil, and (c) a dynamic application with active recoil,
modified after [9]. The dashed line P2 Q represents the stable trajectory with the slope μR known
as the recoil permeability. The blue square indicates the recoil product (BH )u
or soft iron is moved in the magnetic circuit. After several cycles, the working point
follows a stable trajectory, represented by the line P2 Q with the slope μR known
as the recoil permeability. The energy which can be used is described the recoil
product (BH )u as indicated by the blue rectangle in Fig. 26b and is much reduced
compared to (BH )max but is greatest for a broad square hysteresis loop and a recoil
permeability close to μ0 [217, 9].
In the presence of an external magnetic field generated by coils, the slope of the
load line in a fixed permanent magnet assembly remains but shifts parallel moving
the working point P1 to P2 (Fig. 26c). Such a case is called a dynamic application
with active recoil [217, 9]. In order to resist demagnetization, a high coercivity is
generally required for application. There are a number of additional properties of
permanent magnets that need to be considered: a high specific electrical resistivity
ρ in order to minimize eddy current losses, which are a major source of heating
the magnets; a square hysteresis loop to avoid hysteresis losses; as well as the
temperature coefficient of remanence and coercivity (α and β, respectively), which
are the key to evaluating magnetic performance at elevated operation temperatures
and ideally should be close to zero or even positive (as described in [7]). Typical
values are given in Table 6. Beware that the temperature coefficient β can only
describe a linear change in coercivity with increasing temperature, which is not
fulfilled for most of the materials. Furthermore, it must be considered that β also
depends on the degree of alignment and in the case of Nd-Fe-B magnets also on the
Dy content [222].
Permanent magnets are widely used to generate static magnetic fields with relatively
high flux densities but without the need of a continuous energy input such as
electrical current as it is the case for solenoids. However, it is quite challenging to
1414 K.-H. Müller et al.
Table 6 Comparison of the specific electrical resistivity ρ and the temperature coefficients of
remanence α and coercivity β. The data are taken from (1) [9], (2) [218], (3) [89], (4) [219], (5) [220],
and (6) [221]
Material ρ α β
(μΩm) (%/K) (%/K)
SrFe12 O19 sintered(1) 108 −0.20 0.45
SrFe12 O19 polymer bonded(1) −0.02 0.45
Alnico 5 cast(1) 0.5 −0.02 0.03
SmCo5 sintered(1,2) 0.6 −0.04 −0.31
Sm2 Co17 sintered(1,2) 0.9 −0.03 −0.20
Nd2 Fe14 B sintered(1,3) 1.5 −0.13 −0.60
Nd2 Fe14 B die-upset(4,5) 1.2 −0.09 −0.60
Nd2 Fe14 B HDDR polymer bonded(1,6) 200 −0.10 −0.55
design permanent magnet assemblies with desired field uniformity or field gradient
within a specific macroscopic space. The major challenge is that a point dipole of
magnetic moment m measured in Am2 creates a nonuniform field which can be
expressed in polar coordinates [217]:
As Hr is now a factor of 2 smaller than for the point dipole, the magnitude of H
Hr2 + Hθ2 + HΦ2 is independent of θ , and the direction of H with respect to the
magnetization, η, is 2θ . By superimposing the magnetic fields of several line dipoles
or cylindrical segments with a homogeneous magnetization, a uniform field can be
created in a certain region. A prerequisite is that the field of one magnet segment
does not disturb the magnetization of the neighboring segments; in other words,
first the longitudinal and second the transverse susceptibility must ideally be zero.
For rare-earth or ferrite magnets, the first requirement is rather well fulfilled due
to a nearly rectangular M vs. H hysteresis curve, and the second is only in the
order of Ms /Ha = 0.1. This rigidity of magnetization leads to the case that the
superposition of magnetic flux is linear and the magnetic material is magnetically
transparent, behaving like vacuum with permeability μ0 .
In a permanent magnet assembly of such cylindrical segments, the magnetic field
in a certain air gap, Hg , scales with the remanent magnetization Mr :
Hg = Ng Mr (30)
28 Permanent Magnet Materials and Applications 1415
with Ag and Am as the cross-sectional areas of the cavity and the magnet,
respectively. The theoretical upper limit of ε is 0.25. Therefore in reality a value of
0.1 is regarded already as efficient. Other criteria for a good structure are a minimum
of magnet material used to generate maximum uniform fields in a maximum sample
volume. More practically, the sample chamber should be easily accessible, and it
should be possible to vary the applied field between zero and maximum with small
amount of energy and torque.
Fig. 27 Cross sections of some permanent magnet assemblies which create a uniform magnetic
field along the blue arrows (a) from wedge segments, (b) with soft iron return path, (c) from
Halbach array with soft iron pole shoes, (d) from segmented Halbach array, and (e) from a magnetic
mangle, respectively, modified after [217]. The black solid and the black dashed arrows indicate
the direction of magnetization in the permanent magnet as well as in the soft iron. The red dotted
arrows show the sense of rotation
magnetized as shown in Fig. 4 (left) and is fully covered with a thin iron sheet. In
the sense of a dynamic application, the sheet can be moved back and forth in order
to obtain zero or maximum field.
A famous structure is the Halbach array [21], which was already shown in
Fig. 4 but can also be modified by two pole shoes made of soft iron or FeCo
(permendur) in order to concentrate flux density to the saturation magnetization of
the pole shoe material of 2.15 and 2.45 T, respectively (Fig. 27c). This structure can
be considered as the three-dimensional extension of two one-sided flux tapes much
earlier proposed by Mallinson [20]. In this Halbach cylinder, the magnetization
rotates continuously and fulfills the same condition as for the line dipole, that is,
the direction of magnetization with respect to the vertical axis η at the position
P3 is two times the angular position θ , i.e., the angle between the vertical
axis and the position line (see Fig. 27c). For a Halbach cylinder with infinite
length, the geometric factor Ng is ln(r2 /r1 ) as shown in (8). For r2 /r1 = 2.2, the
efficiency is greatest with ε = 0.16 [9]. For a finite length L, (8) is modified
to (34) [225]:
28 Permanent Magnet Materials and Applications 1417
⎛
r2 z0
Hg (r = 0, z = 0) = Mr ⎝ln +
r1 2 z02 + r12
⎛ ⎞⎞
z0 z0 +
z02 + r22
− − ln ⎝ ⎠⎠ (34)
2 z0 + r 2
2 2 z0 + z0 + r 1
2 2
By rotating the rods alternately by ± 90◦ , a low-field configuration with zero field
at the center is obtained [226]. Arranging the magnetization in a ring results in
a larger low-field region, but this configuration cannot be achieved by continuous
rotation from the high-field state. The lower fields, and the much higher torque
needed for rotation, are drawbacks compared to the Halbach array, but lateral access
is convenient for a magnetic microscope stage [230].
1418 K.-H. Müller et al.
Fig. 28 Cross sections of some permanent magnet assemblies which create a nonuniform
magnetic field along the blue arrows, modified after [217, 45]. (a) is an Halbach array with an
internal quadrupole field, (b) a magnetic mangle generating a field gradient, (c) a magnet for a
microwave travelling-wave tube, and (d) a wiggler magnet to generate electromagnetic radiation.
The * indicates the segments which have to be rotated to form an external quadrupole field
28 Permanent Magnet Materials and Applications 1419
with Active Recoil”. Unrolling such an assembly gives a one-side flux pattern which
is used for fridge magnets and other holding magnets made from bonded ferrites
[9]. Similar quadrupole fields are also possible with the magnetic mangle. Here also
very high field gradients are possible in order to exert forces on other magnets as
illustrated in Fig. 28b.
Another assembly of permanent magnets is shown in Fig. 28c. In this config-
uration, again a charged particle, e.g., an electron beam, is kept within a narrow
tube, but in this case, extra energy is coupled from a periodic axial cusp field which
generates longitudinal electron waves. This design is used in microwave power
tubes to amplify radiofrequency signals in the microwave range and to stabilize
molten metal flows. In synchrotron sources or free-electron lasers, a periodic
transverse field is generated from energetic electrons passing a wiggler structure
as shown in Fig. 28d in order to obtain an intense beam of hard radiation (UV and
X-ray).
One of the oldest applications for a permanent magnets is to attract other
permanent magnets or soft magnetic parts and to stick them together. The major
challenge is that permanent magnets are permanent and cannot be switched of in
order to release the attracted material. Switchable magnets which are widely used
for holding components in optical benches such as light microscopes, machine
tools, and magnetic clamps to fix signs and light objects to steel panels all use the
effect that moving a ferromagnetic part transverse to the magnetization direction of
a permanent magnet needs less force than longitudinal to it. In a closed circuit as
shown in Fig. 29, the energy in two infinite small air gaps with distance d is:
Applying a force, F , the work done separating the segments is 2 F d which leads
to the maximum holding force Fh on the steel object in the on-position:
Fig. 29 Schematic illustration of (a) a switchable holding magnet and (b) electromagnetic
separation device, modified after [9]. The solid and the dashed arrows indicate the direction of
magnetization in the permanent magnet as well as in the soft iron. The dotted arrow shows the
sense of rotation
1420 K.-H. Müller et al.
μ0 Hg2 Ag
Fh = . (37)
2
Rotating the magnet to the off-position (mechanical recoil) closes the magnetic
circuit within the holding device, and the steel object can be lifted off. Other designs
of switching magnets use lateral movement of permanent magnet and soft iron
matrices against each other [9].
Nonuniform magnetic fields are furthermore used for mineral and metal
separation as shown in Fig. 29b. Hereby particles are moved over a fast rotating
wheel with an alternating permanent magnet configuration. If the particle has a
magnetic moment m, a volume V , and a susceptibility χ , a force Fm
is induced to it. For rare-earth permanent magnets, the magnetic field gradient
can reach values up to 100 T/m, and separation forces of order 108 Nm−3 are
possible which attract the particle to the spinning wheel [217]. Whereas the force
is proportional to the volume, the resulting trajectory depends on the force density
and is therefore independent of the particle size and only susceptibility-selective. If
the gradient is high enough, paramagnetic particles are also attracted, which is used
for separating paramagnetic deoxygenated red blood cells from whole blood or for
ferrofluid separation [9]. Using a fixed permanent magnet instead of a spinning
wheel is also thinkable; however, separation between metals and nonmetals is not
possible, because the eddy currents induced are not sufficient to significantly push
off the nonmagnetic metal particles from the magnet.
Other applications of permanent magnets are magnetic couplings, magnetic
gears, as well as magnetic bearings [217, 45]. The latter benefit from a cheap,
simple, and reliable design and can be arranged to bear a load linearly or radially.
Unfortunately, from Maxwell’s equation ∇ · B = 0, it is impossible to design a
static field configuration which allows a small magnet to be levitated at a fixed
point in space, i.e., to fulfill the condition that dB dB dB
dx , dy , and dz are all negative.
This impossibility known as Earnshaw’s theorem makes it necessarily to either use a
diamagnet or a superconducting permanent magnet [11,10] for levitation or to apply
mechanical or electromechanical forces in one dimension in order to prevent the
magnetic bearing from shifting or twisting [217]. Nevertheless, magnetic bearings
are widely used in flywheels for energy storage or in turbopumps, where a minimum
of friction is required. For magnetic levitation of a moving vehicle (MAGLEV), a
permanent magnet track provides either attraction to a soft iron sheet or repulsion
via eddy currents which is generally possible but very expensive.
A permanent magnet can also be used for magnetic sensor devices. Here the
change of magnetic flux between a stationary permanent magnet and a rotating
toothed wheel made of soft iron can be probed by a Hall sensor in order to detect
the sense of rotation of the wheel. Further applications are magnetically compen-
sated hinges and eddy current brakes in elevators as well as speedometers in
28 Permanent Magnet Materials and Applications 1421
One major type of dynamic application with active recoil are actuators. Besides
the general meaning that actuators convert other types of energy into kinetic energy,
which a motor also does, actuators are generally understood as motors with limited
linear or angular displacement. In both cases, a coil acts with the field of a permanent
magnet. If the permanent magnet is stationary and the coil is moving back, it is
called a voice coil actuator. In this type of application, the coil moves in and out of
the magnetic flux Φ of the permanent magnet, which induces an electromagnetic
force (emf), that is, a voltage U in the coil due to Faraday’s law of induction
U = − dΦ dt .
In loudspeakers, which are one sort of voice coil actuators, the voice coil is
positioned in a small air gap of a magnetic circuit created by permanent ring magnets
mounted in soft iron rings (see Fig. 30a). Applying a current to the voice coil
moves the coil out (up) or in (down) again depending on whether the magnetic
field in the coil points down or upward. By applying an audio waveform, the
cone will reproduce the sound corresponding to pressure waves with an acoustic
power Pa depending on the field in the air gap Hg , which is maximized near
the (BH )max point. Therefore, loudspeakers made of Nd-Fe-B permanent magnets
can be designed much smaller than with ferrites, and the lightweight permanent
magnet can even be glued to the cone with a stationary drive coil. The reversed
effect is used in moving coil microphones, which are much more robust and cheap
compared to capacitor microphones. Furthermore, higher acoustic pressures are
Fig. 30 Schematic illustration of a voice coil actuator used in (a) loudspeakers and (b) a magnetic
hard disk drive, modified after [9]. The solid and the dashed arrows indicate the direction of
magnetization in the permanent magnet as well as in the soft iron. The dotted arrows show the
sense of rotation and linear movement, respectively
1422 K.-H. Müller et al.
detectable, and no voltage supply is necessary. The same effect is also used in voice
coil linear motors for any kind of linear motion where high precision and high
constant forces over the whole displacement length are necessary, as in moving coil
meters, pneumatic pumps, car door locks, and vibration control devices. Another
configuration is a flat voice coil used for accurate positioning of the read head
in a hard disk drive (see Fig. 30b). Here the coil moves transversely to the coil
axis,
rotating the read head around the pivot point. As access time scales with
1/ Hg , again Nd-Fe-B magnets with the highest energy densities are used. Similar
to microphones, a moving ferrite magnet in a stationary pickup coil converts the
oscillation signal of a magnetic steel string of an electric guitar into an electric
signal.
Another broad class of applications of permanent magnets are electric motors
or, using the reversed effect, generators. In motors, the coil of length L is
carrying a current I which, as a sum of all Lorentz forces of the electrons in
the winding, induces a net force F = L · I × B and rotates the rotor. In
comparison to induction-based asynchronous motors, permanent magnet-driven
synchronous motors are much more efficient, that is, they provide the same power
using smaller volume and mass [7]. A major drawback is that 70% of the material
costs is accounted for permanent magnets [231]. Thinking, for example, of a
3 MW direct-drive wind turbine, which typically uses 1.5 t of rare-earth permanent
magnets, or an electric motor and generator in a hybrid vehicle which needs 1.3 kg
of Nd-Dy-Fe-B magnets, this issue becomes important against the backdrop of
the resource criticality discussed in section “Resource Constraints”. Nevertheless,
electric motors are the major application of permanent magnet material in terms
of mass and quantity. The numerous variations of permanent magnet synchronous
machines can be distinguished by the position of the magnet, that is, whether the
permanent magnet is placed on the stator or on the rotator as shown in Fig. 31a, b.
In a two-pole brushed DC motor shown in Fig. 31a, the permanent magnet on
the stator creates a field which repulses or attracts the current-carrying windings of
the rotor. Mechanical commutation via brushes makes sure that the polarization of
the coil switches at each half turn and that the torque Γ on the rotor is always in the
same sense, leading to a rotation. The torque Γ is given by
Γ = C (U − Cω)/R (39)
with C = nw rw B L as the torque constant of the motor, rw the radius of the rotor
windings, nw the quantity of coils of length L, U the applied voltage, ω the angular
velocity, R the resistance of the windings, and Γ scales with the flux density B
produced by the magnet [9]. If the torque and the angular velocity are controlled by
modifying the applied voltage, it is a DC servomotor. In this case, monitoring of the
back emf or precise positioning is required. In order to eliminate the brushes which
are sources of sparking and wear, permanent magnets can also be placed on the rotor
and the windings on the stator (see Fig. 31b). In this case, electronic commutation
is possible either by applying an AC field or by a DC field. The latter requires
power controller in order to energize the windings in an appropriate sequence [9].
As synchronous motors lack starting torque until they reach synchronous rotation
28 Permanent Magnet Materials and Applications 1423
Fig. 31 Schematic illustration of (a) a two-pole DC electric motor with permanent magnets on the
stator and mechanical commutation (brushes) and (b) a brushless four-pole motor with a permanent
magnet on the rotor. The motor can be driven by a DC current combined with a power controller
(DC servo or spindle motor) or by AC current (synchronous motor). In the middle is a 13-bar
squirrel-cage winding using the principle of an asynchronous (induction) motor and its high startup
torque
vt = 2π rr fr (40)
with rr as the radius of the rotor and fr the rotational frequency of the rotor
[232]. The highest tangential rotor speed of 245 m/s at 120% overspeed has been
1424 K.-H. Müller et al.
realized for a large brown coal power plant induction-based generator at Lippendorf,
Germany, operating at 50 Hz with a rotor radius of only 1.3 m [233, 232]. For
PM motors, the embedded or surface-mounted magnets are more stress-sensitive.
Nevertheless, rotor speeds of 120–220 m/s are possible, for instance, using bonded
Nd-Fe-B ring magnets or Sm2 Co17 surface magnets fixed by a carbon fiber bandage
on a rotor with a radius of several cm [233]. For wind turbines, especially for off-
shore generators, the large rotor blades are the weakest points, and the rotational
speed must be low. In order to match the required power line frequency of 50 Hz
or 60 Hz in direct-drive wind turbines with maximum power output, the number
of poles has to be adjusted, or several generators have to be implemented in one
turbine [7]. Generally, the power output, P , of PM machines (motors or generators)
is indirectly proportional to fr [233, 232] following the relation
P ∼ 1/fr3.6 . (41)
From this point of view and considering the economical constraint (see above),
PM machines strongly dominate the field of machines below 500 kW [233], and
further upscaling of large off-shore wind turbines above the present maximum
of 20 MW will be challenging. For high-speed applications, e.g., miniature gas
turbines, mechanical factors such as stress and vibrations, rather than electromag-
netically induced heating, are the critical aspects which limit rotational frequency to
approximately 100.000 rpm at present [232].
A last important class of permanent magnet applications are stepping motors,
which can be considered as a discretized variant of the brushless DC motor. The
simplest configuration is the two-pole (bipolar) stepping (Lavet) motor called after
its inventor Marius Lavet (see Fig. 32a–d), which is nowadays used in most quartz
clocks. Here a permanent magnet is placed in a round cavity of a soft iron yoke
connected to a coil. Due to two small notches at the cavity, the magnetization
direction of the permanent magnet is energetically favored to lie transverse to the
notches (a). By applying a short current pulse along one direction, the permanent
magnet rotates to be consistent with the magnetization direction of the iron yoke (b).
After the pulse, the magnet rotates back to the nearest remanent position which is
now 180◦ off the initial remanent state (c). A second pulse in the opposite direction
rotates the permanent magnet further to be again consistent with the magnetization
direction of the iron yoke but now 180◦ off compared to the configuration after
the previous pulse (d). In this clever design, the permanent magnet, usually a small
Sm2 Co17 bonded magnet of a few milligrams in mass, rotates always in the same
direction. By increasing the number of notches and coils, a stepping motor which
rotates through a fixed angle of several degrees by driving a current through two
opposite windings is possible (see Fig. 32). In such a hybrid stepping motor shown
in this figure, the small step size of a reluctance stepper motor is combined with
the higher torque and the absence of a position loss in the zero current state of a
permanent magnet stepper motor. A sophisticated control is necessary to realize a
step-by-step rotation back and forth. Nowadays, hybrid stepping motors are almost
exclusively used for every kind of precise angular position control.
28 Permanent Magnet Materials and Applications 1425
Fig. 32 Schematic illustration of two-pole stepping (Lavet) motor in the (a) and (b) remanent
state and (c) and (d) applying a current pulse in the coil forward and backward. (e) shows a hybrid
stepping motor in the front and side view. The solid and the dashed arrows indicate the direction
of magnetization in the permanent magnets as well as in the soft iron. The dotted arrows show the
sense of rotation. (Modified after [9])
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Contents
Losses in Soft Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
Hysteresis Loss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1438
Low-Frequency Losses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1438
High-Frequency Losses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1449
Iron and Low-Carbon Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1452
Electrical Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1452
Composition, Processing, and Texture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1452
Non-oriented Silicon Steel Sheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1455
Grain-Oriented Silicon Steel Sheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1457
Trends in Fe-Si Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1460
Iron-Cobalt Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1461
Equiatomic Fe-Co Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1461
Low-Cobalt Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1463
Iron-Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1463
Ni-Rich Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1463
Fe-Rich Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1465
Thermal Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1466
Amorphous and Nanocrystalline Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1467
Iron-Based Amorphous Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1468
Cobalt-Based Amorphous Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1470
Nanocrystalline Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1470
Soft Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1472
Spinel Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1472
Synthesis of Sintered Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1473
Mn-Zn Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1474
Other Soft Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1478
F. Mazaleyrat ()
SATIE, CNRS, École Normale Supérieure Paris-Saclay, Gif-sur-Yvette, France
e-mail: [email protected]
Abstract
A great variety of soft magnetic material has been developed with the aim
of enhancing the magnetization, increasing the permeability, controlling the
hysteresis loop shape, or raising the working frequency while in all cases
decreasing the magnetic losses. Besides the physical considerations, material
shaping and cost are important parameters. It is thus not surprising to see
that despite natural selection, hundreds of materials of very different natures
(metallic, ceramic, glass) and properties remain on the market. Choosing the
right material for a specific application is often a tricky compromise and, too
often, a question of industrial culture. This chapter aims at helping the user to
make the best choice possible and gives some keys to improving device design.
The first part is devoted to magnetic losses, giving the most used models in
the low-frequency nonlinear regime and the high-frequency linear regime. The
following section describes the different families of materials: low-alloyed steels,
iron-cobalt alloys, iron-nickel alloys, amorphous and nanocrystalline alloys, and
soft ferrites. In each section, the fabrication process is described, and tables of
typical properties of most common materials are given. Finally, there is a table
of applications and matching materials.
From his work on thermodynamics and magnetism, Lord Kelvin proposed that any
change in magnetization should be accompanied by dynamic losses and heat release
or absorption – an effect that was later discovered and named magnetocaloric effect
by Pierre Weiss. Early work of Cazin in this direction has shown that change in
magnetization at constant temperature always produces heat [16], but due to the
geometry of the system and the frequency of magnetization switching, this was due
essentially to eddy currents. In 1881 Warburg proved that this heating was not only
due to dynamic effects [38] but to some kind of friction too, which was confirmed
independently the same year by Ewing [18] who developed the first B(H ) loop
tracer. He showed that the loop area is identical to heat release and named the
phenomenon hysteresis. Immediately, it was recognized that the hysteresis depends
on both flux density and frequency and that, below a certain frequency, the area and
shape of the loop depends no more on the frequency. This floor value of the losses is
known as hysteresis loss. The concept of loss separation was proposed by Braisford
[15] as the sum of the hysteresis loss, Phy , and eddy current loss, Pec . The difference
29 Soft Magnetic Materials and Applications 1437
750
Bpeak=1.5 T
600
excess loss
450
wtot=(Jm-3)
150
hysteresis loss
0
0 50 100 150 200 250
Frequency (Hz)
Fig. 1 Separation of losses in a 2.4 W/kg grade silicon steel. Lines correspond to the model and +
to the experiment
between measured iron loss PF e and these two components was called anomalous
loss Pan = PF e − Phy − Pec (see Fig. 1). The physical origin of what we rather
called excess loss Pex will be found long time later and properly embedded in a
reliable theory only in 1988 (see section “Excess Loss ”). In general, losses have
to be expressed in specific units, either power or energy per unit volume or mass
depending on customs of different communities. Eventually in linear regime, losses
can be expressed as a function of the loss angle δ = π2 − phase lag between voltage
and current. Usual units are:
It must be however emphasized that only the classical term can be determined
a priori. The other terms are determined from experiments. As it will be shown in
section “Excess Loss ”, the exponents of the excess part are n = 1/2 and m = 3/2
in many cases, but this is not a general rule. In a limited range of induction and
frequency, it is always possible to find an expression of losses like PF e = kB η f ξ ,
but this is only a fitting definitively free of physical sense.
Hysteresis Loss
Hysteresis loss is the most difficult loss term to model. At the end of the nineteenth
century, Rayleigh and Steinmetz proposed empirical models for hysteresis loss, and
we must say that more than one century later, there is no better simple model.
Since the 1950s, the Preisach model has been developed and widely studied. It’s
based on the decomposition of the hysteresis loop in elementary loops (hysteron)
defined by a coercive and a shift field. To compute the Preisach distribution , it
is necessary to record a great number of minor loops (or reversal curves) in order
to sweep uniformly the whole area of the major loop. The distribution allows to
compute any trajectory in the M(H ) plane, but, finally, if it is useful for researchers
to study the magnetization mechanisms in soft or even hard materials, it remains
usually too complicated for implementation in industrial software. The recovery
of the distribution is not straightforward and would need developments out of the
scope of this chapter; for more detail, the reader is invited to refer to the monumental
“Science of Hysteresis” [14].
Low-Frequency Losses
Steinmetz Model
The Steimetz model for hysteresis loss has actually no physical basis. It was
discovered purely empirically in 1905 and written in the form kB η . Plotting
hysteresis losses vs induction in log-log scale allows to deduce the coefficient
and the exponent, but the exact value of the exponent η depends somehow on the
considered induction window as it is seen in Fig. 2. As observed by Steinmetz, a
value close to 1.6 is generally observed. This value can’t be easily connected with
the result of Rayleigh because the latter is expressed as a function of H and because
the permeability is not constant. At higher induction, the exponent increases over
2 and then drops to zero in the reversibility region of the major loop (close to
29 Soft Magnetic Materials and Applications 1439
Rayleigh Loops
In the small signal regime, i.e., when B μ0 MS , Rayleigh observed linear and
quadratic behaviors of permeability and initial magnetization curve, respectively:
μ = μi + νH and B = μi H + νH 2 (1)
1
B = (μi + νHm )H ± ν(Hm2 − H 2 ) (2)
2
4 4
Wh = νH 3 or Ph = νHm3 f (3)
3 m 3
To write the loss dependence on B, one has to solve the second-order equation
(1) which single physical solution can be introduced in (3):
μ3 4νB
Wh = i3 1+ 2 −1 (4)
6ν μi
If μ2i 4νB:
4 μ3i 3/2
Wh = B (5)
3 ν
we end up with a Steinmetz exponent of 1.5, which is very close to the experimental
one.
This law is pretty much simple, but its validity is limited to B JS /10. Such
low induction in practice is used only at high frequency, i.e., several tens or hundreds
of kHz. Under these conditions, hysteresis losses are negligible compared to eddy
currents in metals, so this law is more useful in practice for ferrites. Experience
shows that the Rayleigh law is well obeyed in ferrites up to 25 mT and over 100 kHz
in highly resistive NiZn-type ferrites (see, e.g., [1]).
Eddy Currents
When any conductive material is submitted to AC magnetic field, eddy currents are
created inside in such a way they produce a counter field. This contribution to losses
will be added to the hysteresis (DC) component of the losses. Its nature is purely
Maxwellian and refers to an isotropic and homogeneous material at macroscopic
scale, which is not realistic for ferromagnetic materials because of the domain
structure. However, in certain conditions, i.e., if domains are small compared to
dimensions of the sample and isotropically distributed or if the domain walls move
little compared to domain width (Rayleigh regime), eddy currents are as if the
material is magnetically homogeneous.
Classical Losses
This term refers to eddy current loss in the approximation of a weak skin effect, i.e.,
when the magnetic field produced by eddy currents in reaction to the exciting field,
Hex , is very small. In other worlds, the inductive reaction has no significant effect
on the flux density B which is considered uniform in space. From Maxwell-Faraday
equation
∂B
∇ ×E=− (6)
∂t
29 Soft Magnetic Materials and Applications 1441
w j B
j z
d y
x
L
Fig. 3 Geometry of the problem for a thin sheet; eddy currents are everywhere perpendicular to
B and parallel to the surface
and looking at the geometry of the problem (Fig. 3) with L, w d, one can see that
(i) the flux density has only one component along x depending only on time and (ii)
the current density, j, has a single y component independent on x and y, so that the
electrical field has the same symmetry through Ohm’s law j = σ E:
2 d/2
∂Bx
Pcl (t) = σ Ey2 dV = 2Lwσ z2 dz (8)
V ∂t 0
and dividing by the volume dwL, the instantaneous power per unit volume is
derived:
2
1 ∂Bx
Pcl (t) = σ d2 (9)
12 ∂t
Getting the mean power density requires to define the function Bx (t). Usually
in low-frequency applications such as AC machines and transformers, as well as in
standard characterization conditions, the induction is sinusoidal. The average of a
squared sinus being 12 , we end up with the well-known formula, where Bp denotes
the peak value of the induction:
π2 2 2 2
Pclsin = σf Bp d (10)
6
By opposition, in power electronics, the voltage has often a square wave form, so
B(t) is triangular. In this case, the time derivative of B is constant over a half period
so its value is 4f Bp for an induction swing of 2Bp and one gets:
1442 F. Mazaleyrat
4 2 2 2
Pcltri = σf Bp d (11)
3
It is easy to see that the classical losses are 23% lower for triangle waveform
compared to sinus for the same Bp .
Skin Effect
When the low-frequency condition is not satisfied, interaction between electrical
and magnetic fields must be introduced, and Maxwell-Ampère equation can be
combined with Ohm’s law as ∇ × H = j = σ E. Further, the permeability is
introduced:
∂B ∂H
∇ × (∇ × H) = ∇ × j = σ ∇ × E = −σ = −σ μ (12)
∂t ∂t
∂H
ΔH = −σ μ (13)
∂t
∂ 2 h(z)
= iσ μωhx (z) (15)
∂z2
√
where the peak value of the field in the direction x is 2h. A solution of this
equation can be found in the form of either exponential or hyperbolic functions.
In this case, because of the symmetry, the surface field is equal to the applied
field h(d/2) = h(−d/2) = ha so the hyperbolic solution has the simple form
hx (z) = A cosh(kz) where the complex number k is define as k2 = iσ μω. It is
usually convenient to write k = (1 + i)/δ, where the quantity δ, homogeneous with
a length, is called the penetration or skin depth:
2
δ= (16)
σ μω
so a hyperbolic solution is easily found taking into account the boundary conditions:
29 Soft Magnetic Materials and Applications 1443
cosh(kz)
h(z) = ha (17)
cosh(d/2)
The RMS value of the field is obtained by calculating the square root of the
conjugate product:
cosh (2z/δ ) + cos (2z/δ )
h(z) = ha (18)
sinh (d/δ ) + sin (d/δ )
With the present symmetry of the problem, the RMS value of the y single
component of the current density is written from the Maxwell-Ampère equation
as
√
dh 2 cosh (2z/δ ) − cos (2z/δ )
j (z) = = ha (19)
dz δ cosh (d/δ ) + cos (d/δ )
The volumetric Joule losses produced by eddy currents in the sample are obtained
by integration over the thickness divided by the volume
1 d/2
Pec = jy (z)2 dz (20)
σe −d/2
It must be emphasized that this formula is valid only when the permeability is
constant. This condition is a strong restriction when δ d because the field at
the surface is much stronger than in the center (see Fig. 4). As a consequence, even
1444 F. Mazaleyrat
2 2
1.8 1.8
1.6 1.6
1.4 1.4
1.2 1.2
H/H ex
B/ B
1 1
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0 0
-0.5 0 0.5 -0.5 0 0.5
z/t z/t
Fig. 4 Profile of the field H across the thickness reduced to excitation field and profile of B
reduced to the space averaged induction for δ/d =1, 0.5, 0.1. B is calculated in the linear case;
clearly, this model is not adapted for small δ/d when B is close to JS
if B JS , the sample may be saturated close to the surface. In this case, there
is no analytical solution; specific and time-consuming algorithms must be used (see
[17] for more detail.)
Excess Loss
If the domain are very thin (2L d) coth(x) 1/x and one can find the
classical result of (9). On the overside, if 2L d, the coth terms are close to unity
and (24) is reduced to:
2
σG ∂φ
PP B (t) = (25)
2Ld ∂t
by writing 4
π4
1
n3
= G = 0.1356. In grain-oriented Fe-Si sheets, the latter
odd n
condition is rather justified since 2L ≈ 1 mm; d ≈ 0.24 mm and very well justified
for longitudinal field-annealed amorphous ribbons 2L ≈ 5 mm; d ≈ 0.02 mm.
Bertotti’s Model
The basis of Bertotti’s model (see [12] and [11] for more detail) is the application
of Pry and Bean model to a system composed of slab domain regions randomly
oriented in space. From statistical arguments, Bertotti has shown that in this case the
total dynamic loss is equivalent to the sum of classical eddy currents superimposed
with eddy currents generated by periodic slab domains parallel to the field Pdyn (t) =
Pcl (t) + PP B (t). This validates theoretically the concept of loss separation PF e =
Phy + Pcl + Pex , where the excess loss is the time average of (25):
2 2
σG ∂φ σG ∂φ
Pex = = (1 + α) (26)
2Ld ∂t 2Ld ∂t
where α is a form factor depending only on the flux waveform. It is now interesting
to introduce the notion of excess field which is the supplementary field necessary
to obtain the desired change in magnetization due to the dynamical movement of
domain walls:
∂J
Pex = Hex (27)
∂t
∂J
Hex = 2Ldσ G(1 + α) (28)
∂t
Let us now introduce the width of the sheet, ; the area of the cross section
perpendicular to the field, S = d; and the number of domain walls in this section,
nw = /2L. Now we have:
S ∂J σ GS ∂J
Hex = σ G(1 + α) · = · (29)
nw ∂t n ∂t
1446 F. Mazaleyrat
nw
where we substituted n = 1+α to simplify. Thus, n is no more the real number of
domain wall but an effective number depending on the waveform. This is actually
not a problem since n, also called the number of magnetic objects, will be identified
from loss measurements using a given waveform. However, it is reasonable to think
that the number of active magnetic object will depend on the excess field (larger
excess field will activate more magnetic objects), so at first order one can write:
Hex
n = n0 + (30)
V0
where n0 is the number of active objects at zero field and V0 the field necessary to
activate one more object over the total number of magnetic objects available N0 .
Physically speaking, a magnetic object can be a domain or a set of domain moving
coherently, in other words, a crystallographic grain. Introducing (30) in (29) leads
to the second-order equation:
2
Hex ∂J
n0 Hex + n0 = σ GS (31)
V0 ∂t
which admits one physical solution over the two mathematical ones
−n0 V0 + n20 V02 + 4V0 σ GS ∂J
∂t
Hex = (32)
2
The excess loss can now be expressed from (26) after factorization:
n0 V0 4σ GS ∂J ∂J
Pex = 1+ 2 · −1 (33)
2 n0 V0 ∂t ∂t
3
∂J 2
Pex = σ V0 GS (34)
∂t
So obviously in this case the parameter V0 is the most important from physical
point of view. Indeed, in small grain materials, N0 can be understood as the number
of grains of average diameter D in the cross section and
2Hhy
V0 (35)
N0
29 Soft Magnetic Materials and Applications 1447
where Hhy , the hysteresis field, is defined from Phy the same way the excess
field is defined (see 27). So in principle this parameter is directly related to the
microstructure and the time dependents of the magnetization.
In the case of triangular flux waveform, the time derivative of the magnetization
can be simply expressed on a half period as a function of the frequency and the peak
magnetization ∂J ∂t = 4Jp f , so (33) can be written in terms of power or energy per
unit volume:
3 3
Pex = 8 σ V0 GSJp2 f 2 (36)
3 1
Wex = 8 σ V0 GSJp2 f 2 (37)
so we end up with the famous square root frequency dependence of the excess losses
observed experimentally by Brailsford [15]. The classical result of Bertotti (37)
must be considered with caution:
Fig. 5 Plot of losses as a function of square root frequency in non-oriented Fe-Si sheets used for
determination of Bertotti’s model parameters (left). V0 parameter evolution with magnetization
(right) after [8]
1448 F. Mazaleyrat
points and the line at low field is due to the fact n0 cannot be assumed exactly zero.
The right box shows that V0 depends on the peak induction and is not a constant as
it is expected from (30). This however makes physical sense as explained above and
can be related to the Preisach distribution. This doesn’t invalidate Bertotti’s model,
but one has to make a choice between accuracy (which needs determination of V0
dependence on (Jp )) and simplicity (using an average V0 ).
For accurate modeling of high-frequency losses with skin effect, more compli-
cated techniques must be used as in reference [10] based on dynamic Preisach model
[13].
Rotational Losses
Rotational losses are important in classical AC machines where the induction has
usually a constant magnitude and a constant angular speed. It is however a simplified
view because locally the induction locus can be rather ellipsoidal than circular.
Also in three-phase transformers, at the junction between columns and yokes, the
induction has a direction depending on time. In the frame of this chapter, only the
case of circular locus will be discussed.
High-Frequency Losses
From the previous sections, it can be concluded that magnetic power losses
approximately go with the square of B and an exponent of f between 1 and 2. As
a consequence, reasonable losses at high frequency can be obtained only keeping a
reasonable value of the B × f product, which means a very low value of B. In this
case, the material works in the linear regime, and its properties are advantageously
represented in the form a complex permeability. An inductance can be modeled
either by a parallel or series circuit, the latter being the most common:
2
R N μ0 μR A R
Z = R + j Lω = j ω L − i = jω −i (40)
ω ω
where N is the number of turns of the coil and A and are the effective cross-
sectional area and length of the magnetic circuit. From this equation, it is easy to
identify the real part of the permeability and the imaginary part:
(r − R0 )
μ = μR − j = μ − j μ (41)
N 2 μ0 S
where R0 is the ohmic resistance of the coil and r is the series resistance standing
for the iron loss. The loss factor is usually defined as:
1450 F. Mazaleyrat
tan δ = μ/μ (42)
tanh(kd/2)
μ = μS (43)
(kd/2)
Getting an analytical expression of the real and imaginary parts of (43) is not
straightforward, but any mathematical software will easily compute μ and μ
knowing the main physical parameters: low-frequency permeability, conductivity,
and thickness. The permeability spectra have two main features:
and
4ρ
fR = (44)
π μ0 μS d 2
– Debye if α = β = 1,
– Davidson-Cole if α < 1 and β = 1
– Cole-Cole if β < 1 and α = 1
μS fR
μ→ (46)
f
Fig. 7 Complex permeability spectra of different soft magnetic materials. Left, nanocrystalline
wound core: points are experimental, and line is computed using (43) using parameters measured
independently (t=25μm, ρ = 120 · 10−6 m). Right, ferrite showing double relaxation behavior
typical of material having bimodal grain size distribution: points are experimental, and lines are
fitted using the sum two terms with parameters α1 = 0.5, β1 = 0.65, fR1 = 30 kHz, α2 = 1,
β2 = 0.7, and fR2 = 30 MHz (45)
1452 F. Mazaleyrat
Iron was the only soft material used until the very beginning of the twentieth century.
For industrial applications, such as electrical motors and transformers, iron has
usually two functions: magnetic and mechanical. From magnetic point of view,
iron has a high induction and high permeability, but its conductivity is too high for
efficient AC applications. For this reason, iron is today used only in DC applications
such as pole pieces for lab electromagnets. The mechanical function of iron is
very important because the magnetic core carries the coils in transformers and is
subject to magnetic forces in machines or electromagnets. As a consequence, low-
carbon steel is usually preferred for DC application, whereas it can’t be used in AC
application because of the enhancement of the coercivity due to interstitial C atom in
the bcc lattice of iron. The main application of low-carbon steels as magnetic parts
is: rotors of current excited synchronous machines and stators of DC machines.
In power station turbogenerators and claw pole automobile generators, the rotor is
made by forging. In the case of DC machines, the stator can be made by stamping
of thick sheet for several hundred watt machines and casting for bigger machines.
Electrical Steels
Composition
In the beginning of the industrial era, metallurgists tried to reduce the carbon
residue in iron to enhance its magnetic softness at the price of poor mechanical
properties. In 1896, Hadfield fortuitously produced steel with a small percentage
of silicon and observed strong enhancement of its mechanical hardness. By 1900,
he measured its magnetic properties, showing that silicon not only improves iron’s
mechanical properties but also resistivity without prejudice to magnetic properties.
A couple of years later, silicon steel was massively produced in industry. In addition,
silicon improves the resistance to corrosion and elastic limit of iron. Altogether,
Fe-Si is probably the best alloy for low-frequency AC applications from magnetic,
mechanical, and economic points of view since it is composed only of cheap and
abundant elements.
The silicon content can be varied in a very large range and forms bcc solid
solutions up to 25 at.% Si, limit above which the alloys decompose into Fe3 Si
soft phase and a Fe7 Si3 hexagonal hard magnetic phase. Figure 8 shows the main
properties of Fe-Si alloys. By increasing the silicon mass content up to 10%, the
resistivity is multiplied by a factor 10, and the magnetization is reduced by 30%.
However, the increase of the hardness makes the material very brittle above 10
at.% ( 5 mass%). This increase in hardness also makes the rolling more difficult
and reduces lifetime of cutting tools. So, in practice (except the case of 6.5 mass%),
29 Soft Magnetic Materials and Applications 1453
Fig. 8 Silicon dependence of room temperature saturation magnetization and resistivity of Fe-Si
alloys. Coercivity is also given as a trend only since it depends on the manufacturing process
Processing
The mother alloys are produced from recycled silicon steels for a great part and
pure iron (produced from iron ore) and silicon. The alloy is decarburized by blowing
hydrogen in the melt and cast into a 20 cm by several meters slab. Then, it is reduced
down to few mm by several hot-rolling passes, followed by several cold-rolling
passes depending on the silicon content and the final thickness. At this stage, the
sheets are about 1 m wide in the form of a 1 m in diameter coil. The semi-processed
materials are annealed at 800◦ C for a few minutes and rolled again with a small
thickness reduction (skin pass). It is then sent to manufacturer for cutting and must
be annealed in three steps: 750°C for decarburization under partial H2 pressure,
800°C for grain growth, and then in a wet atmosphere for surface insulation by
oxidation. The fully processed materials are annealed immediately after cold rolling
at 800◦ C under partial H2 pressure for decarburization and then up to 1000°C for
1454 F. Mazaleyrat
grain growth and insulated by organic binder. The manufacturer can cut the sheets
and mount them without further treatment.
Texture
Cold rolling produces heavy deformation mainly by slipping in the most dense
plane. In a bcc lattice, the most dense plane is {110}. Accordingly, successive cold-
rolling pass tends to produce a {110} texture (grains have a {110} plane parallel
with the sheet plane). However, cold rolling is not perfectly anisotropic because all
passes are made in the same direction, called rolling direction (RD). Consequently,
a slight anisotropy in the plane is observed corresponding to a small {110}001
texture and/or fiber -type components (mainly {111}112 see, e.g., [35]). This kind
of sheets is called non-oriented silicon steels (NOSS).
Because 001 is the easy magnetization axis, permeability is stronger along RD
compared to transverse direction (TD). Starting from this fact, metallurgists tried to
improve the 001{110} texture in order to maximize the RD permeability. These
materials are called grain-oriented silicon steels (GOSS).
1. A number being hundred times total specific losses in watts per kilograms at a
frequency of 50 Hz and an induction of:
– 1,5 T for fully and semi-processed NOSS and regular GOSS
– 1,7 T for low losses and high induction (Hi-B) GOSS
2. A number corresponding to hundred times the thickness expressed in millimeters
3. A letter corresponding to the type of silicon steel:
For NOSS, standard thicknesses are 0.35, 0.5, 0.65, and 1 mm, but thinner gauge
sheets (down to 100 μm) are more and more proposed by steel companies. GOSS
are usually 0.35, 0.3, 0.27, and 0.23 mm thick, the last two being used generally for
Hi-B.
29 Soft Magnetic Materials and Applications 1455
Designation examples:
M 85-23 P Fe-Si grain-oriented sheet, 0.85 W/kg at 50 Hz under a 1.7 T sine
waveform peak induction, 0.23 mm thick.
M 240–35 A Fe-Si fully processed sheet, 2.4 W/kg at 50 Hz under a 1.5 T sine
waveform peak induction, 0.35 mmm thick
35 A 240 same in Japanese standard with permutation of numbers
36 F 145 same in the US standard, with a small difference in thickness (due to
older inch gauge) and 100×losses in W/lb at 60 Hz
NOSS are used in many different low-frequency applications, because of their good
mechanical and magnetic properties, in-plane isotropy, and low price. They are
proposed in a wide range of quality and price depending on the type of application
and the requirements in terms of performances.
In general, thicker gauges are cheaper and have higher losses and eventually
better permeability. This is illustrated in Fig. 9 where it is seen that thick-gauge
sheets have higher magnetization at low H and lower magnetization at high H (the
cross point is here about 300–400 A/m), but the 50 Hz losses are always higher for
thick gauges. As a consequence, they are used generally for low-power household
applications where price matters more than performance. In industrial applications,
the power is usually higher, and the cost of losses over the whole life of the device
has to be taken into account in the economic balance. As the size of the device
increases, heat is more difficult to release, so higher grade has to be used. If the
working frequency is higher than the network frequency, thinner gauge can be used
to reduce eddy current losses that becomes predominant above several hundred Hz.
Fig. 9 Comparison of different common grades of oriented and non-oriented Fe-Si sheets
1456 F. Mazaleyrat
Fig. 10 Power loss as a function of field angle with respect to rolling direction at 50 Hz (left).
Power loss at 1.5 T, 50 Hz as a function of thickness. Points are for higher grade material; line is
for eddy currents (right)
High-grade NOSS are used essentially in industrial electrical machines where the
flux is not everywhere parallel to lamination directions in stator teeth and rotating
in stator core.
The NOSS are considered isotropic in plane, but this is not exactly observed in
practice. At low field, losses are almost independent of the direction of the field with
respect to rolling direction (RD), though a little bit smaller at 0° as illustrated in the
polar plot (Fig. 10). At 1.4 T losses are quite similar at 0 and 90° , but they show
a marked maximum around 45°. For this reason, according to the standard, losses
have to be measured using strips cut in four different directions (0, 30, 60, and 90°).
Cutting
The fully processed sheets are delivered in the form of annealed and insulated sheets.
The user cuts it in the required shape using punching, water jet, or laser, but losses
are guaranteed only for Epstein format strips (300 mm × 30 mm). Because cutting
always affects locally the magnetic properties, users have to keep in mind that losses
could be higher in narrower zones such as stator teeth.
The semi-processed sheets have to be annealed after cutting. In this case, if the
user anneals cut parts in the conditions given by the provider, losses are guaranteed
in all parts whatever could be the cutting process or the size of cutting. However,
this annealing has a cost for the user, so because semi-processed sheets are cheaper
than fully processed, many electrical machine manufacturers use semi-processed
sheets without annealing. In this case, properties are no longer guaranteed and can
be significantly different from those claimed by the provider. Typical grades of semi-
process silicon steel range between M-50–340-D and M-65-1000-D.
Thin-Gauge Steels
In embedded power applications, in particular in electric vehicles, power density
of electrical machines is the main issue after energy storage. For this purpose,
29 Soft Magnetic Materials and Applications 1457
Conventional GOSS
Typical GOSS process starts by melting of an alloy containing about 3.2% silicon
and 0.03% carbon, followed by hot rolling down to 2 mm after heating to about
1458 F. Mazaleyrat
1300–1400 °C. Then the sheet is annealed and cold rolled with a reduction rate
of about 70% and annealed at 900 °C and cold rolled again with a reduction rate
of 50%. The coil is then decarburized in wet hydrogen and nitrogen at 800 °C,
coated by MgO, wound into a coil, and finally annealed between 1100 and 1200 °C
in dry hydrogen. The MgO coating is necessary to avoid sticking of the turns
during annealing, and it reacts with Si to form an Fe-Mg silicate at the surface,
a glass film also useful to ensure electrical insulation. The last thermal treatment
produces the secondary recrystallization yielding the texture if a proper growth
inhibitor (usually MnS) is used to impede primary recrystallization that would lead
to isotropic texture. The conventional GOSS have much improved permeability and
losses compared to NOSS if the field is applied in the RD, but it is degraded when
the field is applied perpendicularly. As a consequence, transformer cores should be
preferably built from straight parts rather than from EI cuttings (see Fig. 12 in such
a way the flux is always parallel to RD).
1 cm
Fig. 11 Effect of tensile stress along rolling direction (horizontal) on the domain structure . From
left to right, 4 MPa, 12 MPa, 24 MPa (courtesy of R. Barrué). Images are obtained by magneto-
optical Kerr effect microscopy
29 Soft Magnetic Materials and Applications 1459
Cutting
Conventional and HiB GOSS are mostly used in network frequency transformers.
So in most of cases they work at 50 or 60 Hz at high induction over 1.5 T for
conventional and over 1.7 T for HiB. The simplest way to build a transformer core is
to stack sheets cut in E and I shape (Fig. 12). The I is cut to make two windows in two
face-to-face E. EI cores are easy to realize: two stacks are made alternatively with E
and I (or several E/several I); the coils made separately are slipped in one stack, and
the other is slotted in. EI cores have two disadvantages: the flux is perpendicular to
RD in the yoke of the E, and for three-phase types, the window is bigger than the I
so there is always a waste. If low loss and low EMI is required, strip wound cores are
sometimes used in the ring or rectangular form. The single- or double-frame cores
are used for transformers above 1 kVA apparent power because the flux is mostly
parallel to RD except at the corners. To reduce further the losses, the joints are cut
at 45°and overlapped.
Different types of cuttings and grades are used depending on the power of the
transformer (Table 2):
overlaping
joint
– S < 1 kVA, EI core cut in conventional GOSS (low added value products)
– S < 1 kVA, strip wound core from thin conventional GOSS (high added value
products)
– 1 < S < 10 kVA, frame core cut in conventional GOSS
– 10 < S < 100 kVA, frame core cut in low-loss GOSS
– S > 100 kVA, frame core cut in HiB GOSS
GOSS are also used for inductors either using EI cores with air gap (in this case
layers are not alternated) or using cut strip wound rectangular cores. The latter,
often called C cores, are usually made from thin gauge (100 or 50 μm) and used
in power electronic devices up to 10 kHz. In power plant generators, significant
reduction of losses can be obtained using GOSS for the construction of the stator.
Parts containing several teeth are cut and put with RD radial, whereas yoke parts are
arranged with RD tangential.
Low Si Alloys
Reduction of silicon content naturally leads to an improvement of the magnetization.
For example, reduction to 2% Si allows to reach 1.75 T at 5 kA · m−3 at the cost
of higher losses (above 3 W/kg at standard point). These products are laminated
with thickness between 0.5 and 1 mm for mechanical strength reasons. This larger
thickness combined with lower resistivity results in an increase in eddy current loss,
so they are limited to network frequency use (Table 1). Due to their larger ductility,
cutting cost is reduced, but because of larger magnetostriction, the properties are
more dependent on the cutting technique and annealing conditions.
Table 3 Magnetic properties of 6.5% Si steels [24]. The resistivity is not given for graded
materials since it is not constant
Type Thickness (mm) ρ(μΩcm) JS @ B(T ) HC p150 p1400 (W/kg) p11k
2.5 kA/m (A/m) (W/kg) (W/kg)
Graded 0.10 - 1.88 1.44 40 1.10 10.1 30.0
Graded 0.20 - 1.94 1.47 35 1.10 14.5 51.6
Uniform 0.05 82 1.80 1.38 26 0.70 6.50 18.8
Uniform 0.10 82 1.80 1.40 19 0.50 5.70 18.7
brittle and can’t be laminated. A solution was found in the early 1990s by the
Japanese company NKK (now JFE) introducing Si by chemical vapor deposition
(CVD). Starting from a low Si laminated sheet, annealing in an atmosphere
containing silane gas results in diffusion of Si into the metal. Using this method,
the obtained material exhibits excellent mechanical and magnetic properties. 6.5
silicon steel sheets can be made with two different grades: uniform and graded Si
diffusion. Because CVD is a diffusion process from the surface, the lamination is
enriched at the surface only, and then the silicon gradient can be controlled by the
annealing time. Longer annealing leads to homogeneous diffusion in the bulk. The
graded laminations have lower eddy current losses at high frequency because the
eddy currents flow mainly at the surface. In contrast, they have higher hysteresis
loss because there is a gradient of permeability and saturation magnetization across
the thickness (see Table 3.) Thus, the choice of homogeneous or graded material
depends essentially on the working frequency.
Iron-Cobalt Alloys
As shown by Pierre Weiss in 1912, alloying cobalt to iron has a spectacular effect
on magnetic properties since Fe-Co has larger magnetization than iron. This is
due to a modification of iron band structure, where the Fermi level is increased
in such a way that 3d-up sub-band is filled by electrons from 3d-down sub-band
(see Chap. 15, “Metallic Magnetic Materials”).
Fe2 Co has the strongest room temperature magnetization known but is relatively
hard. However, the equiatomic alloy, known as Permindur, has a small anisotropy
constant, a very soft behavior, and still a very high room temperature magnetization,
the reasons why it is preferred in spite of larger cobalt content and higher cost
(Table 4). In some applications, performance is more important than price of
the elements. In airborne systems, the weight of an equipment is paid by fuel
consumption at each takeoff and power of the turbine needed to provide potential
energy at 10,000 m from the ground. Under these conditions, a gain of 20% in
1462 F. Mazaleyrat
Table 4 Main characteristics of Fe-Co alloys. Magnetostriction is given for isotropic alloys, and
ultimate strength σU is given for the hard state (for annealed state, divide by a factor 2 to 3)
Composition Form t mm Density TC (°C) ρμcm JS T λS 10−6 σU MPa
kgm−3
Co49 Fe49 V2 Strips, bars 0.1–1.5 8120 900 40 2.4 70 1200
Co27 Fe73 Cr0.3 Mn0.5 Strips, bars 0.1–3.5 8000 980 20 2.4 40 1000
Co18 Fe79 Cr3 Strips, bars 0.1–3.5 7900 940 30 2.3 30 850
Low-Cobalt Alloys
Because of the price of cobalt, users always try to reduce the cobalt content. Typical
low-cobalt alloys contain about 25 or 18%, to ensure saturation far above iron one
(i.e., 2.2 T). This is however paid by an increase in coercivity and losses as shown in
Table 5. These alloys have lesser performance compared to equiatomic ones but can
be used advantageously in several cases, for example, in landing gear motors which
work only several seconds per flight (so losses have no relevance) or in airborne
transformers because of the smaller magnetostriction producing less noise. Today’s
tendency is to improve the texture of low-Co alloys (easy axis parallel RD) for
transformer applications in order to reduce loss and effective magnetostriction.
Iron-Nickel Alloys
Iron-nickel alloys were studied for the first time by Hopkinson in the 1890s and by
others later for fundamental studies – and in particular by Guillaume who discovered
Invar – but it was only by the 1910s that Elmen from Bell Labs obtained Fe-Ni alloys
with permeability greater than that of pure iron. Invar is not properly speaking a soft
magnetic material as it is used only as a zero thermal expansion coefficient (CTE)
material. It is quoted here for historical reasons and because this feature is due
to compensation of thermal expansion and volume magnetostriction around room
temperature (above TC Invar has thermal expansion comparable to other metals).
Besides Invar, Fe-Ni alloys are of two kinds: bcc Fe-Ni (less than 30% Ni) and fcc
Fe-Ni (more than 30%). In general, there are no applications for the bcc form since
they do not exhibit better properties than Fe-Si at a higher price. By contrast, the
fcc form has many applications because a great variation in JS , μR , HC , TC is
observed with the Ni content. The most striking figure of these alloys is the strong
dependence of magnetocrystalline anisotropy on order. Indeed, when slowly cooled
after annealing in the range of 900–1200 °C, the alloy is ordered and K1 = 0
for 56% of Ni. In contrast, quenched alloys have K1 = 0 for 73% of Ni. As
a consequence, Ni-rich alloys are usually quenched and the Fe-rich ones slowly
cooled.
More detail on the fundamental aspects of Fe-Ni alloy magnetism can be found
in Chap. 15, “Metallic Magnetic Materials”. An overview of industrial Fe-Ni soft
magnetic alloys is given in Table 6; they can be classified into three main families
described below.
Ni-Rich Alloys
These alloys are currently called permalloy after Elmen from Bell Labs in
1920, and their composition is always close to 80% Ni; for this composition,
the material undergoes a spin reorientation transition (say, a change of easy axis
from [111] to [110]) around room temperature and zero magnetostriction together
1464 F. Mazaleyrat
in the disordered state. For this reason, the material properties are very sensitive
to the microstructure and order, so the heat treatment can change drastically the
magnetic characteristics such as coercivity and permeability. Typical heat treatment
consists in heating over 1000 °C, then cooling to 600 °C, and quenching in air.
This procedure retains disorder and promotes high permeability for Ni75 Fe25 .
Alternatively long-time annealing followed by slow cooling (1 day) produces
recrystallization and forms a Ni3 Fe-like ordered alloy. In this case, the maximum
permeability is obtained for lower Ni content. The drawback of Fe-Ni alloys is
the relatively low resistivity because the two elements are from the iron group and
have similar electronegativity. In industrial permalloys, 4 to 6% molybdenum is
usually added to increase the resistivity and to ensure minimum magnetocrystalline
anisotropy and magnetostriction. For example, 5% Mo substituted to Fe in Ni80 Fe20
results in an increase in resistivity from 20 to 60 ·10−8 m, but at the same time,
saturation magnetization is decreased from 1.05 to 0.8 T. Typical Mo-permalloy
contains 5% Mo and 80% Ni, and the magnetic properties can be changed by
the heat treatment: quenched, slowly cooled, recrystallized, or annealed in field.
Annealing is conducted in pure dry hydrogen usually between 1000 °C and 1200 °C
to remove impurities (C, O, S, etc.). The permeability can be enhanced by increasing
treatment temperature (less impurities, bigger grains). Rectangular hysteresis loop
is obtained by slow cooling promoting ordering. For this composition, the easy axis
29 Soft Magnetic Materials and Applications 1465
becomes [111] which (due to the sixfold symmetry) leads, in theory, to a remanence
ratio of 87%, very close to the experimental value. By opposition, flat loops are
obtained by annealing under a magnetic field applied perpendicular to the strip. A
first annealing is conducted at low temperature (about 500°) to adjust K1 = 0 and
followed by field annealing below TC . Mo5 Py is used in any application where
very high permeability and very low coercivity are necessary if magnetization is
not a dimensioning parameter (typically ground fault detector, current transformer).
Rings (toroids) realized by strip winding are the most used shape for permalloy, but
strip wound rectangular cut cores are often used for inductors. In applications where
both K1 = 0 and λs = 0 are required (typically for flexible magnetic shields),
the composition is modified to 6% Mo and 81% Ni. If higher Curie point and
magnetization are required, 4% Mo 80% Ni alloy is preferred (Table 6).
Mumetal is a variant of permalloy in which several % of copper are added
to improve the ductility. This reduces the cost of both lamination and forming
processes, so it is used generally for large rigid magnetic shields or zero field
chambers.
Fe-Rich Alloys
Iron-rich alloys contain at least 30% of nickel; they always have the fcc structure.
Equiatomic alloy is the most used because it offers a nice combination of high
magnetization and permeability together with low coercivity and losses. However,
this alloy exhibits relatively low resistivity which is detrimental to losses in high-
frequency applications (see Table 7). In this case, 36Fe-Ni may be used, but TC is
decreased by 100 K as it is closer to the Invar composition. Iron-rich alloys can be
processed by three routes:
Table 7 Magnetic properties of Fe-Ni alloys. Py is the usual abbreviation for permalloy; R and
F are for rectangular and flat hysteresis loops, respectively
Reference JS (T) HC (A/m) μi μmax BR /JS Loss (W/kg) λS (ppm)
f
static static static % pB
Mumetal 0.78 1.6 40 110 50 = 0.04
p0.5
Mo5-Py 0.80 0.8 75 200 50 50 = 0.02
p0.5 1
Mo5-Py R 0.80 0.8 75 200 85 1
Mo5-Py F 0.80 0.7 100 130 20 1
Mo6-Py 0.66 0.4 300 130 50 0
36Fe-Ni R 1.30 15 3 20 p150 = 1.1 20
36Fe-Ni 1.30 55 2 7
40Fe-Ni 1.45 6 66
50Fe-Ni 1.60 8 4 35 50 p150 = 0.1 24
50Fe-Ni R 1.60 9 100 95
50Fe-Ni F 1.60 1.5 40 100 30
1466 F. Mazaleyrat
1. Moderate hardening (60% skin pass) and 1100 °C annealing under H2 lead to
isotropic texture. This treatment results in an isotropic magnetic behavior and
low losses. The permeability is moderate compared to Ni-rich alloys but much
higher than NOSS. An induction of 1 T is obtained in a field of only 10 A/m, an
order of magnitude lower than NOSS or FeCo. These features are ideal for small
and efficient electrical machines, when the power density is not a key issue. They
are currently used in the form of stamped sheets for stators or rotors and in the
form of bulk parts in electromagnetic relays.
2. Strong hardening (>90%) and >1100 °C annealing produce an anisotropic
cubic texture {100}001, leading to very high rectangularity. Growth inhibitors
(selected impurities) have to be added in the alloy to stabilize the texture and
avoid secondary recrystallization which slightly increases the coercivity. They
are suitable for low-loss transformers, especially at 400 Hz or above, as the
permeability is very high, and in applications where high rectangularity is
needed such as magnetic amplifiers or different types of sensors (fluxgate; see
Chap. 31, “Magnetic Sensors”).
3. Secondary recrystallization at high temperature (>1100 °C) of high-purity alloy
results in anomalous growth of crystals. Subsequent field annealing just below
TC produces uniaxial anisotropy in the direction of the applied field. 55Ni alloy
is preferred because K1 is appreciably smaller in the ordered state compared to
alloy containing 48% of Ni. The field-induced anisotropy is of order 400 Jm−3
which is a bit stronger than the magnetocrystalline one of the ordered alloy (about
200 Jm−3 ) and sufficient to flatten the loop. The remanence to saturation is low,
so the material demagnetizes itself: this feature associated to high induction is
interesting for unipolar transformers (the maximum induction swing is ΔB
JS −BR ) or in any application similar to that of their Ni-rich counterparts (current
transformers, energy meters, etc.) but with smaller price due to the smaller Ni
content.
Thermal Alloys
Thermal alloys have been originally developed to compensate the effect of thermal
fluctuation in magnetic circuits. These alloys have usually a composition close to
Fe30 Ni70 which is at the limit between bcc and fcc phase and has a Curie point of
50 °C. Cr is generally added in the composition since it moves the bcc/fcc limit to
lower Ni content and offers an additional parameter to control TC together with a
reduction the price of the elements.
This is particularly useful for permanent magnet circuits which are usually quite
sensitive to temperature. When a highly stable induction in the gap of a magnetic
circuit containing a permanent magnet is required, a thermal alloy part is used as a
shunt to the magnet. It was used in the past in electrical measurement instruments,
tachometers, relays, etc., but today most of these applications are obsolete. Recently,
a new class of applications appeared for controlled Curie point materials, i.e.,
induction cookware. In this application, a magnetic layer is needed to concentrate
29 Soft Magnetic Materials and Applications 1467
the flux in the pan bottom and maximize the energy transfer. Associated to the
copper layer (needed to ensure thermal homogeneity and strong eddy currents) and
the stainless steel pan body, the alloys must have a similar dilatation coefficient to
the other materials. Advantageously, the Curie point may be adapted to naturally
regulate the temperature to avoid burning the food but also for safety as TC can be
tuned below the ignition point of oil. For frying pans, the Curie point is 260 °C,
whereas for other pans it can be lower (230 °C) or only just above boiling point of
water (120 °C). Eventually, this natural regulation reduces the electrical stress on
the inverter, limiting regulation switching.
The amorphous state of matter, or glassy state, is a solid state having no long-
range order. In a first approach, amorphous solids are considered to have tetrahedral
local order. An amorphous state of matter is natural for silicates formed by rapid
cooling of lava to form obsidian or volcanic glass. However, only metallic glasses
are magnetic, and pure metals (or transition-metal alloys) cannot be obtained in
the glassy state. Thus, some elements called glass formers must be added, and the
quenching rate must be of the order of magnitude of 106 K/s.1 The glass former must
have smaller atomic radius than transition metals, and, eventually, an addition of a
bigger atom (refractory metal) can help. To be magnetic, a glass must contain more
than 60% of transition metals carrying magnetic moment. The general formula is
T1−x−y Mx Ry where for industrial material:
At the industrial scale, the alloys are prepared from pure elements except boron
provided by F3 B or F2 B compounds. The elements are usually melted by induction
in vacuum and poured in a crucible maintained at a temperature several degrees
higher than the melting temperature (1100–1300°C). The liquid metal is projected
by inert gas into a nozzle fitted with a thin slit very close to the rim of a cold wheel
turning with a peripheral speed of about 30–40 m/s. This process is known as planar-
flow casting. The rim is usually made of copper – or copper alloy, e.g., Be brass – to
ensure efficient thermal transfer and water cooled. If the parameters, speed, pressure,
and temperature are properly tuned, the alloy is directly transformed into a ribbon
having a width equal to that of the slit and a thickness of about 20 μm. Depending
on the application, the thickness can be tuned between 18 and 40 μm and the width
from several mm to over 100 mm.
The as-quenched ribbons are in the amorphous state, but they have to be annealed
to release quenching stresses and optimize the magnetic properties. In the case of
cobalt-based alloys, annealing also partly releases free volume. Because iron-based
alloys do not retain free volume, annealing results in a significant embrittlement.
1468 F. Mazaleyrat
Table 8 Composition and structural properties of metallic glasses and nanocrystalline ribbons
[22, 23, 37]
Reference Composition t (μm) TX Density E α
(°C) (MPa) (ppm/K)
Metglas 2605A1 Fe78 B13 Si9 25 550 7.18 <110 2.0
Metglas 2605S3 Fe77 Cr2 B16 Si5 20 535 7.29 <110 6.7
Metglas 2605SC Fe81 B13.5 Si3.5 C2 20 480 7.32 <110 5.9
Metglas 2605CO Fe66 Co18 B15 Si1 25 430 7.56 <110 8.6
Metglas 2826MB Fe40 Ni38 Mo4 B18 20 410 7.90 <110
Metglas 2714A Co66 Fe4 Ni1 B14 Si15 18 550 7.59 <110
Metglas 2705M Co69 Fe4 Ni1 Si12 Mo2 B12 20 520 7.80 <110
Vitrovac 6025 Co66 Fe4 B12 Si16 Mo2 20 530 7.70 <150
Vitrovac 6155 CoBSi 20 480 7.84 <150
Vitrovac 6030 Co70 (Fe, Mo)2 Mn5 (B, Si)23 20 480 7.60 <150
Vitrovac 6006 Ni, Co, Fe)8 0(B, Si)20 20 430 7.80 <150
Vitroperm 800 Fe73.5 Si15.5 B7 Nb3 Cu1 20 630 7.35 190
Vitroperm 500 Fe74.5 Si13.5 B8 Nb3 Cu1 20 630 7.35 190
Finemet Fe73.5 Si13.5 B9 Nb3 Cu1 18 630 7.40 180
t is the thickness, TX the crystallization temperature, E Young’s modulus and α the dilatation
coefficient
The iron-based amorphous alloys exhibit the highest magnetization of all amor-
phous materials due to the large iron content, about 1.6 T (eventually, magnetization
can be improved up to 1.8 T by cobalt addition). As a consequence, they are par-
ticularly fitted for low and medium frequencies when high magnetization is the first
dimensioning parameter. Because of the long-range disorder, the magnetocrystalline
anisotropy is theoretically zero, but the magnetostriction is usually quite strong
(about 25 ppm). This strong magnetostriction has been sometimes used for sensors
or transducers, but in general it is detrimental to the magnetic properties because
internal stresses cannot be totally released, so the permeability remains within the
order of magnitude of 105 “only” and the coercive field is never below several A/m.
In the 1980s, a large variety of iron-based amorphous alloys have been developed,
in particular by Metglas:
Table 9 Magnetic properties of metallic glasses and nanocrystalline ribbons. M is for Metglas
( [22]), VP for Vitroperm (Vacuumschmelze [37]), FT for Finemet (Hitachi [23]), and NP for
NanoPhy (Aperam [5])
Reference JS (T) HC μmax BR /JS Loss TC (°C) ρ (Ωm) λS
(A/m) static % (W/kg) (ppm)
static 100 kHz,
0.2 T
M 2605A1-Z 1.56 2.4 40,000 90 500 415 1.3 27
M 2605A1-F 1.56 2.4 6000 5
M 2605S3-A 1.41 4.8 35,000 50 90 358 1.38 20
M 2605SC 1.61 3.2 30,000 600 370 1.25 30
M 2605CO 1.8 4 25,000 4 90 145 1.23 35
V 6006 0.42 500 95 150 120
M 2826MB-Z 0.88 0.4 80,000 90 500 353 1.38 12
M 2826MB-F 30,000 5
M 2714A 0.55 0.3 115,000 95 50 205 1.42 0
M 2714A 0.55 0.3 30,000 95 45 205 1.42 0
M 2705M 0.77 1.2 600 * 100 365 136 <1
V 6025-Z 0.55 0.3 1000 95 50 210 140 0.2
V 6025-F 100,000 5
V 6155-F 1 0.8 1000 5 58 485 110
V 6030-Z 0.82 1 300,000 95 80 365 130 0.2
V 6030-F 3500 5
VP 800-F 1.2 0.5 100,000 8 40 600 1.15 0.5
VP 500-F 1.25 0.5 20,000 4 40 600 1.15 0.5
FT-3H 1.23 0.6 30,000 89 80 580 1.35 2.3
FT-3M 1.23 2.5 70,000 50 40 580 1.35 2.3
FT-3L 1.23 0.6 17,000 5 34 580 1.35 2.3
FT-3M 1.23 2.5 70,000 40 40 580 1.35 2.3
NP Kμ 1.27 6 200-3000 1 100 580 1.35 <1
• CO, for same applications as SA1 but with higher induction. The magnetic
properties of these alloys are summarized in Table 9
Fig. 13 Left: hysteresis loops of Fe-based Metglas SA1 samples annealed in longitudinal and
transverse field. Right: comparison of magnetization and iron loss curves of Metglas SA1 and HB
new alloy with improved induction (HB) obtained by using a larger amount of Fe
(about 85 at.%) but still not available.
Iron-based amorphous metals are used also in the form of C-cores cut from rolled
rectangular frame or powder cores.
Due to the smallest magnetic moment of cobalt atoms compared to iron, cobalt-
based alloys have markedly lower magnetization than iron-based ones (see Table 9).
In contrast, because they have a very low magnetostriction and low internal stresses
(as they retain free volume), they have the smallest coercivity of all magnetic
materials known and the highest permeability (see Table 9). In addition, thanks
to this nearly zero magnetocrystalline and magnetoelastic anisotropy, uniaxial
anisotropy can be induced by field annealing resulting in perfectly square or
perfectly linear hysteresis loop (Fig. 14 left box). These features are particularly
interesting for saturable cores or when both high permeability and linearity are
required. Because the cobalt is expensive, they are limited to high value-added
applications (sensors) or to applications where a small quantity of material is
required (anti-theft tag).
Nanocrystalline Alloys
Copper forms very small clusters playing the role of nucleating agent for Fe-Si
particles, whereas Nb acts as a growth inhibitor. The result is a homogeneous
distribution of 10–15 nm Fe80 Si20 particles representing about 65 vol.% in the
optimal state, embedded in the remaining amorphous matrix [33]. Owing to the
small grain size, the anisotropy is averaged over the exchange length resulting in a
nearly zero anisotropy following the mechanism proposed in [2] and demonstrated
conclusively in nanocrystalline materials by Herzer [20]. In addition, because
the Fe80 Si20 nanocrystals have negative magnetostriction, whereas the amorphous
remaining phase (composition close to Fe70 B30 ) has a positive one, proper tuning
of the Si content and the annealing leads to compensation down to nearly zero [21].
As a consequence, Finemet-type nanocrystalline materials have advantages of both
iron-based and cobalt-based amorphous, namely, high magnetization and extreme
softness (see Table 9). As cobalt-based metallic glasses, longitudinal field annealing
produces squares loops and transverse field annealing flat loops with high linearity
and low squareness (Fig. 15 left box). Compared to amorphous alloys, Finemet
exhibits loss much lower than Fe-based alloys and equal to Co-based at lower price
and possibly higher induction (Fig. 14 right box).
The most striking figure of this alloys is the effect of stress applied during
annealing. As shown firstly by Glaser [19], stress annealing induces a very strong
anisotropy perpendicular to the tension direction and directly proportional to the
tension applied. This results in very flat and linear loops; those permeabilities can
be directly controlled by the stress according to μR 7 × 104 /σ where the stress
σ is expressed in MPa [3]. Stress annealed strips are currently produced using
Arcelor-CNRS process [4] and usually rolled into ring shape. These components
have the capacity to store energy, not in an air gap as usual but in the material itself.
1472 F. Mazaleyrat
Soft Ferrites
Spinel Ferrites
Spinel ferrites are iron oxides having the crystal structure of the mineral MgAl2 O4 .
The general formula of ferrites is MFe2 O4 where M is a divalent metal or a
combination having an ionic radius compatible with available octahedral (B) and
tetrahedral (A) sites of the lattice. Depending on the ionic diameter of the divalent
metal, the spinel can be normal (divalent metal in A site, like Zn) or inverse (divalent
metal in B site, like Fe, Co, Ni) or sometimes mixed (like Mn or combination of
two divalent ions or even a combination of univalent and trivalent ions). Actually
the position of M2+ depends both on its diameter (big ion goes in bigger B site)
and electrostatic interactions (more charged ion goes in the B site). Because all
magnetic exchange interactions are antiferromagnetic, the energy of the lattice is
usually minimized for the minimum magnetic moment. Consequently, because Fe3+
has the largest magnetic moment (5 μB ), Fe3+ moments cancel. In simple ferrites
29 Soft Magnetic Materials and Applications 1473
Table 10 Distribution of ions in spinel sites for simple ferrites and example of a mixed ferrite
Normal Inverse Zn0.25 Ni0.75 Fe2 O4
(A) [B] (A) [B] (A) [B]
2+
3+ 3+
3+ 2+ 3+
3+
M Fe2 O4 Fe Fe M O4 Zn 3Fe 5Fe 3Ni2+ O16
tetra octa tetra octa tetra octa
↑ ↑↓ ↓ ↑ ↑ · ↓↓↓ ↑↑↑↑↑ ↑↑↑
(when M is one element), the net magnetic moment per formula is given by that of
M2+ , as illustrated Table 10. The situation is a little bit more complicated for mixed
ferrites but very interesting when M is a combination of Zn and another ion holding
a magnetic moment. Because Zn goes in (A) and because it has a zero magnetic
moment, the moment associated to (A) is reduced, and if Zn content is smaller than
0.5, the magnetic order keeps that of the inverse spinel so the net moment increases
(see Table 10). This is often used in commercial ferrites in the aim of enhancing the
magnetization. However, increasing the Zn content over 0.5 yields partial normal
spinel magnetic order and thus a reduction of the magnetization. The reader would
find more detail in Chap. 17, “Magnetic Oxides and other Compounds”.
In spite of a strong magnetic moment, iron ferrite – aka magnetite, load stone –
is not used as a soft magnetic material because of its relatively high coercivity.
Fe2+ has a nonzero orbital moment that leads to strong spin-orbit coupling
and consequently strong spin-lattice coupling (in other words magnetocrystalline
anisotropy). Another drawback of magnetite is its conductivity. Indeed, the Fe2+
is the octahedral site, which is favorable from ionic diameter point of view but
unfavorable from electrostatic point of view, so hopping of an electron from Fe2+ to
A site Fe3+ yields little change in energy, and this hopping is made easier by thermal
excitation. As consequence, magnetite is an intrinsic semiconductor; its conductivity
is typically 10−4 m at room temperature. It is thus important for high-frequency
application to replace totally all ferrous ions. Technically speaking, hundred kinds
of ferrites can be (and have been) made since elements from Ti to Zn plus Mg, Li,
Al, etc., can be substituted. Fortunately, Darwin’s theory also applies to technology
so few families only of ferrite have markets, mainly Mn-Zn and Ni-Zn and, in a
much smaller extent, Li and Mg ferrites.
Raw Materials – industrial ferrites are produced by the ceramic route. In general,
the precursor materials are simple oxides: Fe2 O3 , MnO, ZnO, NiO, CuO, CoO, etc.
The purity and the grain size of the powders have significant influence on the final
properties. Ideally, they should be fine and homogeneous in grain size to ensure the
chemical homogeneity.
Milling – after weighting the oxides as a function of the expected composition,
the powder is milled in order to get a homogeneous mix with finer grains. This
1474 F. Mazaleyrat
operation is important to optimize the reaction. Usually the mill is made from
stainless steel so excess iron may be brought at this stage.
Firing – the mix is heated in air at a temperature between 900 and 1100°C,
depending on the grain size, to produce the solid-state reaction. At this stage, the
spinel phase is formed.
Milling – because firing produces grain growth, a second milling is necessary to
refine the grains, preferably below 1 μm, before sintering. At this stage, different
additives can be introduced in small quantities such as V2 05 , to reduce sintering
temperature, Si02 , to limit grain growth, CaO, to increase the resistivity, etc.
Forming – the powder is now mixed with an organic binder (usually PVA) and
pressed in a mold to give the final shape of the core. There is a great variety of
shapes that can be made industrially: rings, E, I, U, pots, rods, screws, plates, tubes,
etc. Pressing is generally uniaxial; isostatic pressing is used only at laboratory scale
to realize big cores or with complex shapes.
Sintering – To densify the core and to obtain good properties, sintering must
be conducted with caution. Depending on the composition, the grain size before
sintering, and the expected grain size after, the temperature is usually above 900°C
and up 1350°C. Sintering takes several hours, and cooling rate must be low,
particularly for bigger cores, in order to avoid cracking. NiZn ferrites are sintered
in air, but MnZn ones must be sintered in controlled atmosphere. Indeed, the partial
oxygen pressure in air is such that it would oxidize Mn2+ , so it must be controlled
according to ln p02 = −K/T .
Mn-Zn Ferrites
Manganese simple ferrite is a mixed type one: Mn ions are found in both sites.
Mn2+ substitution is very interesting because this ion exhibits a strong spin (5/2)
and a zero orbital moment. Thus, Mn-based ferrites can be extremely soft.
– Enhances the magnetic moment (within the limit of 0.5 per f.u.) as said before
– Affects AB exchange coupling resulting in a decrease in Curie temperature (TC )
– Reduces the magnetocrystalline anisotropy (K1 ) and thus tends to increase the
permeability (μR )
Interestingly, because higher magnetic moment can be obtained only at the price
of a reduction in Curie temperature, the highest magnetization at room temperature
is obtained for a relatively small Zn content (x 0.15).
Mn ferrite has a low magnetocrystalline anisotropy (due to 3d5 configuration of
ions) with a [111] easy axis, whereas Fe ferrite has strong anisotropy (due to Fe2+ )
with a [110] easy axis. As a consequence, a controlled excess of Fe can produce a
29 Soft Magnetic Materials and Applications 1475
Fig. 16 Permeability and loss dependence of high-frequency MnZn power ferrite on temperature
Table 11 Main applications of Mn1−x Znx Fe2 04 and typical compromise on Zn content
Application Main parameter Zn TC (°C) μ0 MS (T) μ0 MS (T)
content 0K 300 K
Telecom transformers MS 0.2 250 0.7 0.54
Power transformers TC , MS 0.3 230 0.78 0.5
Wide-band transformers μR , TC , loss 0.5 150 0.9 0.4
Signal transformers μR 0.55 130 1 0.39
1 JS D
μR ∝ ∝√ (47)
HC K1
1476 F. Mazaleyrat
where D is the grain size. So getting the highest permeability means large Zn
content and coarse grains. However, MnZn ferrite, like magnetite, has a relatively
low resistivity (even without ferrous ions) due to electron hopping between divalent
and trivalent Mn ions. The intrinsic resistivity of MnZn ferrite is about 0.1 m
so in high-frequency applications eddy currents in the core would produce high
losses (see section “Eddy Currents”). CaO is added for this purpose because it’s an
electrical insulator and because the ionic radius of Ca2+ is too big to enter in the
spinel lattice. Thus, after sintering CaO segregates at grain boundaries forming an
insulating barrier of thickness t. The electrical resistivity can be written in a first
approximation ρeff (t + D) = ρCaO t + ρMnZn D. As ρCaO t ρMnZn D and t and
D are several nm and μm, respectively:
t
ρeff ρCaO (48)
D
μR
μeff = (49)
1 + μR Dt
Table 12 Main Mn1−x Znx Fe2 04 materials used for broadband transformers, pulse transformers,
common mode chokes, and delay lines. References starting with a letter are from TDK, with a
number from Ferroxcube
Ref. x B1k (T) B1k (T) μi fR (Hz) HC (A/m) TC (°C) ρ (m) fmax (Hz)
(approx) 25°C 100°C ± 30% 25°C
T46 0.55 0.40 0.24 15000 400 k 7 130 0.01 100 k
T38 0.55 0.43 0.26 10000 300 k 8 130 0.1 100 k
T36 0.55 0.40 0.24 7000 300 k 22 130 0.2 100 k
T37 0.55 0.38 0.24 6500 700 k 9 130 0.2 300 k
N30 0.55 0.38 0.24 4300 1M 12 130 0.5 400 k
3E6 0.55 0.39 0.22 12000 400 k 5 130 0.1 100 k
3E7 0.55 0.39 0.22 15000 250 k 4.5 130 0.1 100 k
Table 13 Main Mn1−x Znx Fe2 04 materials used for power transformers and power electronics.
References starting with a letter are from TDK, with a number from Ferroxcube.B1k is the
induction measured at 1 kAm−1
Ref. x B1k (T) B1k (T) μi fR (Hz) HC (A/m) TC (°C) ρ (m) fmax (Hz)
(approx) 25°C 100°C ±30% 25°C
N72 0.37 0.48 0.37 2500 20 M 23 210 12 300 k
N27 0.35 0.50 0.41 2000 15 M 33 220 3 150 k
N49 0.3 0.49 0.40 1500 30 M 42 240 17 1M
3C93 0.3 0.52 0.43 1800 20 M 13 240 5 300 k
3F35 0.3 0.5 0.42 1400 50 M 40 240 10 1M
sufficient, there is a risk of thermal runaway. Losses of selected ferrites are given in
Annex 1, Table 17, and compared with competing materials (Table 13).
Ni-Zn Ferrites
The simple nickel ferrite is an inverse spinel: this means that the Ni2+ ion goes in the
octahedral site only. The effect of Zn substitution on intrinsic magnetic properties is
very similar to that in MnZn ferrites, except that Ni gives lower magnetic moment
(2 μB ) and higher Curie point and anisotropy constant than Mn. This means that
NiZn ferrites can be used at higher temperature than MnZn ones in general and
that their permeability will be lower. However, the great advantage is that Ni can
be divalent only and iron trivalent only, so conduction by electron hopping is
impossible. As a consequence, the resistivity is within the order of magnitude of
>105 m. A very small excess of iron results in a spectacular drop in resistivity
(six orders of magnitude); it is thus usual to prepare the ferrite with a slight iron
default (e.g., 1.96 instead of 2) in order to compensate iron pollution from steel
balls and vial of the mill. NiZn ferrites can be sintered in air (no control of the
oxygen pressure needed) without prejudice of the magnetic or electrical properties.
As a consequence, there is no need to introduce interfacial resistive oxide. The
magnetic properties of NiZn ferrites are controlled by two parameters, the zinc
content and the microstructure. As in MnZn ferrite, the Zn lowers the Curie point
and by consequence the magnetocrystalline anisotropy and in turn enhances the
1478 F. Mazaleyrat
Table 14 Main Ni1−x Znx Fe2 04 materials. References starting with a letter are from TDK, with
a number from Ferroxcube. B5k is the induction measured at 5 kAm−1
Ref. x B5k (T) B5k (T) μi fR (Hz) HC (A/m) TC (°C) ρ (m) fmax (Hz)
(approx) 25°C 100°C ± 30% 25°C
K1 0.30 0.31 0.28 80 50 M 400 425 105 12 M
4C65 0.35 0.38 0.34 125 55 M 280 350 105 1M
4B1 0.38 0.36 0.31 250 25 M 150 260 105 1M
4A11 0.60 0.34 0.23 850 7M 33 180 105 1M
K10 0.65 0.32 0.24 800 4M 165 115 105 1M
4A20 0.72 0.26 0.15 2000 1.4 M 11 100 105 300 k
permeability. In Table 14, a clear correlation is seen between TC and μi . Also the
sintering temperature plays a role since it affects the grain size and the density (49).
For example, in order to have a large bandpass, 4C65 has low zinc content and is
sintered at lower temperature to get low density (4500 kg · m−3 , 86%) and small
grain size. In contrast, to get a large permeability, 4A20 has high content of Zn
and is sintered at higher temperature to get high density (5000 kg · m−3 , 96%) and
coarser grains.
Ni-Zn-Cu Ferrite
This family of ferrite is basically issued from NiZn one. It was developed for the
manufacturing of micro-inductances. A micro-inductance is a component made by
co-sintering of a metallic coil embedded in ferrite (typically from 1 × 0.5 × 0.5 mm
to 2 × 1.25 × 1.25 mm). This is realized by stacking bonded ferrites and silica tapes
on which coils are printed. In principle, noble metals (Pd, Pt) are compatible with
ferrites, but they are too expensive. As a consequence, the sintering temperature is
decreased by substitution of copper to Ni to be compatible with silver (about 950°C).
The typical formula is Ni1−x−y Znx Cuy Fe2 04 , where 0.3 < Zn < 0.6 and 0.1 <
Cu < 0.2. In principle, manufacturers provide properties of the components but not
that of the material. However, properties of these ferrites are comparable to that of
NiZn, i.e., a permeability in the range of several hundreds with substantially lower
magnetization [25]. Also Ni-Zn-Cu ferrites show very low loss at high frequency
(about 300 mWcm−3 at 1.5 MHz, 25 mT) when a small amount of Co is substituted
to Ni in order to produce a SRT close to room temperature [31, 32].
Microwave Ferrites
The term microwave usually refers to UHF to mm waves (300 MHz to 300 GHz
according to IEEE standard), but ferrites are used only below 110 GHz (W-band).
In microwave applications, the main quantity characterizing the material is not the
permeability or the magnetization but the gyromagnetic resonance frequency. In soft
29 Soft Magnetic Materials and Applications 1479
magnetic materials, the anisotropy field is by definition low, so the main field is the
dipolar field produced by the magnetization itself. As a consequence, the resonance
frequency is mainly defined by
γ
fR = JS (50)
2π
γ
where 2π 28 GHz/T. The working frequency is usually chosen in the vicinity of
fR , higher in the upper band, lower in the lower band. So from (50) it is clear that a
low magnetization is necessary for UHF, whereas a high one is needed in W-band.
At constant frequency, the material shows an absorption peak (a maximum in μ ) as
a function of the DC field. This absorption peak is characterized by its FWHM, ΔH
expressed in A/m and is the main characteristic of microwave ferrites. Depending
on the application, the line width ΔH should be sharp or large and can be tuned
according to [28]
3 μ0 K1
ΔH = ΔHi + pJS + 2.07 3 (51)
2μ0 JS
where the first term – due to gyromagnetic damping – is intrinsic (see Chap. 26,
“Electron Paramagnetic and Ferromagnetic Resonance”), the second term corre-
sponds to the broadening due to porosity (p), and the last one is due to spin wave
broadening (the factor 2.07 is for a sphere). Because porosity is not desirable, as
it is detrimental to the losses, ΔH is tuned by adjusting JS with substitutions. In
nonreciprocal applications, such as gyrators or isolators, the DC field is constant and
can be produced by a magnet. In reciprocal applications, a DC field is applied to the
material by a permanent magnet, and the microwave field is applied perpendicularly
(or less commonly parallel in some applications). In tunable phase shifter, the field
is of course variable and produced by an electromagnet. In applications exploiting
the Faraday effect (rotation of the polarization plane), the ferrite is not polarized.
Microwave ferrites are of two types: spinels and garnets; their main characteris-
tics are given in Table 15.
Microwave spinels are very similar to other soft ferrites except the substitution
type or rate:
– NiZn microwave ferrites contain less Zn in general (between 0 and 0.3); they
are cheapest microwave ferrites since they are massively produced for other
purposes.
– Magnesium ferrites, in which Mg is combined with Mn as divalent element,
which exhibits lower loss than NiZn ones.
– Lithium ferrite , where Li+ is combined with trivalent iron according to the
formula (Li+ 3+
0.5 Fe0.5 )1−x Znx Fe2 04 , which has sharper absorption line.
1480 F. Mazaleyrat
Table 15 Properties of selected microwave ferrites [39, 6, 30]. For gadolinium-iron garnets,
the compensation point of the magnetization is indicated with the Curie point. The dielectric
permittivity lies in the range 13–16
Composition JS (T) TC (°C) ΔH (kA/m) Frequency of use (GHz)
25°C
NiFe2 04 0.34 585 32 10–40
Ni0.6 Zn0.4 Fe2 04 0.5 350 13 10–40
Li0.5 Fe0.5 Fe2 04 0.36 640 28 10–40
Li0.3 Fe0.3 Zn0.4 Fe2 04 0.50 425 8 10–40
Y3 Fe5 012 0.19 290 6 1–10
Y1.5 Gd1.5 Fe5 012 0.096 −150/290 14 1–10
Gd3 Fe5 012 0.009 27/290 broad 1–10
Y2.4 Ca0.6 Fe4.7 V0.3 O12 0.122 235 4 1–10
Y1.4 Ca1.6 Fe4.1 V0.8 O12 0.036 225 40 1–10
Y3 Fe4.75 In0.25 O12 0.19 207 3 1–10
Y1.8 Ca1.2 Fe3.8 V0.6 In0.6 O12 0.1 109 1 1–10
Among microwave spinels, lithium one shows the best properties (small ΔH , high
TC , low loss), but they are much more difficult to produce since Li partly evaporates
during firing.
Yttrium iron garnet (YIG) has the canonical composition (Y3 Fe5 012 ) where
all metal ions are trivalent. Here, again, there are a lot of possible substitutions
providing the ion has charge and ionic radius compatible with the crystallographic
site in which it is supposed to go. Most common substitutions are:
YIG is the only magnetic material transparent to light (in the near infrared) and
displays strong Faraday effect ; it is thus also used in magneto-optical devices. Due
to its compensation point, Gd-YIG thermal variation of the saturation magnetization
is rather low around room temperature. Upon all microwave ferrites, YIG has the
lowest dielectric loss (tan δ = 2 · 10−4 at 8.2 GHz and ≈5 for spinels).
Microwave ferrites are produced using the same processes as spinel ferrite but
in particular shapes: sphere (in the past), disk, square, or triangle (usually with cut
corners) from 0.5 to 3 mm thick and up to 50 mm large.
29 Soft Magnetic Materials and Applications 1481
Cores with gap are used in every application where inductive energy storage is
necessary such as smoothing chokes or coupled inductors because most of soft
magnetic material cannot store energy (except stress annealed Finemet and in a
lower extent transverse field-annealed amorphous alloys and permalloy). Gaps can
be either lumped or spread depending on the application.
Core with lumped gap is made of any kind of soft magnetic materials depending
essentially on the frequency of the device (silicon steel, Fe-Ni, Mn-Zn ferrite,
amorphous, etc.). They are exactly similar to single-phase transformer cores except
the fact stacked cores are stacked without overlapping joints and that tape wound
cores are more frequently used. Rectangular tape wound core is cut into two pieces
after impregnation (C-cores), whereas ring cores are molded in resin before cutting
a single gap. The effective permeability of the core (assuming a constant cross-
sectional area along flux lines) is expressed in a very similar way as (49):
μR
μeff = (52)
1 + μR σg
where g is the length of the gap, is the length of the magnetic path, and σ is the
dispersion coefficient due to flux spreading in the gap. For small gaps, i.e., when
g is small compared to and to the dimensions of the cross section, σ 1. If
this condition is not realized, μeff = σg
and σ is usually smaller than 0.5. The
advantage of lump gap core is the possibility to tune the permeability by the user.
However, flux leakage around the gap is responsible for electromagnetic emission
and additional losses due to the nonuniformity of the induction at the gap edges.
Cores with spread gap are used to overcome the drawbacks of lumped cores,
especially in the RF bands. They are realized from metallic powders mixed with
a resin and pressed. The filling factor is adjusted to the target permeability. The
effective permeability can be expressed as a function of the filling factor, φ, the
volume ratio occupied by ferromagnetic particles in the core:
μR
μeff = (53)
1 + μR (1 − φ 1/3 )
1 + 2φ
μeff = (54)
1−φ
The main advantages of powder core compared to lumped gap cores are lower
losses for a given effective permeability and the possibility to shape cores by
pressing or injection molding in the form of rings, E, L, screws, pots, cups, tubes,
rods, etc.
Table 16 Magnetic properties of selected powder cores. φ is the filling factor; D is the mean
grain size [26, 9]
Composition μR JS B10k HC φ D ρ fmax loss mW
(T) (T) (A/m) (%) (μm) (Ωm) (Hz) cm3
Carbonyl iron 11 1.6 0.15 1600 60 4–8 5.105 80 M P125mT
MHz =550
Carbonyl iron 20 1.9 0.3 1600 70 < 10 1 60 M P125mT
MHz =800
Iron 40 1.0 0.9 1200 45 1 2M 25mT
P100 =450
kHz
powder cores, aka soft magnetic composites (SMC), exhibit permeabilities between
200 and 1000; they are used for chokes and electrical motors, respectively.
– Fe50 Ni50 is a compromise between high B iron and low-loss MPP, for μR = 160,
25mT = 70 mWcm−3 .
P100 kHz
– Sendust is an iron alloy containing 9% Si 6% Al, a composition very close to
the ordered Fe3 (Si, Al), that shows characteristics quite similar to MPP (K1 and
λS 0) but with higher magnetization (up to 1 T), for μR = 160, P100 kHz =
25mT
−3
30 mWcm .
– 6.5 silicon steel is also used for its zero magnetostriction (low noise in the audio
band like MPP or Sendust) but with higher losses and lower permeability due to
nonzero K1 .
Table 17 Comparison of losses in different magnetic materials used in power electronics. All
values are indicated for the same B × f = 25 kVm−2 . Losses are expressed in mW · cm−3
B (mT) 1000 250 100 50 25 10 5
f (kHz) 25 100 250 500 1000 2500 5000
3C93 1000 800 300
3F35 80 120
4F1 100 80
N27 1400 1000
N49 1000 300 120 80
N72 400
MP205 7000 6000 6000
Sendust160 4000 2700 2000
2714A 683 759
Finemet 1900 759
1484 F. Mazaleyrat
Table 18 In the following table, different classes of applications are reviewed, and materials are
proposed for the purpose. These propositions are only guidelines; the grade must be adapted to the
application specifications (frequency, shape, cost, etc.). VH stands for very high, H for high, VL
for very low, and L for low
Application Required properties Material type Typical grade
Network transformer H B, VL 50 Hz loss GO Fe-Si M090-23P
HV/LV network transformer H B, VL 50 Hz loss Fe-based glass Metglas SA
H B, VL 50 Hz loss GO Fe-Si M110-27S
LV industrial transformer H B, L 50 Hz loss GO Fe-Si M110-35-N
Airborne transformer VH B Fe-Co 49%Co
Household transformer L cost L Si steel M600-50-A
Power station generator stator H B, VL loss GO Fe-Si M090-30-N
Power station generator rotor strength Forged steel 95%Fe+Ni, Cr, Mo, C
Boat/train motors H B, L loss NO FeSi M235-35-A
Industrial motors H B, L 50 Hz loss NO FeSi M330-35-A
High-speed motors H B, L VF-band loss NO FeSi M270-20-A
Automobile motors H B, VL loss NO FeSi M210-27-A
Automobile generators H B, L cost NO FeSi M400-50-A
Claw pole rotor Forgeability C steel C05E
Airborne generators VH B, Strength FeCo 25%Co
Electromagnetic motor valve VH B FeCo 49%Co
Household AC motors L cost L Si steel M600-50-A
Small DC motor stator Stampability Steel Low C
Small DC motor rotor L cost L Si steel M600-50-A
Watch step motor H B and μ Fe-Ni 50%
Inductive encoders Fe-Ni 50%
Forward SMPS transformer L 10kHz loss Co amorphous F loop
Co-based F loop
Nanocryst. F loop
MnZn ferrite Power grade
Flyback SMPS transformer BR = 0, L μ MnZn ferrite Power grade+gap
Nanocrystalline Stress annealed
Smoothing choke Linearity, f<10 kHz FeSi Wound core+gap
Linearity, f<100 kHz MnZn Gap
Linearity, f<100 kHz Powder core MPP or iron
Linearity, f<100 kHz Nanocrystalline Stress annealed
Linearity, f>100 kHz Carbonyl iron
Resonance SMPS L LF-band loss MnZn ferrite Power grade
Powder core MPP
L MF-band loss NiZn ferrite Power grade
MPP Carbonyl iron
Wideband transformer Hμ Signal grade
Drive transformers for IGBT H μ, linearity FeNi Field-annealed permalloy
(continued)
29 Soft Magnetic Materials and Applications 1485
Table 18 (continued)
Drive transformer for GTO H BR , H dynamics FeNi Textured 50%Ni
Network inductor HB GO FeSi N-grade wound core +
gap
Pulse transformer H BR , H dyn. Co amorphous Z loop
Spike killer H BR , H dyn. Co amorphous Z loop
Delay lines H μ, bar shape MnZn ferrite Signal grade
Magnetic amplifier H BR GO FeSi N-grade wound core
Current transformer Hμ Permalloy F loop
Co amorphous F loop
Nanocryst. F loop
Thick-layer micro-inductor Low sintering temp. Ni-Zn-Cu ferrite Tape casting
On-ship inductance Integration YIG RF sputtered on
substrate
On-ship transformer Hμ Fe-Ni Electrodeposited
Flux-gate sensor VH BR , VL HC Co amorphous F loop
Hall effect sensors L BR , L HC MnZn ferrite Signal grade
Magnetostrictive sensor HλS Amorphous Fe/FeNi based
Proximity sensors H MF-band μ MnZn ferrite
Ground fault circuit breaker VH μ Co amorphous F loop
Nanocryst. F loop
FeNi Permalloy
Common mode filter VH μ MnZn ferrite Signal grade
Nanocrystalline Field annealed
LF filter Lμ MnZn ferrite Signal grade + gap
MF-UHF filter Lμ NiZn ferrite
Telecom transformer Hμ MnZn ferrite Signal grade
LF antennae Linearity, high μ MnZn ferrite
MF antennae Bandwidth NiZn ferrite μ < 1000
HF antennae Bandwidth NiZn ferrite μ < 250
VHF antennae Bandwidth NiZn ferrite μ < 100
UHF antennae Bandwidth NiZn μ < 20
Radar absorber UHF absorption NiZn Plate, structured surface
Faraday effect uniline HC < 100A/m Li ferrite Rod
Resonator filter L loss, L ΔH (Ga)YIG Single crystal sphere
Circulator, phase shifter f < 1.5 GHz Gd-YIG Plate, rod
1.5 < f < 10 GHz Al-YIG id.
f > 10 GHz Li or NiZn spinel id.
Wireless energy transfer H B, L MF-band loss Ferrite MnZn
Zero Tesla chamber Hμ FeNi mumetal
MF magnetic shielding MnZn ferrite Signal grade
Flexible magnetic shielding H μ Nanocrystalline film-coated ribbon
Large bandwidth MnZn ferrite Powder in polymer film
Induction cooking pan Controlled TC FeNi Thermal alloy
DC electromagnet HB Fe/low C steel Bulk
AC electromagnet HB FeSi M600-100-A
1486 F. Mazaleyrat
Notes
1 Bulk metallic glasses have been successfully produced by the end of the 1990s, but they have
relatively low magnetization. In addition, the bulk state is a drawback for applications, so they
have never been produced at industrial scale.
2 The compensation point, see Chap. 17, “Magnetic Oxides and Other Compounds.”
References
1. Ahmadi, B., Zehani, K., LoBue, M., Loyau, V., Mazaleyrat, F.: Temperature dependence of
magnetic behaviour in very fine grained, spark plasma sintered NiCuZn ferrites. J. Appl. Phys.
111(7), 07A510 (2012)
2. Alben, R., Becker, J.J., Chi, M.C.: Random anisotropy in amorphous ferromagnets. J. Appl.
Phys. 49, 1643 (1978)
3. Alves, F., Simon, F., Kane, S.N., Mazaleyrat, F., Waeckerle, T. Save, T., Gupta, A.: Influence
of rapid stress annealing on magnetic and structural properties of nanocrystalline Fe74.5 Cu1
Nb3 Si15.5 B6 alloy. J. Magn. Magn. Mater. 294(2), e141–e144 (2005)
4. J-B; Hérission, D., Benchabi, A., Waekerlé, T., Fraisse, H., Boulogne, B.A., Desmoulin,
F.: Nanocrystalline material strip production for the formation of magnetic torus comprises
annealing cast amorphous ribbon of specified composition defiling under tension (2002)
5. Amperam.: Nanocrystalline Core Solution (2012)
6. Anderson, E.E., Cunningham, J.R. Jr, McDuffie, G.E.: Magnetic properties of the mixed
garnets (3-x) Y2 O3·x Gd2 O3·5 Fe2 O3 . Phys. Rev. 116(3), 624 (1959)
7. Appino, C., Khan, M., de la Barrière, O., Ragusa, C., Fiorillo, F.: Alternating and rotational
losses up to magnetic saturation in non-oriented steel sheets. IEEE Trans. Magn. 52(5), 1–4
(2016)
8. Barbisio, E., Fiorillo, F., Ragusa, C.: Predicting loss in magnetic steels under arbitrary
induction waveform and with minor hysteresis loops. IEEE Trans. Magn. 40(4), 1810–1819
(2004)
9. BASF.: Carbonyl Iron Powder for Inductive Electronic Components
10. Beatrice, C., Appino, C., de la Barrière, O., Fiorillo, F., Ragusa, C.: Broadband magnetic losses
in fe-si and fe-co laminations. IEEE Trans. Magn. 50(4), 1–4 (2014)
11. Bertotti, G.: Hysteresi in Magnetism. Academic Press, San Diego (1998)
12. Bertotti, G.: General properties of power losses in soft ferromagnetic materials. IEEE Trans.
Magn. 24(1), 621–630 (1988)
13. Bertotti, G.: Dynamic generalization of the scalar preisach model of hysteresis. IEEE Trans.
Magn. 28(5), 2599–2601 (1992)
14. Bertotti, G., Mayergoyz, I.D. (eds).: The Science of Hysteresis: Physical Modeling, Micromag-
netics, and Magnetization Dynamics. Academic Press, Oxford (2006)
15. Brailsford, F.: Physical Principles of Magnetism. van Nostrand, London (1966)
16. Cazin, A.: Sur les effets thermiques du magnétisme. J. Phys. Theor. Appl. 5(1), 111–118 (1876)
17. de la Barriere, O., Ragusa, C., Appino, C., Fiorillo, F., LoBue, M., Mazaleyrat, F.: A
computationally effective dynamic hysteresis model taking into account skin effect in magnetic
laminations. Phys. B Condens. Matter 435, 80–83 (2014)
18. Ewing, J.A.: Induction in iron and other metals. The Electrician, 3rd edn. The Electrician
Publishing co, London (1901)
19. Glaser, A.A., Kleynerman, N.M., Lukshina, V.A., Patapov, A.P., Serikov, V.V.: Thermome-
chanical treatment of the nanocrystalline alloy fecunbsib. Phys. Met. Metal. 72, 53 (1991)
20. Herzer, G.: Grain structure and magnetism of nanocrystalline ferromagnets. IEEE Trans. Magn.
25, 3327–3329 (1989)
21. Herzer, G.: Grain size dependence of coercivity and permeability in nanocrystalline ferromag-
nets. IEEE Trans. Magn. 26, 1397–1402 (1990)
29 Soft Magnetic Materials and Applications 1487
Contents
Introduction: The Magnetocaloric Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1490
Cooling at Low or Intermediate Temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1494
A Brief History of the Magnetocaloric Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1494
Adiabatic Demagnetization (ADR) Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1495
Nuclear Adiabatic Demagnetization (NDR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1497
The Magnetocaloric Effect Near Room Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1498
Room Temperature Magnetocaloric Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1498
Room Temperature Magnetic Cooling Engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1509
Power Conversion and Spin Caloritronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511
Power Conversion via Pyromagnetic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511
Spin Seebeck and Spin Nernst Effects and Spin Caloritronics . . . . . . . . . . . . . . . . . . . . . . 1513
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1518
Abstract
K. G. Sandeman ()
Department of Physics, Brooklyn College of the City University of New York, Brooklyn,
NY, USA
The Physics Program, The Graduate Center, CUNY, New York, NY, USA
e-mail: [email protected]
S. Takei
The Physics Program, The Graduate Center, CUNY, New York, NY, USA
Department of Physics, Queens College of the City University of New York, Flushing, NY, USA
e-mail: [email protected]
magnetocaloric effect. Then, the range of materials, often with first-order phase
transitions, that are the feature of current magnetocaloric effect studies near room
temperature is presented. Lastly, progress is examined in utilizing the reverse
magnetocaloric (pyromagnetic) effect for power generation and in using the
spin Seebeck, spin Hall, and spin Nernst effects in thin-film heterostructures for
spintronics and caloritronics.
dG = −SdT − MdH + Ki dσi + . . . , (1)
i
where the symbols here have their usual meanings: S is (total) entropy; M is the
magnetisation; Ki are the anisotropy constants, and σ i is the relevant direction
cosines for the crystal symmetry of the particular material. If we consider variations
in the magnitude (rather than direction) of the magnetization, then from this free
energy, a Maxwell relation that connects the thermal variation of magnetization to
the field dependence of total entropy may be written:
30 Magnetocaloric Materials and Applications 1491
∂S ∂M
= . (2)
∂H T ∂T H
This Maxwell relation may be integrated to obtain the change of total entropy
that results from the isothermal application of a magnetic field:
Happlied ∂M
S T , Happlied = dH. (3)
0 ∂T H
Happlied T ∂M
Tad T , Happlied = − dH (4)
0 c (T , H ) ∂T H
Fig. 1 A schematic of the conventional MCE associated with a material that can possess a
sharp first-order or gradual second-order phase transition with ∂M
∂T < 0, depending on material
composition or magnetic field. The first-order region is associated with larger magnetization
gradient and hence larger S and Tad . (Aspects of this figure have been reproduced from I.
Takeuchi and K.G. Sandeman, Phys. Today 68, 48 (2015) [5] with the permission of the American
Institute of Physics. An inverse magnetocaloric material possesses the opposite sign of ∂M
∂T , S,
and Tad )
dG = −SdT − MdH + Ki dσi + V dp − P d + . . . , (5)
i
By analogy with the above analysis, we can see that the electrocaloric effect,
the temperature change induced by a change in the magnitude of an electric field,
applied , is
Eapplied T ∂P
Tad T , Eapplied = − dE. (6)
0 c (T , E) ∂T
The last of these relations is in fact key to conventional, gas compression cooling.
The temperature change of a material induced by a change in applied pressure is
greatest when there is a large variation of material volume with temperature ∂V ∂T .
For this reason, a material with a liquid-gas phase transition is an ideal candidate for
observation of a large barocaloric effects, and such materials have been the majority
of (gas-compression) refrigerants to date. In gas-based cooling devices, a volatile
liquid is expanded through a nozzle and cools (Fig. 2). It then exchanges heat with
the items to be cooled, before being compressed. The compression stage raises the
30 Magnetocaloric Materials and Applications 1493
Fig. 2 A schematic comparison of a gas-based cooling cycle (a) and a solid-state ferroic cooling
cycle (b). (These figures have been reproduced from I. Takeuchi and K.G. Sandeman, Phys. Today
68, 48 (2015) [5] with the permission of the American Institute of Physics. We note that, in the
latter case, a separate fluid is needed to exchange heat with the ferroic refrigerant)
refrigerant’s temperature, and so the last stage in the cooling cycle is an exchange
of heat with the surroundings (e.g., via a radiator).
At this point, it is instructive to take stock of the basic thermodynamics presented
above to distinguish two means of providing (magneto)caloric effects. The first is
in when the applied field does not induce a phase transition; then the values of
Tad (and S) will be moderate or small. Exceptions occur when the temperature
is low enough either for the phononic part of the heat capacity to be quenched
or for the magnetic susceptibility – especially in the case of a paramagnet – to
become large. Stated in another way, without a phase transition, the entropy change
associated with magnetic moment rotation (the paraprocess) is small compared
to the entropy required to change the ordering of phonons, especially at elevated
temperatures. As a result, this version of the magnetocaloric effect has been used
in low temperature research applications and has become known as adiabatic
demagnetization refrigeration (ADR; see Sect. “Adiabatic Demagnetization (ADR)
Materials”), although the process of adiabatic demagnetization can apply to a
cooling cycle with or without a phase transition in the refrigerant.
The second type of magnetocaloric effectarises around a phase transition. In that
case, larger (potentially infinite) values of ∂M ∂T H can be found, and – especially
in the case of a first-order phase transition – large values of Tad and S can be
observed, not just at low temperatures but also at elevated temperatures. In this case,
the applied field can induce a large (phase) change in the entropy of the magnetic
subsystem and thereby a large change in the phononic subsystem. Some numerical
values for both Tad and S around room temperature will be provided for the
materials discussed in the following sections.
The surge in interest in magnetic cooling during the last 20 years has stemmed
primarily from interest in the latter examples of MCEs observed in first-order
transition materials, motivated by the potential use of magnetic refrigerants in the
room temperature range as replacement working materials in a gas-free cooling
1494 K. G. Sandeman and S. Takei
engine. There are two main drivers. Firstly, many of the refrigerants used around
room temperature in gas compression systems are greenhouse gases. The volatility
that is vital to their operation therefore poses a risk of environmental damage
if a leak or improper recycling occurs. Some predictions put the fractional CO2
equivalent contribution of refrigerant and aerosol gases as high as 45% by 2045
[6], while the choice of alternative gas-based refrigerants is somewhat restricted
[7]. Secondly, improvements to the efficiency of modern refrigerators are costly
and involve the use of variable speed compressors that modulate the delivered
cooling power depending on demand. Cost-effective improvements of efficiency
from magnetic (or any other gas-free) cooling method are welcome. The relevance
of this statement is heightened by the large percentage of energy (at least 15% in
general) that is used for cooling, depending on the country, or type of cooling (air
conditioning, refrigeration, and so on) [8].
Before discussing examples of magnetic refrigerants and magnetic cooling in
different temperature ranges, we will first recap the history of the magnetocaloric
effect (Sect. “Cooling at Low or Intermediate Temperatures”), including a short
discussion of low-temperature cooling using electronic paramagnets and nuclear
magnetic moments. Then, in Sect. “The Magnetocaloric Effect Near Room Tem-
perature” we will focus on room temperature effects. Whichever mechanism of the
MCE (paraprocess, rotation, etc.), the search for ever larger MCEs around room
temperature remains the motivation for much of the current materials research in the
field. Since this chapter focuses on caloric material properties, we refer the reader to
references [9,10,176] for a discussion of the status of magnetic cooling prototypes
and magnetic field sources used in such devices. Section “Power Conversion and
Spin Caloritronics” contains a brief survey of two materials research fields: power
generation using pyromagnetic effects (the corollary of the magnetocaloric effect)
and thin-film caloritronics, where a thermal gradient can be used to generate a spin
current.
The history of the magnetocaloric effect has recently been re-examined by Anders
Smith [11]. While theoretical studies may be traced to Lord Kelvin’s prediction
that iron in its ferromagnetic state will cool when demagnetized [12], experimental
work began with Pierre Weiss and Auguste Piccard’s observations, in 1917, of a
magnetic field-induced, reversible, heating effect in ferromagnetic nickel around its
Curie temperature (354 ◦ C) [13]. In what follows, we will see that Kelvin, Weiss,
and Piccard’s works are important foundations for room temperature magnetic
cooling.
Quite separately, in 1905 Paul Langevin had predicted the existence of a
temperature change of a paramagnet when exposed to a magnetic field. It was
Langevin’s work that seems to have inspired theoretical comments on adiabatic
demagnetization at low temperature by Debye in 1926 [14] and by Giauque in 1927
30 Magnetocaloric Materials and Applications 1495
[15]. The first experimental studies of cooling by removal of a magnetic field from
paramagnetic salts at low temperature were reported by Giauque and MacDougall
in 1933 [16] and soon after by De Haas, Wiersma, and Kramers [17]. Giauque and
MacDougall were able to reach a temperature of 0.53 K when a magnetic field
of 0.8 Tesla (T) was removed from a sample of Gd2 (SO4 )3 ·8H2 O at a starting
temperature of 3.4 K. When starting from 1.5 K, they were able to reach 0.25 K and
could infer that multiple demagnetizations would result in yet lower temperatures.
From this brief history, we may see that the use of magnetic cooling at different
temperatures evolved somewhat independently. Giauque received the 1949 Nobel
Prize in Chemistry for his work on the thermodynamic properties of substances at
low temperatures, and particular mention during the presentation speech was made
of his work on magnetic cooling and the subsequent low temperature research that
had been enabled by it [18]. The field of higher-temperature magnetic cooling,
using a refrigerant at a temperature near its magnetic phase transition, received
sporadic interest after Weiss and Piccard’s experiments and, until the 1990s,
lacked the fundamental or commercial motivation for a large effort by the research
community. Proposals to use magnetic phase transitions in the opposite process,
namely, conversion of heat to power, were also sporadic and arguably predate
magnetic cooling investigations. They are described in Sect. “Power Conversion
and Spin Caloritronics”.
An introduction to ADR materials and their uses in a cooling cycle in the millikelvin
range is given by Wikus et al. [1]. As the authors detail, a range of paramagnetic
materials can be used for different temperatures, ranging from GdLiF4 (minimum
operating temperature 500 mK) and GGG (minimum temperature 200 mK) down
to Ce2 Mg3 · (NO3 )12 · 24H2 O at temperatures as low as 0.6 mK. In each case, the
basic principle is the same: the (para)magnetic dipoles are aligned by the applied
magnetic field, causing a change of entropy that can be predicted from Boltzmann
thermodynamics:
sinh(xy)
S = R x (coth x − y coth(xy)) + ln , (8)
sinh x
where R is the molar gas constant, x = μkBBgB T , and y = 2J + 1. The symbol g is the
Landé g-factor, and J is the total angular momentum of the dipole.
The ADR effect is of most use below a characteristic temperature where the
magnetic component of the total entropy saturates or is close to saturation, Tsat .
This is because other entropies, principally the lattice entropy, begin to dominate at
higher temperatures , and so the action of a magnetic field is less pronounced. Below
Tsat , the change of (total) entropy of the refrigerant material observed by applying
a magnetic field is sufficient to allow for heat exchange (Tad is large) and for heat
flow (S is large). A schematic ADR cycle is shown in Fig. 3.
1496 K. G. Sandeman and S. Takei
2.00
B=0
(1)
1.50
(4)
S/R [1]
1.00
(3) (2)
0.50
B=2T
0.00
0.01 0.1 1 10
T [K]
Fig. 3 Adiabatic demagnetization cycle, employing the entropy curves of a paramagnet at two
different fields, 0 and 2 T. Here, the starting temperature is 2 K (step 1), and the refrigerant finishes
the 4-step process at 100 mK (step 4). (This figure is reprinted from Cryogenics, 51, P.Wikus et al.,
“Optimum operating regimes of common paramagnetic refrigerants”, 555–558, Copyright 2011,
with permission from Elsevier [1])
Ti
Tf = h . (9)
H
For electronic paramagnets, the internal field is governed by that of the magnetic
dipole. As a result, we can expect to reach temperatures of the order of 1 mK.
Current ADR research continues to explore new materials, especially superparam-
agnetic clusters [20] and other molecular magnets [21], as potential low-temperature
ADR refrigerants.
In addition to magnetic cooling using paramagnetic salts, there are two other
topics in which research into magnetic cooling away from room temperature has
been extensive: studies of hydrogen liquefaction at intermediate temperatures using
magnetic cooling and adiabatic demagnetization using nuclear moments for ultra-
low temperature research. Regarding the former, we point the reader to a review of
30 Magnetocaloric Materials and Applications 1497
After completing a brief survey of low temperature MCE materials research, we now
focus on the use of the magnetocaloric effect for cooling around room temperature.
This has been the subject of the majority of MCE studies, especially since the mid-
1990s.
From Eq. (4), we see that any magnetic alternative to gas-based cooling around
room temperature must have a large value of ∂M/∂T, which is most readily found
when a change of magnetic state can be invoked by the applied field. The search for
magnetic refrigerants near room temperature therefore becomes a search for phase
transitions in this temperature range. However, there are a few more conditions
that come with a room temperature magnetic refrigerant search. A large value
of ∂M/∂T is more likely when the saturation magnetization is high. Similarly,
ferro- and ferrimagnets are more viable candidates than most antiferromagnets,
since magnetization can be induced by a field around the Curie point, whereas
the appearance of a finite magnetization around a Néel point depends strongly on
the strength of the antiferromagnetic coupling. Due to the reduced magnitude of
∂M/∂T found in superparamagnets (SPMs), the MCE in that class of compounds is
generally lower at room temperature than that of a ferromagnet near its Curie point.
For further information on the MCE in SPMs, the reader is referred to [31, 32].
In terms of room temperature application, further desirable properties include
low heat capacity (to maximize Tad , see Eq. (4)); moderate thermal conductivity
(to minimize thermal equalization while still allowing rapid heat transfer to occur);
corrosion resistance (since a heat exchange fluid is required); shapeability; low
cost; toxicity; and zero critical element content. A further requirement is low
magnetothermal hysteresis (to minimize energy loss upon cycling) unless, as has
been proposed, a second driving parameter such as applied stress is used (see
later [33]). These requirements restrict the number of materials that are currently
considered as room temperature magnetic refrigerants to two principal families:
30 Magnetocaloric Materials and Applications 1499
8.0
8
S
7.8
6
7.6
4 0-1.1 Tesla
7.4
2
7.2
0
150 200 250 300 350 250 260 270 280 290 300 310 320 330
Temperature (K) Temperature (K)
Fig. 4 (a) Adiabatic temperature change data for Gd taken in a field of 0–1.1 T [35] and 0–7 T
[34]. The 0–1.1 T data have been reproduced from C. R. H. Bahl and K. K. Nielsen, J. Appl. Phys.
105, 013916 (2009), and the 0–7 T data have been reproduced from G. V. Brown, J. Appl. Phys.
47, 3673 (1976), both with the permission of the American Institute of Physics; (b) Isofield total
entropy curves in zero applied field and in 7 T. (This figure has been reproduced from G. V. Brown,
J. Appl. Phys. 47, 3673 (1976) with the permission of the American Institute of Physics)
1500 K. G. Sandeman and S. Takei
For the testing device designs, Gd has been the benchmark magnetic refrigerant
for over 40 years as, by using a single compound, a temperature span of several
tens of degrees can be achieved, depending on the applied field. In this respect,
pioneering experimental work on the use of Gd in a magnetic cooling cycle was
performed by Gerald Brown at NASA’s Lewis Research Center in 1976 [34]. In
particular, Brown mapped out the entropy vs temperature diagram of the material
from heat capacity measurements and made direct observations of the adiabatic
temperature change in a 7 T field. Brown’s S(T) data are shown in Fig. 4b together
with examples of how S and Tad relate to the S(T, B = 0) and S(T, B = 7 T)
curves. (The 0–7 T Tad data in Fig. 4a were used by Brown to construct the
S(T, B = 7 T) curve in Fig. 4b from the S(T, B = 0) curve.)
There are several important features in Fig. 4 and in the conclusions that Brown
drew. Firstly, we see that there is a large, reversible Tad response associated
with the Curie transition in Gd. As may be expected, the peak in Tad is to be
found at the Curie temperature. The S(T) data reveal a change of total entropy of
around 0.2 R per mole, where R is the molar gas constant. Brown concluded that a
Carnot cycle would not efficiently use the available change in magnetic subsystem
entropy. This is because of the presence of the phonon entropy term. From his work,
Brown concluded that an efficient use of the magnetic entropy for such a phase
transition magnet would be a magnetic Stirling cycle, involving a constant field
step rather than a constant entropy step. Brown constructed a simple regenerator
using the magnetic Stirling cycle, demonstrating that 47 K temperature span could
be developed between the hot and cold ends of a regenerator system of 1-mm-thick
Gd plates. The regenerator comprised a heat exchange fluid, which cooled or heated
the Gd in between magnetization or demagnetization steps, respectively. This kind
of regeneration had previously been studied at low temperature by van Geuns in
cycles employing paramagnets [36, 37] and would be pursued further as “active
magnetic regeneration” (AMR) by Steyert and Barclay in later studies [38,39]. The
term “active” in AMR refers to the dual function of the magnetic refrigerant as (a)
the source of the magnetocaloric effect and (b) the medium via which a thermal
gradient is established, through heat exchange with a separate working fluid [176].
As highlighted above, given that the adiabatic temperature change is of the order of a
few kelvin but that it can exist over several tens of kelvin, a regenerator is necessary
to maximize the temperature span of the cooling device. Nowadays, almost all
prototype room temperature magnetic coolers employ a regenerator, as a means of
turning a modest single-shot temperature effect into a viable thermodynamic cycle
operating between hot and cold ends of the device that are separated in temperature
by more than the single-shot Tad .
If we again examine the peak-shaped response curves shown in Fig. 4a, we
may also conclude that, in order to optimize the cooling power delivered at a
given temperature, it is desirable to use a material or multiple materials that
have magnetic phase transitions that span the required temperature range. In early
studies of regenerative magnetic cooling cycles, and in patents that resulted, lists
of ferromagnets with Curie points that vary between liquid helium temperature and
room temperature may be found [40, 41]. One may alloy Gd with, for example, Y,
30 Magnetocaloric Materials and Applications 1501
to tune the Curie temperature below room temperature. The Curie temperature of
Gd (294 K) is suppressed by approximately 2 K per percent of Y substitution [42,
43]. Other Gd-R (where R is a rare earth) alloys with reduced Curie points have
been investigated in terms of their magnetocaloric performance and even trialled in
cooling engines (see [44] for a review). However, there are very few Gd alloys that
have ordering temperatures above that of elemental Gd, with the notable exceptions
being Gd6 Mn23 (ferromagnetic, with Curie temperature 461 K) [45], the Gd-Co
alloy system (ferromagnetic, with Curie temperatures up to 1000 K), and Gd5 Si4
(ferromagnetic, with Curie temperature 336 K) [46]. The last of these materials
was the source of renewed interest in magnetic cooling following the observation,
by Vitalij Pecharsky and Karl Gschneidner Jr., of a giant magnetocaloric effect
(GMCE) in Gd5 Si2 Ge2 in 1997. The key to their discovery of a GMCE was a phase
transition that was not continuous (second order) but instead was discontinuous (first
order), mirroring the physics of the liquid-gas phase transition.
The observation of magnetocaloric effects in the neighborhood of first-order
magnetic transitions is essential to the development of new materials that satisfy
more of the requirements for application outlined above. Principally, the need for a
tunable Curie point means that alloying is typically required. However, any dilution
of the magnetic species can result in a reduction of the magnetocaloric effect, since
all atoms in the refrigerant need to be heated and cooled, not just those that are
associated with magnetic (dis)ordering. This point is especially vital when trying to
reduce refrigerant cost and criticality by moving away from rare earth gadolinium
to 3d metal-based magnetic refrigerants. Since the ordering temperatures of Fe,
Ni, and Co are much higher than room temperature, significant dilution (alloying)
is required. In order to offset the increase in heat capacity per unit volume that
comes from alloying, an increase in ∂M ∂T beyond that associated with simply using
a continuous phase transition is required. For this reason, GMCEs have all been
associated with first-order magnetic phase transitions. The following subsections
summarize the magnetocaloric effects associated with some key examples of
materials with first-order magnetic transitions near room temperature. For recent
work on the large magnetocaloric effect associated with the second order transition
in AlFe2 B2 -based compounds, we refer the reader to [180,181,182].
350
300
O(II ) M O(I )
250
200
TN, TC(K)
150
100
, , , Tc
50 TN
Gd5(SixGe1-x)4
0
0.0 0.2 0.4 0.6 0.8 1.0
Gd5Ge4 x(Si) Gd5Si4
Fig. 5 Magnetic and structural phase diagram of the Gd5 Si4 -Gd5 Ge4 system. We note the
large range of competing magnetic states (separated by solid and dashed lines) and structural
states (separated by dot-dashed lines) and the region of greatest interest for room temperature
magnetocaloric studies, the Gd5 Si2 Ge2 composition, that exhibits a magneto-structural phase
transition involving magnetic ordering and a change of crystal symmetry. O(H) phase properties are
indicated by circles, while triangles are for the M phase and squares for the O(I) phase. (This figure
is reprinted from Journal of Alloys and Compounds, 260, V. Pecharsky and K.A. Gschneidner Jr.,
“Phase relationships and crystallography in the pseudobinary system Gd5 Si4 -Gd5 Ge4 ”, 98–106,
Copyright 1997, with permission from Elsevier [49])
For this reason, while the isothermal entropy change associated with field-induced
increases in magnetization is large, the adiabatic temperature change is not wholly
reversible [108]. Initially reported maximum values were around 7 K in 0–2 T and
around 15 K in 0–5 T [48]. At this point, it is worth noting that there is currently no
agreed definition of a “giant” magnetocaloric effect. In Gd5 Si2 Ge2 , an isothermal
entropy change of around 20 Jkg−1 K−1 was observed in a field change of 0–
5 T. This level of entropy change is normally termed “giant,” although it does not
guarantee that there is also a large reversible Tad (T).
Subsequent work on the Gd5 Si4 -Gd5 Ge4 system examined how to tune the
material so as to reduce the thermal hysteresis at the magnetic ordering transition
while maintaining the MCE. It was found that small amounts of impurities drove
30 Magnetocaloric Materials and Applications 1503
a b
20 20
MnxFeP1-95-xP1-ySiy
Gd5Ge2Si2 MnFeP0.45As0.55
15 15
- Δ Sm (Jkg-1 K-1)
- Δ Sm (Jkg-1 K-1)
10 10
5 Gd 5
0 0
260 280 300 320 340 200 250 300 350 400
T (K)
T (K)
Fig. 6 (a) Isothermal entropy curves of MnFe(As,P), where a favorable comparison with
Gd5 Si2 Ge2 and with Gd can be made. Reprinted by permission from Springer Nature: Nature,
415, 150, O. Tegus et al., copyright 2002 [62]. (b) The arsenic in this material series has been
successfully replaced by Si to provide large magnetocaloric effects in Mnx Fe1.95−x P1−y Siy . Again
the S(T) for Gd is shown for comparison. (This figure is copyright © 2011 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim and is reproduced from [63] by permission of Wiley. In the plot,
0–1 T (open symbols) and 0–2 T (solid symbols) effects are shown for x = 1.34, 1.32, 1.30, 1.28,
1.24, 0.66, 0.66 and y = 0.46, 0.48, 0.50, 0.52, 0.54, 0.34, 0.37 (left to right))
the parent Fe2 P compound, causing a loss of magnetic moment. This results from
covalent bond formation between Fe and P/Si. By comparison, the 3f site moment is
relatively well maintained into the paramagnetic state. Consequently, the action of a
magnetic field not only orders the magnetic moments but increases their size. Such
mixed magnetism physics is not unique to (Mn,Fe)2 (P,Si), but it clearly improves
the MCE.
Fe-Rh
While all of the GMCEs presented so far in this section have been associated with
ferromagnetic ordering transitions, there is an example of a first-order, magnetic
order-order transition that is also associated with a giant MCE. The Fe-Rh binary
phase diagram contains a small region near to the equiatomic FeRh composition
which crystallizes in a cubic CsCl structure and has an antiferromagnetic (AFM)
ground state. Upon raising temperature, this ground state gives way to a ferro-
magnetic (FM) state, and the resulting metamagnetic transition between the two
states is first order. This phase transition has been the subject of applied research
interest in the field of heat-assisted magnetic recording and the focus of fundamental
interest for more than 50 years [183]. As with the case of (Mn,Fe)2 (P,Si), there is
the development of an increased moment in one phase: in this case, the Rh atom
takes on a ∼ 1 μB moment in the ferromagnetic state. This, combined with the large
1506 K. G. Sandeman and S. Takei
saturation magnetization and low dilution of magnetic species, yields a material that
has the largest Tad values (per Tesla applied field) of any MCE compound. In a
field of 2 T, the single-shot adiabatic temperature change reaches 12 K [79].
The reversibility of the MCE in Fe-Rh has been a subject of debate [80–84].
Manekar and Roy have presented a comprehensive discussion of the impact of the
thermomagnetic hysteresis at the AFM-FM transition on the reversibility of the
GMCE [80]. Instead a particular path in field and temperature space has to be chosen
for a giant MCE to be observed after a first adiabatic application of a magnetic
field. Whereas early studies were concerned with the diminution of the MCE with
magnetic field cycling [82, 83], recent studies have tried to ascertain the reversible
component and have surmised that it is 15% higher than in Gd [85]. Work by the
Mañosa group has confirmed that, within a given window of temperature, both the
magnetocaloric effect and the barocaloric effect (using an applied pressure to couple
to the volume change at the AFM-FM transition) are giant and reversible [84]. The
two effects can even be combined to yield large so-called multicaloric effects [81].
FeRh arguably highlights the potential for yet greater Tad to be found in d-metal
materials. A summary of the peak values of Tad and S is given in Fig. 7 using
reversible Tad unless noted. As Wood and Potter [86] found, a material coefficient
of performance can be constructed by examining the ratio of Tad × S to the input
magnetic work. They evaluated the resulting coefficient of refrigerant performance
(CRP) for a number of second-order materials. As many of the available materials
have somewhat similar saturation magnetizations, we chose to show Tad and
S as a guide to the state of material development and in order to demonstrate
avenues for exploration. In Fig. 7 we see that the two d-metal material systems that
are closest to commercialization, La(Fe,Co,Mn,Si)13 Hy and (Mn,Fe)2 (P,Si), exhibit
similar values of Tad (6 K in a 0 to 2 T field change). Fe-Rh has a considerably
higher peak Tad value, and it indeed the quantity μ0 −1 ∂Tt /∂H has a close to
optimal value in this case. (For a fixed saturation magnetization, there is a value
of ∂Tt /∂H or ∂TC /∂H that maximizes the adiabatic temperature change. However,
this value of ∂Tt /∂H or ∂TC /∂H will not simultaneously maximize the isothermal
entropy change. For more details, see refs. [87,88]). We note that, with the exception
of Fe-Rh, there is plenty of room for optimization of the adiabatic temperature
change.
16
Fe-Rh model
0 to 2 Tesla
Fe-Rh
Mn-Fe-P model
Fe-Rh
14 La-Fe-Si model
La-Fe-Si
Fe-Rh
12 increasing
| (K)
Mn-Fe-P | dTc/dH |
10 La-Fe-Si dTc
<
dH
max
8 La(Fe0.88Si0.12)13Hy Mn-Fe-P
GdSi2Ge2
| Tad
MnFe(As,P)
6 Gd La(Fe,Mn,Si)H13
MnxFe1.95-x P1-ySiy
La(Fe1-xCox)11.9Si1.1
4
2 La1-xAgyMnO3
La0.6Ca0.4MnO3
MnAs
0
0 5 10 15 20 25 30 35 40
max -1 -1
| S | (JK kg )
Fig. 7 A comparison of the isothermal entropy and adiabatic temperature change found in a
selection of room temperature magnetocaloric materials, after Ref. [88]. Where available, the
relevant reversible effect is shown in 2 T. This has a deleterious effect on the magnitude of the
effect seen in MnAs, in particular. (The exception is FeRh, where the irreversible effect is shown
to draw attention to the possibility of higher Tad values in future compounds.) The solid line gives
a theoretical limit to the combination of (S, Tad ) available in a typical transition metal alloy of
saturation magnetization 120 Am2 /kg. (This figure is reprinted from Scripta Materialia, 67, K.G.
Sandeman, “Magnetocaloric materials: The search for new systems”, 566–571, Copyright 2012,
with permission from Elsevier)
associated with the Curie point in ferromagnetic Ni2 MnGa, an alloy best known for
the shape memory effect associated with its martensitic transformation. It is possible
to merge the martensitic and Curie transformations [90], but doing so generally
brings about a strongly first-order phase transition with large thermal hysteresis,
and an inability to drive the transition out of any remanent metastable state solely
with a magnetic field since the field sensitivity of the martensitic transition is
low.
Heusler compounds have been a fertile playground in which to explore inverse
magnetocaloric effects, with giant inverse effects first being reported by Krenke
et al. in Ni-Mn-Sn at room temperature [91]. These effects were associated with re-
entrant ferromagnetism – the Curie point of the low-temperature martensite; TC M
is lower than that of the austensite (TC A ), and so, on heating through the structural
transition, ferromagnetism emerged. Such an inverse MCE is common to both Ni-
Mn-Sn and Ni-Mn-In alloys, as can be seen from the relative positions of TC M and
TC A in the magnetic phase diagrams shown in Fig. 8.
1508 K. G. Sandeman and S. Takei
x (at%)
20 10 0 20 10 0
1200
Ni50Mn50-xSnx Ni50Mn50-xInx Ni-Mn-Ga
1000
MS MS MS
800 Cubic Cubic Cubic
(K)
PM PM PM
600
T
14M
200 T CM T1
T CM
FM (a) FM (b) (c)
0
7.5 8.0 8.5 7.5 8.0 8.5 7.5 8.0 8.5
10M e/a 10M 14M
14M
10M
Fig. 8 Magnetic and structural phase diagrams for the three Heusler alloys most studied in the
context of the magnetocaloric effect: Ni-Mn-Sn (a), Ni-Mn-In (b), and Ni-Mn-Ga (c). Magnetic
and structural (martensitic) transformations are indicated by circles and triangles, respectively.
Dotted lines demarcate regions of each phase diagram with different (modulated) structures.
Premartensitic transition temperatures are shown as small solid circles in (c). (Figure reproduced
from [89] with permission from IOP Publishing)
Of the materials outlined above, the (Mn,Fe)2 (P,Si) and the La-Fe-Si series are
closest to commercialization at the time of writing. While this chapter does not
examine the nature of the cooling engine itself, it is worth noting that almost
all magnetic cooling engine prototypes documented in a review by Yu et al. in
2010 used gadolinium or gadolinium alloys [98]. The relative availability of Gd
and its large MCE make Gd a good material with which to test engineering
models, thermodynamic cycles, and regenerator conformations. In all prototypes,
the refrigerant and magnet must undergo relative motion, and a fluid heat exchange
medium is circulated over the solid refrigerant. Early prototype ideas used either
linear actuation, such as Brown’s prototype [34] or rotational motion, such as was
employed in Steyert’s design [38] and in the prototype of Kirol and Dacus [178,
179].
Table 1 Example compounds from various families of magnetocaloric material, with MCEs from low temperature to room temperature
Peak |S| in
Material family Type of transition Transition temperature (K) 0–1 T(Jkg−1 K−1 ) Peak |Tad | in 0–1 T (K) Refs.
Cu N/A (nuclear Microkelvin regime – – See text
paramagnet)
GGG N/A (para-magnet) Millikelvin regime – – See text
Gd 2nd order Curie 294 3.0 2.5 [86]
Gd5 Si2 Ge2 1st order Curie 272 11 3.5 (irrev.) [47]
[Gd5 (Si,Ge)4 family]
LaFe11.384 Si1.26 Mn0.356 H1.52 1st order Curie 290 11 3.5[in 1.2 T] [102]
[La(Fe,Si)13 family] [in 1.2 T]
MnFe0.95 P0.605 B0.065 Si0.33 1st order Curie 274 (warming) 12.5 2.4 [103]
[(Mn,Fe)2 (P,Si) family]
MnAs 1st order Curie 318 (warming) 32 (irrev.) 2.5 (irrev.)0.2 (rev.) [104][105]
316 (warming)
Fe49 Rh51 1st order AFM-FM 310 (warming) 12 (rev.) –6.2 (rev. in 2 T) [106][85]
∼12 (rev.)
Ni2.19 Mn0.81 Ga 1st order Curie 338–348 (warming) 5.5 (rev.) 0.6 (after 6 cycles to 1.85 T) [107, 108]
[Ni-Mn-Ga family]
Ni45.7 Mn36.6 In13.5 Co4.2 1st order 287 (max. irrev. effect) 13.8 (full transition) 8 (irrev.)3 (rev.)[in 1.95 T] [109]
[Ni-Mn-In and Ni-Mn-Sn AFM/PM-FM 282 (max. rev. effect)
families]
Data shown are the transition temperature of relevance (if any); peak values of Tad and S in a field change of 0–1 T (where known); and references to relevant
measurements. Where possible, reversible values of Tad and S are shown; in the case of MnAs and the inverse, both irreversible (irrev) and reversible (rev)
values are given. For the NDR and ADR refrigerants, Cu and GGG, respectively, cooling is associated with no change of magnetic state, and therefore no data
associated with a magnetic transition are noted. We also note that all of the materials with first-order transitions can be driven second order by some change in
composition, external field; for this reason a sample of only their first-order properties are reported below since those have formed the focus of research in each
case
K. G. Sandeman and S. Takei
30 Magnetocaloric Materials and Applications 1511
a field change of zero to 1 T are given. As there is not yet a consistent approach
to the measurement of the MCE in the literature, where data is not available in the
same field change, this is noted. We note that such a table can only present a small
fraction of the total number of materials studied. For this reason, we have focused
on presenting material families as in the above subsections, along with appropriate
references for the reader to begin further research.
We finish with some remarks about two developing areas that relate to the reverse
of the magnetocaloric effect. Instead of generating a thermal gradient from an input
of magnetic work, both of these areas use a thermal gradient to generate either a
change in static magnetization via the pyromagnetic effect or a spin current via the
spin Seebeck effect.
The first area is the pyromagnetic effect (PME), whereby input heat is converted
into work, rather than vice versa. This “magnetocaloric effect in reverse” arguably
predates the magnetocaloric effect as it was considered by both Tesla and Edison in
the late nineteenth century as a means of generating power from heat.
Applied studies of pyromagnetic energy conversion can be divided into two main
types. The first is direct conversion of a thermal gradient to electrical energy, for
example, through the change of magnetic flux, through a coil that has in its core
a working (pyromagnetic) material that undergoes a change of magnetization when
heated. Tesla first proposed this in 1889 [110]. The pyromagnetic voltage, V, is then
δ
V =− ; = B.dA
δt coil
Fig. 9 A schematic power generation cycle in M(H, T) space based on the conversion of heat
energy using a pyromagnetic working material that changes magnetization with temperature. In the
case shown, the working material is ferromagnetic at the cold sink temperature and paramagnetic
at the hot sink temperature. (Figure reproduced from C.-J. Hsu, S. M. Sandoval, K. P. Wetzlar,
and G. P. Carman, J. Appl. Phys. 110, 123923 (2011) [115], with the permission of the American
Institute of Physics)
Tcold
ηCarnot = 1 − .
Thot
waste heat. However, these materials are by no means the only options for use as
power conversion materials [184]; for example, it has been shown that a martensitic
Ni-Mn-Ga thin-film cantilever can be flexed to produce milliwatts of power [116].
While in a cooling cycle a latent heat may be a desirable property of a working
material (where heat transfer is an output), a latent heat actually provides an
additional heating requirement in the case of a heat engine (where heat transfer is an
input). For this reason, there is ongoing discussion as to the optimal requirements
for a pyromagnet in a heat engine, in particular due to the trade-off between power
output and efficiency that occurs when the temperature span of the pyromagnet is
varied [117].
We also note that, while the Carnot efficiency of a power conversion cycle
is optimized by reducing the cold sink temperature, it has been shown that the
percentage of Carnot efficiency achievable with a pyromagnet increases as the
temperature difference between Thot and Tcold decreases [115]. There is therefore
a balance to be struck between the Carnot efficiency and the achievable efficiency.
Rapid progress in spintronics was triggered by the discovery of spin Hall phe-
nomena in heterostructures consisting of interfaces between a magnetically ordered
material and a non-magnetic metal with strong spin-orbit coupling (SOC). SOC
(in the metal and at the interfaces) together with exchange coupling (between the
conduction electron spins and the magnetization) at a normal metal/magnet interface
allows angular momentum to be transferred from the metal’s crystal lattice to the
magnetization and engenders macroscopic coupling between the electrical current
in the metal and the magnetic order parameter. These magnetic heterostructures
have played a central role in modern spin caloritronics, where they are subjected
to an additional thermal gradient to study the coupled propagation of charge,
spin, and heat through them [118–120]. A spectacular development in the field of
spin caloritronics came from the discovery of the spin Seebeck effect (SSE) [121]
in which spin currents are thermally excited by a temperature gradient across a
magnetic system. The spin currents are then injected into an adjacent spin-orbit
coupled metal, converted into a charge current or an electromotive force transverse
to the current direction via the inverse spin Hall effect (SHE) and electrically
detected. From the viewpoint of device applications, the field has strong relevance,
as it may lay the foundations for new devices with superior thermoelectric figures of
merit and more efficient energy harvesting as well as new means to manage immense
Joule heating expected in future high-density silicon electronics [122].
The SSE has been studied using two configurations depending on the relative
orientation of the spin current with respect to the thermal gradient: longitudinal
[123–132] (see Fig. 10a) and transverse [123, 133–135] (see Fig. 10b). Historically
speaking, the transverse configuration was investigated first, but the current status
of the field is such that the physics of the longitudinal SSE is more well-understood
relative to its transverse counterpart. Thus far, experiments have focused on insulat-
1514 K. G. Sandeman and S. Takei
Fig. 10 Two configurations with which spin Seebeck effect has been investigated: (a) the
longitudinal and (b) the transverse. Spin current is denoted above by Js , and the transverse
electromotive force generated by the spin current via the inverse spin Hall effect is labeled
by EISHE . (Figure reproduced from K. Uchida et al., J. Appl. Phys. 111, 103903 (2012) with
permission of the American Institute of Physics)
ing magnets, as longitudinal SSE signals are indistinguishable from classical Nernst
signals if ferromagnetic conductors are used [136, 137]. We will therefore begin by
focusing on insulating ferromagnets and then comment on antiferromagnets later.
General theories of the longitudinal SSE have been discussed in refs. [138–142].
The phenomenon can be explained in terms of a spin current inside the ferromagnet,
generated by magnetic quasiparticles (i.e., magnons) drifting under the thermal
gradient, that is, injected into the metal and converted into a transverse electric field
EISHE via the inverse SHE,
Here, θ SH is the spin Hall angle quantifying the efficiency of conversion between
spin and charge currents, ρ is the electrical resistivity of the metal, and Js is the
spatial direction of the spin current polarized along σ . Time-averaged spin current
Jsp pumped into the metal from the magnet by magnetic thermal noise is given by
spin pumping and reads [143]:
Jsp σ = Gr m × ṁ + Gi ṁ , (11)
2e
where . . . denotes time averaging, m is the unit vector parallel to the mag-
netization, and Gr or Gi (in units of −1 ) is the real or imaginary part of the
spin mixing conductance [144] that determines the magnitude of the pumped spin
current. Thermal spin fluctuations in the metal also subject the magnetization to a
stochastic spin torque, which can be expressed using a stochastic magnetic field h(t),
and give rise to time-averaged spin current Jn polarized normal to the magnetization
30 Magnetocaloric Materials and Applications 1515
Jn σ = − m × h , (12)
with the Cartesian components of h(t) obeying hi (t)hj (t ) = (Gr /2π )kB Tn δ ij
δ(t − t ) (Tn being the metallic electron temperature) in accordance with the
fluctuation-dissipation theorem. When the ferromagnet and the metal are in thermal
equilibrium, there is no net flow of spin across the interface, and we have
Js = Jsp + Jn = 0 [126]. However, since Jsp and Jn are proportional to the magnon
temperature Tm and Tn , respectively, a difference in the two temperatures destroys
the balance, and a net spin current Js ∝ Tm − Tn results [138–141]. In particular, one
notes that a sign reversal in the inverse SHE signal occurs as a result of reversing
the temperature gradient across the device. This was indeed observed in one of the
first longitudinal SSE experiments [130].
The temperature difference Tm − Tn at the detector end can be related to the
magnon spin current flowing toward the detector due to the thermal gradient [138].
One would expect that only magnons from distances smaller than their propagation
length contribute to the magnon spin current at the cold end and that this propagation
length depends on the quality factor of the ferromagnet (as spin damping would
lead to the decay of magnons into, e.g., the lattice). Reference [128] experimentally
determined this magnon propagation length ξ by studying the dependence of the
inverse SHE signal on the thickness of the magnetic film. The experiment was
conducted on a yttrium iron garnet (YIG)/platinum (Pt) bilayer. They observed
a saturation in the SSE signal once the thickness starts to overcome the mean
propagation length of the magnons and fitted their signal to
flop transition [149, 150]. At low temperatures (T = 15 K) and under high magnetic
fields (B = 14 T), the spin Seebeck coefficient for MnF2 [150], in particular, was
calculated to be 41.2 μV/K, which is larger than even the largest values of the SSE
in bulk single crystal YIG at low temperatures. The antiferromagnet insulator NiO
has also emerged recently as an attractive system for longitudinal SSE studies [151,
152]. Non-trivial magnetic anisotropy in NiO lifts the degeneracy between the two
magnon modes associated with the two-sublattice structure and, therefore, permits
spin transport at small magnetic fields [148]. Reference [151] proposed that the SSE
signals are generated mainly by thermally driven magnons from the low-energy part
of the spectrum, consistent with the high-field suppression of the SSE mentioned
above.
In relation to the longitudinal SSE, the transverse SSE has been much more
controversial. The precise mechanism behind the transverse SSE is still not well
understood, mainly because of its sensitive dependence on the details of the
magnon/phonon temperature profiles across the devices and the possible role played
by phonons in the substrate on which the active device is grown [134]. Initially, an
unexpectedly high transverse SSE signal was observed in permalloy [153], where
thermally induced spin voltages extended over distances many orders of magnitude
larger than the spin diffusion length. Subsequently, a giant transverse SSE signal was
detected in YIG over several millimeters and was attributed to long-ranged magnon-
mediated spin transport resulting from YIG’s exceptionally high quality factor
(and the correspondingly long magnon diffusion lengths) [138, 139]. However,
an experiment on a ferromagnetic semiconductor GaMnAs reported a similarly
long-ranged SSE signal even after cutting the magnetic coupling in the material
along the direction of the thermal gradient [154], casting doubt on the long-ranged
magnon-mediated SSE idea. The giant enhancement of the SSE signal for YIG was
subsequently interpreted as a phonon-drag effect: the temperature gradient drives a
stream of phonons, which then drags the magnons and causes their convection [155].
This phonon drag idea was also supported by an experiment that involved a detail
of characterization of the temperature dependence of the spin-Seebeck coefficient,
magnetization, and thermoelectric power of the ferromagnetic semiconductor GaM-
nAs (in which transverse SSE was measured), alongside the thermal conductivity
and specific heat of the GaAs substrate on which the ferromagnet was grown [156].
In further experiments a curious sign reversal in the transverse SSE voltage signal
at a certain heater-detector distance was observed and was reported to depend
both on the YIG/heater interface opacity and the YIG thickness [135, 157]. The
results were qualitatively explained by a complex interplay between the temperature
dependences of the interfacial transparency, i.e., angular momentum transfer across
the YIG/metal interface and the diffusive properties of the thermally excited non-
equilibrium magnons [157], providing evidence for the magnon-mediated transverse
SSE.
The SHEs, collectively referring to a transverse pure spin current Js ∝ θ SH Jc × σ
generated by a longitudinal charge current Jc and the inverse effect (used extensively
in the detection scheme for the SSE), have fueled extraordinary advances in the field
of spintronics [158]. Here, θ SH is referred to as the spin Hall angle quantifying
30 Magnetocaloric Materials and Applications 1517
the charge-to-spin conversion efficiency, and σ is the unit vector parallel to the
spin current polarization. The spin Nernst effect (SNE) [159–161] refers to the
generation of a transverse spin current Js in the presence of a longitudinal heat
current Jh , i.e., Js ∝ θ SN Jh × σ , where θ SN is the so-called spin Nernst angle.
Very recently, the effect has been detected directly in platinum films by selectively
changing the spin transport boundary conditions at the platinum film boundaries
and recording the ensuing spin Nernst-driven changes in the thermopower in the
Fig. 11 Various magneto-electric and thermal effects involving charge and spin and their first
experimental measurements. (Left column reprinted by permission from Springer Nature: Nature
Materials, 16, 977, S. Meyer et al., copyright 2017)
1518 K. G. Sandeman and S. Takei
longitudinal direction, i.e., along the heat gradient [162]. The effect may have also
been observed in tungsten as well [163].
New and interesting theoretical directions for realizing the SNE have been
proposed. In the intrinsic SHE, time reversal symmetry prohibits transverse charge
current but allows transverse spin current originating from Berry curvature of
electron bands [164, 165]. By analogy, it has been predicted that a temperature
gradient can induce a transverse magnon spin current in systems with magnon Berry
curvatures both in ferromagnets [166, 167] and antiferromagnets [168, 169] with
Dzyaloshinskii-Moriya interactions.
We conclude with a table (Fig. 11) that summarizes the magneto-electric
and thermal effects described in this section, along with their first experimental
measurements.
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Contents
Magnetic Sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1528
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1528
Relevant Parameters for Choice of a Magnetic Sensor Source Signal Parameters . . . . . . 1528
Field or Flux Sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1529
Sensor Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1530
Flux Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1530
Field Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1533
Noise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1541
Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1541
Noise Sources [31] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1542
Detection Schemes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1542
Magnetometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1542
Gradiometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1543
Closed Loop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1544
Bridge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1544
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1544
Field/Flux Sensing and Flux Transformers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1544
Current Sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1545
Position Sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1545
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1548
Abstract
Here the fundamentals of magnetic sensing are introduced and several types
of magnetic flux and field sensors are presented. Flux sensors are inductive
coils, fluxgates, and SQUIDs. Field sensors depend on Hall effect, anisotropic
magnetoresistance, spin electronics (giant magnetoresistance and tunnel mag-
netoresistance), optical pumping, giant magnetoimpedance, and magnetoelectric
effects. Some specific readout schemes are discussed. The noise aspect is dis-
cussed and comparative tables are provided of the various sensors including their
sensitivity, field range, minimal detectable noise, advantages, and drawbacks.
Magnetic Sensing
Introduction
A sensor is an entity which converts a physical quantity into another. Like our
sensory system, which changes the physical inputs (light and color, sound . . . ) into
electrical signals which can be conveyed through the nervous system towards var-
ious brain areas, a manufactured sensor will change a physical quantity containing
relevant information to another which can be easily interfaced and treated, most
often an electrical signal. Sensing the magnetic field H is a powerful approach as it
does not require physical contact with the source of the signal. Magnetic sensors
give an output signal containing information on B, which can be related to its
magnitude (scalar magnetometer) or to its components (vector magnetometer).
The magnetic field H is given in A/m or Oe. The magnetic induction B is given
in tesla T (or gauss G). As for magnetic field detection (in a free space), they are
proportional, magnetic sensor performance like sensitivity, field equivalent noise,
and response are given in tesla which is the most convenient unit.
Magnetic fields can be produced by many sources, either from a magnetic object
(from nanoscale magnetic particles to celestial objects such as planets or stars) or
induced by an electrical current. As the variety of magnetic signals which can be
explored is broad, many parameters influence the choice of a sensor for a particular
application (Fig. 1).
The nature of the source defines the characteristics of the magnetic signal emitted
and hence drives the choice of sensor. For instance, the source size and shape (point-
like source, dipolar or distributed and homogeneous sources) will define the field
shape and extension. The possible distance between the sources and the measure-
ment site will lead to the field strength. From these pieces of information, the sensor
type, size, and configuration will be chosen. Additional important parameters are the
frequency of the emitted signal (DC up to GHz or THz frequencies), the temporal
31 Magnetic Sensors 1529
Fig. 1 Schematic of a magnetic measurement: the source characteristics, the distance from the
sensor to the source, the allowable size, and the environmental conditions are among the parameters
that drive the choice of sensor
response (continuous or transient). These parameters will fix the sensor dynamic
range and required bandwidth.
Sensor Characteristics
Magnetic sensor characteristics are complex and strongly dependent on the physical
principle underlying the sensor operation [1]. Sensitivity and field equivalent noise
are key parameters, but dynamics, frequency, and temperature range are also to be
considered. Sensors can also be operated as vector magnetometers, measuring one,
two, or three components, or in scalar mode, where only field strength is sensed.
Depending on their principle, sensors can be absolute or relative magnetometers.
Sensors can also be defined in terms of energy resolution versus volume [2].
External Parameters
The choice for a particular sensor will be based upon the conditions under which
the sensor has to be operated (temperature range, electromagnetic perturbations,
allowable size and weight, price . . . ).
Some sensors are designed for flux sensing where H is integrated over a finite
surface area defined by the sensor shape. If size is not a limitation and if the source
1530 M. Pannetier-Lecoeur and C. Fermon
is distant, flux sensors can be appropriate, whereas for local measurements or when
miniaturization is required, field sensors will be a better option.
Flux sensors can be either inductive, such as coils, and dedicated to high
frequency (≥10 kHz) measurements, or sensitive to a static or low frequency flux
such as SQUIDS and fluxgates. Main types of flux and field sensors are detailed
below.
Sensor Types
Flux Sensors
In this section, sensors which measure the magnetic flux Φ are addressed. Such
sensors can be extremely field sensitive when their size is large, hence Φ is large
as well. Coils, which are the most common flux sensors, are very sensitive for
high frequency signals, whereas fluxgates and SQUIDs address low frequency or
dc signals.
Principle
When an open metallic coil is submitted to an external varying field, a voltage
proportional to the time derivative of the magnetic flux appears at the ends of the
coil. This simple sensor is still used extensively as a high frequency receiver. The
intrinsic level of noise of a coil, only given by the thermal noise of the residual
resistance, is very low and the sensitivity is directly proportional to the frequency.
Hence at high frequencies, coils can easily reach sub-femtotesla detection [1, 3, 4].
From the simple coil, two main alternative sensors have been developed. The first
consists of placing the coil in a resonant circuit by adding a capacitance (Fig. 2a).
This is very useful as a radio receiver or as an NMR spectrometer. The output
voltage is:
d
V = −Q (1)
dt
for a resonant coil where Q is the quality factor of the coil and it depends on the
resonant circuit characteristics and on the frequency (Fig. 3). The second consists
of a ferrite core with a high permeability for detecting low frequencies (Fig. 2b).
Search coils used for petroleum research or long wave radio receivers use this latter
method.
Main Applications
Receivers, NMR, and MRI spectrometers are using tuned coils for frequency-
specific detection. Low-frequency detection is performed with search coils compris-
ing a large ferrite core. Proximity inductive sensors and nondestructive evaluation
31 Magnetic Sensors 1531
Fig. 2 Coil sensors: (a) Resonant coil circuit; (b) Search coil, where a ferrite is placed within the
winding. The increased μr leads to an effective increase of sensitivity, equivalent to an enlarged
pickup surface
Fig. 3 Output voltage amplitude as a function of frequency for a simple coil (grey line) and for a
resonant coil (dashed line) tuned at 5 kHz
use the same approach: a small coil creates a RF field which induces an eddy current
in the metallic target and the same coil (or another one) is used to detect the field
created by these currents. This can also be seen as a change of inductance of the
emitting coil.
Fluxgates
Principle
Fluxgates are also designed with a soft magnetic material core surrounded by a
coil. However, the working principle is quite different. The coil is used to apply
an alternating magnetic field in the kHz range (at a frequency f ) able to saturate
the core. A second sensing coil is placed around the system (Fig. 4). In absence of
1532 M. Pannetier-Lecoeur and C. Fermon
Fig. 4 Fluxgate principle: A soft magnetic core, often in a ring shape is symmetrically excited
by an ac coil creating field large enough to saturate the core. The material hence experiences a
complete hysteresis loop at each cycle. Due to the symmetry, in absence of external field, there is
no magnetization created by the ring. When an external magnetic field is applied, the left and right
hysteresis loops are shifted in opposite directions and a net magnetization appears, detected by the
reception coil. The signal at 2f is proportional to the magnitude of the external field
external field, the response of the core is symmetrical and there is no signal in the
sensing coil. When an external field is applied, the response of the core is no longer
symmetrical and a response at 2f, the double of the applied frequency, is detected
[1, 5].
Fluxgates have been extensively developed with small, μm (micro-fluxgates) or
cm sizes and are able to detect fields in the range of picoteslas to nanoteslas. Unlike
classical coils, they are sensitive to dc fields and have a reasonably flat response up
to several kHz [6].
Main Applications
The main application of fluxgates is to detect fields in the range of 100 pT to
1 μT. This applies mainly for earth and planetary magnetic field measurements,
compasses or for laboratory instrumentation. Due to their low 1/f noise, fluxgates are
often used as references for active magnetic shielding of rooms used for biomagnetic
measurements.
SQUIDs
Principle
Superconducting quantum interferences devices (SQUIDs) [7] are based on two
main properties of superconductivity; the first is the quantization of the flux and
the second is the tunneling transport of Cooper pairs through a weak link in a
superconducting film, also called a Josephson Junction (JJ). SQUIDs comprise a
31 Magnetic Sensors 1533
Fig. 5 Principle of SQUID measurement. The field of interest is captured in a pickup coil which is
coupled to a second loop (primary coil) directly coupled to the SQUID. Such flux transformers are
made of superconducting material, like the SQUID, which is a superconducting loop interrupted
by Josephson Junctions, which are tunnel junctions or weakly superconducting links. Both flux
transformer and SQUIDs require a cryogenic environment to operate. Usually, SQUIDs are used
with a flux-locked loop scheme (see Sect. “Closed Loop”), which allows operating at the most
sensitive part of the output voltage
Main Applications
SQUIDs are used in metrology, laboratory magnetometry, explosives detection, or
geophysical measurements and mapping [8] with the main commercial application
being magnetoencephalography [9]. Nevertheless, the need of cryogenic cooling
limits their practical applicability to detect extremely weak low frequency signals,
such as biomagnetic ones (heart or brain magnetic activity for instance) [8]
(Table 1).
Field Sensors
Field sensors directly measure vector components or the absolute value of H. Here
we present the main types of magnetic field sensors.
1534 M. Pannetier-Lecoeur and C. Fermon
range
Typical field 1fT–10 T 1fT–10 mT 5 pT–100 μT
range 1 fT–100 μT
Frequency range ac >50 Hz ac >5 mHz [10] dc-5 kHz dc-100 kHz
Linearity Excellent Excellent Good Requires feedback
Size 0.1 mm–1 m 0.1 mm–1 m 0.1 mm–5 cm 0.1 mm–1 cm
Material Metal Ferrite core Ferromagnet Metal/oxide
Technology Bulk Bulk Bulk Thin film
a Sensor operating temperature range
b Limited by the material permeability range
c Given by the superconducting transition temperature
Principle
Discovered by E.H. Hall in 1879 [11], the Hall effect describes charge carrier
deflection in a metal or a semiconductor under the Lorentz force towards the edge
of a strip, leading to a transverse voltage, directly proportional to H (Fig. 6).
In first approximation, the Hall voltage is given by:
Rh
VH = BI. (2)
t
with t the thickness of the slab and where the Hall resistance is defined as
1
Rh = . (3)
q.nc
Main Applications
A Hall sensor can be a simple strip connected with two contacts to inject the
current and two transverse electrodes reading the output voltage. Best materials for
Hall sensors are semiconductors due to their large Rh . Because of its simplicity
and compatibility with microelectronics, Hall effect is the main physical principle
widely exploited in consumer and automotive sensor applications.
AMR Sensors
Principle
Anisotropic magnetoresistance (AMR) appears in a magnetic material as a resistiv-
ity change when the relative orientation of the current is altered in respect to the
magnetization direction.
Discovered by W. Thomson in 1857 [12], it can be expressed by
with
where ρ par is the resistivity when the current flows parallel to M, i.e., for θ = 0,
and ρ perp the resistivity when the current flows perpendicular to M, i.e., for θ = 90◦
(Fig. 7).
Fig. 7 AMR principle: The resistance of a ferromagnetic slab in which a current flow depends
on the field H applied in the plane of the slab, and varies as cos (θ)2 ; θ being the angle between
the current and the magnetization (see in Fig. 8a). To linearize the sensor response, the best way
is to set this angle to 45◦ , for instance, by adding some conducting lines (shown here in gray) to
force the current flow at 45◦ to the magnetization. This configuration is called “barber pole.” The
resistance variation as a function of field is given in Fig. 8b
1536 M. Pannetier-Lecoeur and C. Fermon
Fig. 8 (a) Resistance variation of the AMR as a function of the angle between the applied field
H and the current. (b) Resistance as a function of a field aligned at 45◦ of the current flow. The
response is linear at low field
Main Applications
AMR thin films were once used to replace the inductive coils in computers read
heads, thanks to their good sensitivity and to their miniaturization. They are used
for linear sensors and current sensors.
Principle
Giant magnetoresistance appears in ferromagnetic materials which are magnetically
coupled through a very thin metallic layer [13]. First observed in Fe/Cr multilayers
[14], it has been extended to more elaborate stacks, such as the spin valve proposed
by Dieny in 1991 [15] which includes a reference layer by coupling a ferromagnet
to an antiferromagnet and a free layer comprising a ferromagnet; both pinned
and free layers are separated by a nonmagnetic metal, such as copper. In tunnel
magnetoresistance (TMR), the metallic spacer is replaced by an insulating layer
through which the conduction electrons from the pinned (or the free) layer tunnel
to the free (or pinned layer). In GMR sensors, magnetoresistance ratios as high as
20% can be obtained, whereas in TMR sensor with an MgO spacer, it can exceed
200% at room temperature [16, 17]. The physical origin of these effects is the spin
polarization of conduction electrons in metallic magnetic layers, hence in a spin
valve structure, for example, a first magnetic layer acts as a spin polarizer whereas
the second magnetic layer (usually made of soft ferromagnet) operates as a spin
analyzer. The whole structure filters electrons according to the relative orientation
of the two layer’s magnetization.
31 Magnetic Sensors 1537
Fig. 9 GMR in angle sensing mode. (a) The structure comprises a pinned layer (PL) – here shown
pointing perpendicularly towards the bottom – whose magnetization is set by the choice of material
and deposition process conditions, and a free layer (FL), made of layers of ferromagnetic material
with a very low Hc , such as a NiFe/CoFe bilayer. The two sets of layers, PL and FL are separated
by a spacer of nonmagnetic material, conducting for GMR (copper being the most commonly used)
and insulating (such as MgO or Al2 O3 ) for TMR. When a field H > Hsat is applied in the plane of
the sensor, it aligns the FL layer and the resistance of the sensor is proportional to the cosine of θ,
the angle between the PL and the FL. (b) Output voltage of the GMR in the angle sensing mode
In a spin valve, which is the most commonly used stack for magnetic sensing,
the output voltage is given by:
Rap − Rp
V = R0 + cos θ I, (6)
2
Rap (resp. Rp ) is the resistance when the pinned and free layer are antiparallel
(resp. parallel), R0 the mean value, and θ the angle between the pinned and the free
layer (see also Fig. 9).
The sensor response can be linearized around H = 0 by means of an additional
in-plane magnetization (Fig. 10) to obtain an output voltage proportional to H .
Main Applications
Devices based on GMR or TMR have replaced AMR technology in hard disk read
heads, which has been the largest application of spin electronics. Now magnetic
random access memories (MRAMs) based on TMR are marketed, and sensing
applications in the area of automotive or other large-scale application (mobile
phones . . . ) are developing. GMR and TMR can be integrated to CMOS in a back-
end process, allowing small size integrated devices.
1538 M. Pannetier-Lecoeur and C. Fermon
Fig. 10 GMR in field sensing mode. (a) On the same type of GMR stack as shown in Fig. 9a,
the addition of a magnetization M0 in plane and perpendicular to the FL leads to a voltage change
proportional to the angle between the applied field and M0 , therefore proportional to the magnitude
of H . (b) Corresponding output voltage of the GMR sensor
Principle
First demonstrated in the 1960s [18, 19] on a principle shown in 1957 [20], optical
magnetometers use alkali atoms which are spin polarized by resonant light. Under
magnetic field, electron spins precess and the light transmitted through the atomic
vapor is reduced. The resolution of these magnetometers is limited by the spin
exchange relaxation which brings decoherence, but by increasing the density of
the atoms in the vapor in the cell (by heating), field detection levels down to
√
1fT/ Hz have been demonstrated in so-called SERF (for spin exchange relaxation
free) optical magnetometers [21] (Fig. 11).
Sensitivity to magnetic field for a time of measurement tM is given by [22]:
1
δB = √ (7)
gμ0 Nτ tM
g being the Landé factor, μ0 the Bohr magneton, the Planck constant, τ the
coherence time, and N the number of atoms.
Main Applications
Thanks to their high sensitivity and low noise, optical magnetometers are used
for geomagnetic field mapping, biomagnetic signal detection, material science, or
NMR and MRI. They do not require cryogenics and can be made in relatively small
size/chip-scale devices [23]. The main limitation is the dynamics, which is limited
in field range for the most sensitive magnetometer, and requires a heavy magnetic
shielding to ensure sufficient screening of electromagnetic perturbations.
31 Magnetic Sensors 1539
Fig. 11 SERF optical magnetometer principle: The alkali vapor contained in the gas cell is
polarized by circularly polarized light (pump laser). The probe laser light, partially absorbed when
a field is applied to the alkali atoms, is detected by an array of photodiodes
Principle
Nitrogen vacancies (NV) centers are one of the point defects in diamond. They are
particularly useful as individual center can be detected by photoluminescence. NV
fluorescence is spin-state dependent. Hence a microwave sent at 2.88 GHz induces
a change in the fluorescence intensity. In presence of an external field, the frequency
of absorption is split in two lines with a separation given by the g factor [53, 52]. By
measuring the splitting, the field can be deduced. The present detectivity of a single
√ √
center is in the range of 1 μT/ Hz and for an assembly of centers, sub-nT/ Hz
detectivity are achieved.
Main Applications
NV centers are very attractive for two applications: a very local detection of
magnetic fields with resolution achieving today 50 nm [51, 50] and magnetic
imaging at larger scale. More recently NV centers have been also used for nanometer
scale NMR spectroscopy [49]. NV centers have also a long coherence time which
make them very attractive also or quantum storage and quantum computing.
Giant Magnetoimpedance
Principle
Discovered in 1994 [24, 25], giant magnetoimpedance (GMI) is based on a physical
phenomenon totally different from the spin electronic-based sensors. When a
1540 M. Pannetier-Lecoeur and C. Fermon
metallic wire is subject to an ac voltage, due to the skin effect, the current flows
mainly at the surface of the wire. If this wire is made of magnetic material, its
permeability has an impact on the conductivity and hence the impedance of the wire
will be dependent on its static magnetic configuration. An external dc magnetic field,
by changing this configuration, induces a change in the measured impedance. This
effect is highly nonlinear but can be rather large and in a closed loop design, highly
sensitive devices have been proposed [26, 27, 28, 29].
Main Applications
Presently, GMI is investigated for applications such as current sensors, position
sensors, or for biochip applications but its nonintegrability and the necessity of
having high ac frequency and data treatment limit its use to specific high-sensitivity
applications.
Magnetoelectric Sensors
Principle
The magnetoelectric response is the appearance of an electric polarization P
upon applying a magnetic field H and/or the appearance of a magnetization M
upon applying an electric field E (inverse magnetoelectric effect). This effect is
extensively studied in multiferroic components for applications such as magnetic
sensors. However, based on strain-induced by magnetostriction, magnetoelectric
sensors can also be built. If a piezoelectric material such as PZT (Lead Zirconate
Titanate) is strongly coupled to a soft magnetic material, a voltage applied to the
PZT creates a strain in the material which can modify the direction or the amplitude
of the magnetization. Inversely, if a magnetic field is applied on a magnetic material,
due to magnetostriction, a strain is created in the piezoelectric material inducing a
voltage (Fig. 12). The interest of this kind of sensor is that it is passive, as a voltage
is directly created by a field change with no external power supply (Tables 2 and 3).
Fig. 12 Example of a
magnetoelectric device. A
soft magnetic material like Ni
with a relatively large
magnetostriction is coupled
to a piezoelectric material.
When a magnetic field is
applied, the magnetostrictive
material is creating a strain on
the piezoelectric material
leading to the appearance of a
voltage
31 Magnetic Sensors 1541
Noise
Definitions
To fully define a sensor’s performance and its ability to detect a signal defined by
several parameters (field strength, frequency . . . ), the signal-to-noise ratio (SNR) in
the operating conditions is given. Once this value is known, it indicates if the sensor
is adequate for the detection of the targeted signal (if the SNR is larger than 1) or
the number of averages required
√ to extract the signal from the noise (knowing that
the SNR is multiplied by N, N being the number of repeated measurements).
Any macroscopic quantity (such as the output voltage of a sensor) experiences
fluctuations around its mean value, which gives rise to the sensor’s intrinsic noise.
This noise will give the lowest SNR achievable, in absence of external perturbations.
Applying a spectral analysis of the signal (here taking V as an example) via a
Fourier transform allows separating and understanding the various noise sources.
Under Fourier transformation, V can be expressed in the frequency domain as:
1542 M. Pannetier-Lecoeur and C. Fermon
t0
1
VT = V (t) eiωt dt. (8)
2π 0
t0
1
P = V (t)2 dt. (9)
t0 0
From the above, one can express the power spectral density (PSD):
VT (ω)2
SV = lim 2π . (10)
T →∞ t0
√
SV
SB = . (11)
s
√ √
where s is the sensitivity in V/T, and SB is expressed in T/ Hz.
A precise expression for the PSD and its field equivalent can be only theoretically
given when all the noise sources in the sensor are identified and when their origin is
known, but most of the time, the PSD can only be evaluated from phenomenological
approaches and measurements of the parameters specific to the sensor.
Among the various noise sources, one may cite (for resistor-type sensor) thermal
noise [32] and shot noise (can be fully described theoretically), low-frequency noise
and random telegraph noise; the latter can be only expressed by phenomenological
expressions (Hooge formula [33] for 1/f noise in resistors). For sensors based on
quantum properties, exact expressions can give the theoretical noise limit, such as
in optical magnetometers or SQUIDs.
Detection Schemes
Magnetometer
Magnetic field sensing in magnetometer mode is the simplest; the sensor is used to
record at a single location and its output depends on the H component for a vector
magnetometer, or on the H magnitude for scalar one.
31 Magnetic Sensors 1543
Gradiometer
When the field source is local, it may be very useful to use the sensor in a
gradiometer configuration, which eliminates distant sources and environmental
noise. According to the location of the source and to the sensing direction of the
magnetometer, gradiometers can be axial or radial. When a gradiometer comprises
two magnetometers, one close to the source and the second at a larger distance, it is
a first-order gradiometer. More complex gradiometers (second, third order) integrate
three or four magnetometers to reject higher order of noise contamination and refine
the signal of interest (Figs. 13 and 14).
Fig. 14 First-order gradiometer: (a) radial along z and (b) axial along x and y
1544 M. Pannetier-Lecoeur and C. Fermon
Fig. 15 Closed-loop measurement: The sensor output is compared to a reference value (fixed
voltage, temperature-compensated voltage, or dummy sensor-sensor insensitive to the external
field). The difference is amplified and sent to a coil through an inverting amplifier. It generates a
field HF which is directly proportional to the applied field H . Appropriate filtering can be inserted
in the feedback loop
Closed Loop
A number of magnetic sensors are inherently nonlinear. This is the case for SQUIDs,
GMI, or optical sensors and to a lesser extent for all magnetoresistive sensors. For
that reason, a closed-loop scheme is often used even in integrated sensors. The prin-
ciple is to have a feedback coil (or wire) which creates a field on the sensor in order
to maintain it in a field where the sensor is the most sensitive. When the external
applied field varies, the current in the feedback coil is adjusted by an analog or
digital electronic loop in order to maintain the sensor output constant. The read value
is not the actual sensor output, it is the current sent to the feedback coil. This scheme
has two advantages; firstly, it linearizes the sensor and secondly, it suppresses sensor
sensitivity variation (as function of temperature, for example) (Fig. 15).
Bridge
Applications
Magnetometers are used for field and flux sensing, either directly when the source
is a magnetic element (bulk magnet, Earth’s field, magnetic nanoparticles . . . ) or
31 Magnetic Sensors 1545
Fig. 16 Bridge configuration (i) with four sensors and (ii) with two sensors and equivalent
resistances RFeed
when the source produces a magnetic field, such as induced by an electrical current
running in a conductive wire or medium.
Field sensors can be used in combination with a flux concentrator, which
transforms the flux caught on a surface to a locally enhanced field in the vicinity of
the sensor. This can be applied by either using soft ferromagnetic flux concentrators
[34, 35] or a superconducting loop combined with a GMR sensor [36], leading to
an increase of sensitivity and/or a change in the direction of the field sensed.
Current Sensing
Position Sensing
Magnetic sensors are also widely used, in particular in the automotive market, to
detect the position of a moving element (such as a gear or a crank) either by placing
the magnetic sensor in front of the moving magnetized element or by using a back
bias solution where the magnet is placed on the sensor, and where the moving
or rotating metallic element is changing the magnetization landscape seen by the
sensor. The repetition of a known pattern can be detected and indicates the speed of
the target (Fig. 17).
1546 M. Pannetier-Lecoeur and C. Fermon
Fig. 17 Speed sensor. (a) The sensor is facing a rotating magnetized target. (b) A magnet, placed
on the back of the sensor, generates a field landscape which changes when the metallic target,
containing specific features – here teeth – rotates. (c) Sensor output as a function of the target
rotation angle for (a) and (b) configurations. Plateau or edge detection gives the rotation speed of
the target
Fig. 18 Field range for various sensors. Field sensors are shown in the upper part of the figure
and flux sensors in the bottom part. Note that optical magnetometers usually require heating up to
180 ◦ C and SQUIDs require liquid helium (4 K) or liquid nitrogen (77 K) temperature to operate
Figure 18 summarizes the field range for various sensors based on the physical
principles presented in this chapter. Field sensors (on the top part of the figure) have
in general lower sensitivity than flux sensors, but can be miniaturized.
Table 4 gives an overview of sensitivity and noise for the main sensors type
presented in this chapter, detailing also their maximal measurable field as well as
their main advantages and drawbacks.
31 Magnetic Sensors 1547
Table 4 (continued)
Intrinsic
Sensor sensitivity Field equivalent noise Maximal Advantages Drawbacks
Standard
√ Best √ Measurable
(V/T) T/ Hz T/ Hz Field
SQUIDS 106 –107 10 fT 1 fT [7] 10 μT Ultrasensitive Cryogenic
cooling
a For Si-Hall sensors
b Sensitivityand range are dependent and can be tuned by shape anisotropy for instance
c Optical detection
d For tuned coils
e Depends on the number of windings
f With flux concentrators
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Contents
Introduction: Magnetic Memory and Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1554
Magnetic Hard Drive Memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1554
Hard Drive and Its Road Map . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1555
Giant Magnetoresistance and RKKY Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1556
Tunneling Magnetoresistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1557
Magnetic Random-Access Memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1559
Magnetic Random-Access Memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1560
Spin-Transfer Torque Magnetic Random-Access Memory . . . . . . . . . . . . . . . . . . . . . . . . 1560
Spin-Orbit Torque Magnetic Random-Access Memory . . . . . . . . . . . . . . . . . . . . . . . . . . . 1562
New-Type Magnetic Memories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1564
Domain Wall Racetrack Memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1565
Skrymion Racetrack Memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1567
Antiferromagnetic Memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1570
2D van der Waals Magnets Memory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1572
Magnetic Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1573
Nanomagnet Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1574
Magnetic Domain Wall Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1576
Magnetic Tunnel Junction Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1578
Spin Current Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1578
All Spin Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1578
Graphene Spin Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1581
Magnetoelectric Spin-Orbit Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1583
Spin Wave Logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1584
Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1586
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1587
W. Han ()
International Center for Quantum Materials, School of Physics, Peking University, Beijing, China
e-mail: [email protected]
Since the institution of the International Olympic Committee in 1894, the three
Latin words “Citius, Altius, and Fortius,” which mean “faster, higher, and stronger,”
are the motto of the Olympic Games. Similarly, “faster, denser, and longer” is the
motto that could be adopted by the scientific community behind the development of
the magnetic memory and logic devices for information technology. The storage
density of the magnetic hard drives used as primary memory has seen more
than a thousandfold increase since the first application of giant magnetoresistance
into the read head around 1997. The integration of memory and logic in the
same device, together with progressive miniaturization, is expected to break the
energy and time constraints of the classic Neumann architecture. This chapter
of magnetic memory and logic focuses on the discussion of using magnetic
materials, magnetoresistance, and spin current for information storage and logic
applications. It is organized as follows: The second section discusses the magnetic
hard drive memory and its road map in terms of the storage density, mainly
arising from the physical discoveries of giant magnetoresistance and tunneling
magnetoresistance. The third section presents the magnetic random-access memory
and its development from current-induced magnetic field switching, then spin-
transfer torque switching, to recent spin-orbit torque switching. The fourth section
discusses the new types of magnetic memories, including domain wall racetrack
memory, skyrmion racetrack memory, antiferromagnetic memory, and 2D van der
Waals magnets memory. The fifth section discusses the logic in magnetic memory
devices, such as nanomagnet logic, domain wall logic, and magnetic tunnel junction
logic. The sixth section discusses the spin current logic devices, including all
spin logic, magnetoelectric spin-orbit logic, and spin wave logic. The summary
and future outlook of magnetic memory and logic are discussed in the final
section.
Magnetic hard drives have been the prime repository of digital data for more than
half a century. It is one of the biggest technological and commercial successes of
spintronics and magnetism so far. Just over 10 years ago, the storage capacity of
all the world’s magnetic disk drives surpassed that of analog data storage devices.
Together with complementary metal-oxide-semiconductor (CMOS) technology,
magnetic hard drives have brought consumer the information storage and computing
for our daily lives. The basics of magnetic hard drive memory and the major physical
discoveries that lead to a higher storage density of the magnetic hard drives, such as
giant magnetoresistance and tunneling magnetoresistance, will be discussed in this
section.
32 Magnetic Memory and Logic 1555
Fig. 1 Magnetic hard drives and its road map. (a) An optical image of the magnetic hard drive and
the read-and-write head. (b) The schematic of the magnetic head and recording medium for a hard
drive. B is the minimum length of the magnetic domains. The GMR read sensor is based on giant
magnetoresistance. The inductive “ring-type” head is used for writing information by switching the
local domain’s magnetization. (Reproduced from [1]). (c) The evolution of the hard drive storage
density from 1996 to 2019. (The illustration of the magnetic medium is reproduced from [2])
Magnetic hard drives, first created in 1953 by IBM engineers, have provided the
storage devices with high capacity and low cost. The main parts of a magnetic hard
drive include a magnetic disk platter that has a thin magnetic layer on the surface, the
actuator arm that mechanically controls the motion of the read-and-write head, and
the read-and-write head (Fig. 1a). The write head uses conducting current-induced
magnetic field to switch the magnetic domains of the magnetic materials, and the
read head uses magnetic sensor to read the magnetization as the stored information
(Fig. 1b).
The first step to increase the capacity of a hard disk drive was made by using
the anisotropic magnetoresistive device as the magnetic sensor in 1991 by IBM
[1, 3]. Shortly in 1997, the giant magnetoresistance sensor, a more sensitive and
scalable read technique, was used in the read head, which has led to an increase
of the storage density in hard disk drives by more than two orders of magnitude
to ∼300 GB/in2 in 2007 (Fig. 1c). Then, the tunneling magnetoresistive sensor
1556 W. Han
was incorporated into the read head, which further increased the storage density
of hard disk drives. Many great scientists contributed to the fast increase of the
storage density that has led to the transition of the hard disk to consumer electronics.
Among them, Prof. Albert Fert and Prof. Peter Grunberg won the 2007 Nobel
Prize in physics for their discovery of giant magnetoresistance. Prof. Stuart Parkin
was awarded the 2014 Millennium Technology Prize from Technology Academy
Finland, the prominent award for technological innovation, for his discoveries that
have enabled a thousandfold increase in the storage capacity of magnetic disk drives.
In the following, the giant magnetoresistance and tunneling magnetoresistance will
be discussed.
As discussed earlier, the application of giant magnetoresistance into the read heads
in 1997 greatly contributed to the fast increase of the storage density of hard
disk drives. This is probably the biggest commercial success of spintronics so
far that could detect small magnetic fields sensitively at room temperature. The
discovery of the giant magnetoresistance in magnetic multilayer heterostructures
was made by two independent research groups in the late 1980s [1, 4–6]. The
magnetic multilayer heterostructures consist of the ferromagnetic Fe layers that
are separated by nonmagnetic Cr spacing layers (Fig. 2a), which can be grown
by thin film growth techniques, such as molecular beam epitaxy and magnetron
sputtering. The observed giant magnetoresistance ratio in Fe/Cr multilayers was
shown to be highly dependent on the thickness of Fe and Cr layers. The maximum
of the magnetoresistance ratio (MR = (RAP − RP )/RP × 100) is found to be
∼80% measured on the multilayer heterostructures of (Fe (3 nm)/Cr (0.9 nm))60
(Fig. 2b).
The physical origin of giant magnetoresistance is the spin-dependent scattering at
the interfaces of the magnetic multilayers. At zero magnetic field, the magnetization
states of the neighboring Fe layers are antiparallel to each other. In such states, the
electrons of each channel are slowed down every second magnetic layer, leading
to a high-resistance value. On the other hand, when the external magnetic field is
large enough, the magnetizations of the all the Fe layers point to the same direction.
In such parallel magnetization states, the majority spin-polarized electrons can go
easily through all the Fe layers, leading to a small resistance value.
Later, it was found that the giant magnetoresistance highly depended on the
thickness of the nonmagnetic spacing layers [7]. The multilayers consisting of
Fe/Cr, Co/Ru, and Co/Cr were investigated, and an oscillatory behavior of the
giant magnetoresistance was observed. The experimental results measured on the
Fe/Cr multilayer heterostructures are shown in Fig. 2c, where the maximum of
the giant magnetoresistance was observed for the Cr thickness of ∼1 nm with
the antiparallel exchange coupling between the Fe layers. The oscillatory behavior
of the magnetoresistance has been attributed to the oscillatory exchange coupling
(between ferromagnetic and antiferromagnetic) of the Fe magnetizations as a
function of the thickness of the nonmagnetic layers [8]. This mechanism is identified
32 Magnetic Memory and Logic 1557
Fig. 2 Giant magnetoresistance and RKKY coupling. (a) Illustration of the magnetic multilayer
structures consisting of nanometer-thick magnetic Fe and nonmagnetic spacing Cr layers. (b) The
observation of the giant magnetoresistance effect in Fe/Cr/Fe multilayers. HS represents the exter-
nal magnetic field that aligns the Fe magnetizations from antiparallel to parallel configurations. The
largest giant magnetoresistance is ∼80%. (Reproduced from [4]). (c) The giant magnetoresistance
of Fe/Cr multilayers as a function of the thickness of the Cr spacing layer. Inset: illustration of the
RKKY coupling, the oscillatory exchange coupling between ferromagnetic and antiferromagnetic
coupling as a function of the nonmagnetic layer thickness. (Reproduced from [7])
Tunneling Magnetoresistance
Fig. 3 (continued)
32 Magnetic Memory and Logic 1559
The first proposal of the magnetic random-access memory (MRAM) based on spin
valves [14] ignited a race to achieve a successful prototyping. The long endurance,
high density, and fast writing time have made MRAM an ideal candidate to replace
silicon-based RAMs [15]. The giant TMR in MgO-based magnetic tunnel junctions
Fig. 3 Giant tunneling magnetoresistance at room temperature with a crystalline MgO tunnel bar-
rier. (a) Transmission electron microscopy photograph of the CoFe/MgO/CoFe junction. (b) Large
tunneling magnetoresistance (TMR) of the CoFe/MgO/CoFe magnetic tunnel junctions annealed
at 120 ◦ C, 360 ◦ C, and 380 ◦ C, respectively. The magnetoresistance curves are asymmetric with
respect to the external magnetic field due to an exchange bias from an antiferromagnetic IrMn
pinning layer. (Reproduced from [11]). (c, d) The MgO spin filtering effect that gives rise to giant
tunneling magnetoresistance ratio. Dominant tunneling states are the fully spin-polarized 1 band
Bloch states. (Reproduced from [13])
1560 W. Han
gave a strong boost to MRAM technology [11, 12]. Recently, many semiconductor
companies have announced the large-scale production of MRAM products. In this
section, the basics of the magnetic random-access memory, the two major advances,
and the recent development of spin-orbit torque magnetic random-access memory
will be discussed.
• For reading, the magnetoresistance of the addressed magnetic tunnel junction cell
is measured between the “bit” and “word” lines [1].
• For writing, a magnetic field, generated by current carrying wires, is used as
the oldest method. The current pulses are sent through one line of each array,
and only at the crossing point of these lines, the resulting magnetic field is high
enough to reorient the magnetization of the free layer.
‘Word’ ‘1’
lines Transistor
‘0’
(b) (c) 10
No. of cycles
9
e- e-
Resistance (kΩ)
8
‘0’
7 ‘1’
6 100 ns
1 cycle operation
Transverse
component 5
F1 F2 4
-10 -8 -6 -4 -2 0 2 4 6 8 10
Current (a.u.)
(d) (e)
m Free Layer
mp Hard Layer
Fig. 4 Magnetic random-access memory and two major advances that contributed to the devel-
opment of the magnetic random-access memory, namely, the discovery of spin-transfer torque
and material engineering of CoFeB with perpendicular magnetic anisotropy. (a) Schematic of
magnetic random-access memory device. “1” corresponds to the high-resistance value when
the two magnetic layers are antiparallel, and “0” corresponds to the low-resistance state for the
parallel magnetization of the two magnetic layers. (Reproduced from [1]). (b) Illustration of the
spin-transfer concept introduced by Slonczewski and Berger [16, 17]. A spin-polarized current
is prepared by a first ferromagnetic layer (F1 ) with an obliquely oriented spin polarization with
respect to the magnetization axis of a second ferromagnetic layer (F2 ), thus applying a spin-
transfer torque acting on F2 magnetization. (Reproduced from [1]). (c) The tunneling resistance
versus current hysteresis loop of a magnetic tunnel junction cell with CoFe/NiFe as the free layer
and 1.0 nm MgO as the tunnel barrier. The No. of cycles are 1, 10, 100, 1K, 10K, 100K, 1M,
10M, 100M, and 1G (from top to down), respectively. (Reproduced from [18]). (d) Illustration
of the MgO-based magnetic tunnel junction with perpendicular magnetic anisotropy. (e) Current-
induced magnetization switching of the magnetic tunnel junction (40 nm diameter) with current
pulse durations of 300 μs and 1.0 s. The top CoFeB layer is 1.0 nm and the bottom CoFeB layer is
1.7 nm. The MgO thickness is 0.85 nm. (Reproduced from [19])
1562 W. Han
in Fig. 4b, the outflowing current from electrode F1 is spin-polarized. When such
current enters the right ferromagnetic electrode (F2), the spin polarization of the
electrons is not aligned with the magnetization of the ferromagnetic layer; thus,
the spins precess rapidly around a momentum-dependent internal field of the right
ferromagnetic electrode. As a result, the component of spin polarization transverses
to the magnetization decays, transferring spin angular momentum to the ferromag-
net. A typical demonstration of the spin-transfer torque switching of a magnetic
tunnel junction with 1 nm single crystalline MgO tunnel barrier is shown in Fig. 4c.
The current generated by the voltage bias switches the magnetic tunnel junction
between the parallel state with low resistance and antiparallel state with high
resistance via the spin-transfer torque physical mechanism. Under positive bias, the
positive current leads to the switching from antiparallel to parallel magnetization
configurations, while negative voltage leads to the opposite switching. The excellent
stability is also demonstrated after 109 cycles using 100 ns pulses of successively
positive and negative current pulses. The long endurance of spin-transfer torque
makes magnetic random-access memory standing out compared to flash memories
(typically ∼105 cycles) [15].
Magnetic electrodes with perpendicular magnetic anisotropy (out-of-plane easy
axis) can improve thermal stability in MRAM devices (Fig. 4d). Prof. Ohno’s
group in Tohoku University fabricated the first CoFeB thin films with perpendicular
magnetic anisotropy on single crystalline MgO tunnel barriers in 2010 [19].
Figure 4e shows the magnetoresistance as a function of the current bias measured
on a Ta/CoFeB/MgO/CoFeB/Ta MTJ with a diameter of 40 nm. The interfacial
anisotropy between CoFeB and MgO is the origin of the thin CoFeB magnetic
easy axis switching from in-plane to perpendicular axis as the CoFeB thickness
decreases below ∼1.5 nm. These results demonstrated MTJs with small size (40 nm
diameter), sufficient thermal stability, low switching current (49 μA), and high
tunnel magnetoresistance ratio (120%).
Fig. 5 SOT-MRAM. (a) Schematic of the three-terminal SOT-MRAM device. The reading circuit
is separated from the writing current loop, thus eliminating the risk of current-induced breaking
of the MgO tunnel barrier. (b) The large spin-orbit torque from β-Ta thin film that switches
the magnetization of the bottom CoFeB electrode. (c) The tunneling magnetoresistance of the
CoFeB/MgO/CoFeB as a function of the DC current in the Ta layer. At the positive DC current
of ∼0.9 mA, a lower magnetoresistance is achieved, indicating the switching of the CoFeB
magnetization. (Reproduced from [21]). (d) The comparison of the spin Hall angle of topological
insulators, Pt and β-Ta, for switching the CoTb magnetization. (Reproduced from [23])
[21]. A positive DC current in β-Ta layer switches the magnetic tunnel junction
from antiparallel to parallel configurations, while a negative current switches it
to the antiparallel state with high resistance (Fig. 5c). Compared to STT-MRAM,
one disadvantage of SOT-MRAM is its three-terminal feature, which makes it quite
challenging for high density stoarge.
The magnetization switching arising from the spin current torque can be
generated via two physical mechanisms, namely, spin Hall effect [24–27] and
Rashba-Edelstein effect [28–30]. Quantum materials are a class of materials
whose quantum properties stem from a complex interplay between factors such
as reduced dimensionality, quantum confinement, quantum coherence, quantum
fluctuations, topology of wavefunctions, relativistic spin-orbit interactions, and
fundamental symmetries. Recent developments have exhibited many unique spin-
dependent properties of quantum materials, which can be used as promising material
1564 W. Han
Fig. 6 Quantum materials for spin and charge conversion and spin-orbit torque for magnetization
switching applications. These materials include the topological insulator with spin-momentum
locked surface states, Rashba-split two-dimensional electron gases (such as LaAlO3 /SrTiO3 ,
Bi/Ag, etc.), 2D materials, superconductors, as well as non-collinear antiferromagnetic IrMn3 with
Berry curvature-induced large effective spin-orbit coupling. (Reproduced from [31])
candidates for efficient spin and charge conversion (Fig. 6) [31]. For example,
the spin-momentum locked surface states on three-dimensional topological insu-
lators provide a potentially efficient route for the spin current generation and
magnetization switching [23, 32]. The effective spin Hall angle and the switching
energy of topological insulators have exhibited better properties than conventional
metals with large spin-orbit coupling (Fig. 5d). Besides topological insulators, the
Rashba interface states (Fig. 6), such as LaAlO3 /SrTiO3 and Bi/Ag, also exhibited
considerably large spin-orbit torque [33–35]. The effective spin-orbit torque of
LaAlO3 /SrTiO3 can be tuned by a gate voltage [34, 35]. Other quantum materials,
such as two-dimensional material WTe2 [36], superconductors [37], and non-
collinear antiferromagnetic IrMn3 [38] (Fig. 6), also exhibited interesting spin and
charge conversion properties.
For the purpose of high reliability, performance, and capacity memory, scientists
have never stopped searching for a new type of magnetic memories based on novel
physical mechanisms and materials. This section will describe several emerging
magnetic memories, including the domain wall racetrack memory, skyrmion race-
track memory, antiferromagnetic memory, and 2D magnets memory.
32 Magnetic Memory and Logic 1565
Compared to the two-dimensional feature in hard disk drives where the information
is stored in a magnetic film determined by its magnetization, domain wall magnetic
racetrack memory can be developed as a three-dimensional intelligent memory chip
with similar storage density but faster random read/write speed (Fig. 7) [39]. One
key development toward the domain wall racetrack memory is the moving of a train
of several domain walls by nanosecond current pulses via spin-transfer torque [39].
The current in a magnetic material is spin-polarized, thus generating a spin-transfer
torque on the magnetic domains and derives the domain wall motion (Fig. 7a). The
reading of stored information of domain wall racetrack memory can be realized
using magnetoresistive sensing devices based on magnetic tunnel junctions that are
close to the racetrack nanowires (Fig. 7b). The writing of domain walls (Fig. 7c) can
be done using either the Oersted field of currents passing along neighboring metallic
nanowires or spin-transfer torque from adjacent magnetic nanoelements.
As discussed earlier, the domain wall racetrack memory relies on the current-
driven domain wall motion in the magnetic nanowires. The evolution of the domain
wall racetrack memory can be divided into several major versions (Fig. 8a),
including the first one that uses in-plane magnetic anisotropy nanowires, the
second version based on the perpendicular magnetic anisotropic nanowires, the third
version that uses perpendicular magnetic anisotropic nanowires with adjacent heavy
metals to provide spin-orbit torque that drives high-speed domain wall motion,
Fig. 7 Magnetic domain wall racetrack memory. (a) A vertical-configuration racetrack stores the
information in a U-shaped nanowire. Pulses of spin-polarized current move the entire pattern of
domain walls coherently along the length of the wire past read-and-write elements. (b, c) The
illustration of the reading and writing of the data in magnetic domain wall racetrack memory.
(d) Three-dimensional arrays of racetracks for high-density storage applications. (Reproduced
from [39])
1566 W. Han
Fig. 8 Evolution of racetrack memory and the high-speed domain wall motion. (a) The evolution
of racetrack memory from in-plane magnetic anisotropy nanowire, perpendicular magnetic
anisotropic nanowire, and spin-orbit torque-driven domain wall motion to the high-speed domain
wall motion by both spin-orbit and exchange coupling torques. (Reproduced from [2]). (b) High-
speed domain wall motion of ∼750 m/s using synthetic antiferromagnetic nanowires driven
by exchange coupling torque. (Reproduced from [40]). (c) High-speed domain wall motion of
ferrimagnetic CoTb nanowires driven by magnetic field. A high domain wall velocity that is larger
than 1000 m/s is observed around the angular momentum compensation temperature. (Reproduced
from [41])
and the fourth version that uses synthetic antiferromagnetic coupled nanowires
with exchange coupling torques [2]. One of the major benefits from in-plane to
perpendicular magnetic anisotropic nanowire is the reduced width of the domain
wall, allowing for higher bit density. Both of the first and second versions of
racetrack memories rely on the spin-polarized current in the nanowires themselves
to generate the spin-transfer torque that drives the magnetic domain walls to move.
The domain wall motion direction is opposite to the current pulse direction.
Elevated domain wall velocity is required to achieve high-speed reading and
writing. It has been demonstrated that the perpendicular ferromagnetic domain
wall on an adjacent heavy metal can lead to high-speed domain wall motion
with velocities of ∼350 m/s with the pulsed current densities of ∼108 A cm−2
[42, 43]. For this type of racetrack memory, the domain wall motion and the
32 Magnetic Memory and Logic 1567
pulsed charge current have the same directions, which is different from the early
versions (Fig. 8a). Both the spin Hall effect-induced spin-orbit torque and the
interfacial Dzyaloshinskii-Moriya interaction contribute to the high-speed domain
wall motion. The spin current generated in the heavy metal layer diffuses into the
neighboring magnetic layer and causes the moments within each domain walls to
rotate toward the spin direction accumulated at the interface. The Dzyaloshinskii-
Moriya interaction exchange field, which has same chirality of spin Hall effect, then
provides a torque on these rotated moments that causes all the domain walls to move
in the same direction.
Recently, scientists have pushed the current pulse-driven domain wall velocity
to 750 m/s using synthetic antiferromagnetic nanowires (Fig. 8b) [40]. The high
speed is accounted by an exchange coupling torque on the Néel domain wall, which
is directly proportional to the strength of the antiferromagnetic exchange coupling
between the two sub-layers. The closer the magnetization of the racetrack is zero, the
faster the domain wall moves. Besides, the net small magnetization also removes the
dipolar coupling, which will be helpful for closely packed domain walls and high-
capacity memory. Another approach is using ferrimagnetic materials, such as CoTb
[41], which also has net zero magnetization at the angular momentum compensation
temperature. The domain wall velocity is remarkably enhanced up to ∼1500 m/s
driven by an external magnetic field of 100 mT (Fig. 8c).
Skyrmions are topologically stable field configurations, named after the physicist
Tony Skyrme [44]. Magnetic skyrmions are chiral spin structures with whirling
configurations in magnetic materials. For example, a typical Néel-type skyrmion
has the magnetization pointing up on the edges and pointing down in the center,
and the magnetization rotates by 2π around an axis perpendicular to the diameter
(Fig. 9a).
Their robustness against external perturbations and small size, together with the
low current density needed to move them along a magnetic wire, make them suitable
for a racetrack-like memory concept. The stability of nano-size skyrmions, the
generation by current pulses, the detection via electrical means, and the high-speed
motion of the skyrmions are all necessary elements for a real-world implementation
of a skyrmion racetrack memory (Fig. 9a). Due to their “topological” spin texture,
magnetic skyrmions are theoretically able to move past the defects that can be
found at the edges of nanowires. Results from micromagnetic simulations of spin-
polarized current-induced motion of individual skyrmion Co stripes are shown in
Fig. 9b to support this claim [45]. The skyrmion moves away from the notch
structure on the nanowire under a larger current pulse and stops at the notch under
a smaller current pulse.
Recently, a lot of breakthroughs have been achieved in terms of both physical
mechanisms and materials engineering. For example, it has been shown that
skyrmions are stable in the multilayers consisting of a ferromagnet and a material
1568 W. Han
with large spin-orbit coupling (Fig. 10a). At the interface of magnetic multilayers,
the Dzyaloshinskii-Moriya interaction results a non-collinear chiral spin texture
[30]. Following the technique, the stabilization of nanoscale skyrmions down to
∼50 nm at room temperature in tri-layer structures has been achieved at the Pt/Co/Ir
interfaces, where the interfacial Dzyaloshinskii-Moriya interaction is enhanced due
to the opposite signs for Pt/Co and Co/Ir interfaces [46].
The electrical generation and detection of magnetic skyrmions have also been
experimentally realized in magnetic multilayer heterostructures. The creation of
magnetic skyrmion in the Ta(5 nm)/Co20 Fe60 B20 (1.1 nm)/TaOx (3 nm) tri-layers
has been performed at room temperature via a current pulse in a geometrical
constriction (Fig. 10b) [47]. After applying an electric current, the chiral bubble
domains on the left side of the sample transform into magnetic skyrmions on
the right side next to the geometrical constriction. Under the current pulses, the
inhomogeneous current distribution at the neck gives rise to an inhomogeneous
spin-orbit effective field, which causes the continuous expansion of the stripe
domains into circular magnetic skyrmions. The electrical detection of sub-100 nm
magnetic skyrmions has been demonstrated via the anomalous Hall resistance
measurement at room temperature in a Hall bar structure sample made of multilayer
films (Ta(5 nm)|Pt(10 nm)|[Co(0.8 nm)|Ir(1 nm)|Pt(1 nm)]20|Pt(3 nm)) [48].
Before the current pulses on the nano-structured sample with a track width of
400 nm (Fig. 10c), a larger anomalous Hall resistance (red symbols) is observed.
This larger resistance state corresponds to the magnetically saturated state, which
is consistent with the magnetic force microscopy measurement (red frame in
Fig. 10c). The current injection induces a single skyrmion formed in the area
of the Hall cross (green frame in Fig. 10c), and a subsequent decrease of the
Hall resistivity is observed (green symbols), corresponding to 254 n cm per
skyrmion.
32 Magnetic Memory and Logic 1569
Fig. 10 Skyrmions in magnetic multilayer heterostructures: the generation and detection via
electrical means and the high-speed motion. (a) The interfacial Dzyaloshinskii-Moriya interaction
(D12 ) in magnetic multilayers with larger spin-orbit coupling, resulting in a non-collinear chiral
spin texture of the magnetic moments. (Reproduced from [30]). (b) The electrical injection of
multiple skyrmions transferred from the magnetic domains via a confined geometrical constriction.
Top and bottom panels represent the polar magnetic optical Kerr images before and after the current
pulse. The sample is made of Ta/CoFeB/TaOx tri-layer. (Reproduced from [47]). (c) The electrical
detection of a single skyrmion via anomalous Hall measurement. (Reproduced from [48]). (d) The
high-speed motion of the skyrmions up to 120 m/s driven by spin-orbit torque of heavy metallic Pt
and Ta. (Reproduced from [49])
The high-speed motion of magnetic skyrmions at room temperature has also been
achieved using current-induced spin-transfer torque [49]. A skyrmion velocity up
to 120 m/s is observed on the [Pt(3 nm)/Co(0.9 nm)/Ta(4 nm)]15 sample under a
current density of 5 × 107 A/cm2 at room temperature characterized by magnetic
transmission soft X-ray microscopy (Fig. 10d). The current-driven skyrmion motion
is due to the Slonczewski-like torque arising from the spin Hall effect in Pt
and Ta, which is similar to the physical origin that drives high-speed Néel-type
domain wall motion in ferromagnetic/Pt bilayer structures [42, 43]. These important
progresses of the stable skyrmions at room temperature without magnetic field,
electrical generation, and detection of magnetic skyrmions, as well as the high-speed
motion, might pave the way for the future racetrack memory based on magnetic
skyrmions.
1570 W. Han
Antiferromagnetic Memory
Fig. 11 Antiferromagnetic memory based on the antiferromagnetic material CuMnAs. (a) The
spin configuration of two sub-lattice Mn atoms in the CuMnAs. The full CuMnAs crystal is
centrosymmetric around the interstitial position highlighted by the green ball. (b) Schematic of
the generation of spin current via spin-galvanic effect. The applied current (J) results in a net
in-plane spin polarization (thick red arrow). (c) The optical image and measurement geometry
of the antiferromagnet CuMnAs device. (d) Schematic for the X-ray magnetic linear dichroism
photoemission electron microscopy measurements. X-rays are incident at 16◦ to the sample
surface, with polarization vector in the film plane. (e) Difference between X-ray magnetic linear
dichroism photoemission electron microscopy images taken after applying alternate orthogonal
current pulse trains of 6.1 MA cm−2 . (f) The transverse resistance (R⊥ ) after applying alternating
current pulses along CuMnAs [100] and [010] directions at 273 K. The current density is
4 × 106 A cm−2 . A constant background is subtracted from transverse resistance. (g) Experimental
proof of the functionality of the antiferromagnetic memory in the presence of an external magnetic
field of 12 T. (Reproduced from [52, 54])
magnetic field. Consistent with the antiferromagnetic nature, even a large external
magnetic field of 12 T is not sufficient to overwrite the signal set by the current
pulses at zero magnetic field (Fig. 11g).
Besides the antiferromagnetic CuMnAs films, other non-centrosymmetric anti-
ferromagnetic Mn2 Au can also be switched by Neel spin-orbit torque, which
exhibits the potential to be used in future antiferromagnetic memories [55].
Furthermore, spin-Hall orbit torque from an adjacent heavy metallic Pt layer has
1572 W. Han
been used to switch the magnetic moments of antiferromagnetic NiO thin films
[56], which might expand the antiferromagnetic material candidates toward memory
applications.
Fig. 12 Emergence of 2D van der Waals magnets for future magnetic memory applications.
(a–c) Illustration of several typical 2D van der Waals magnets, CrI3 , Cr2 Ge2 Te6 , and Fe3 GeTe2 .
(Reproduced from [61–63]). (d) The Kerr rotation of the monolayer and bilayer CrI3 . In bilayer
CrI3 , the interlayer exchange coupling between two CrI3 layers is antiferromagnetic, illustrated
by the blue and red spins. (Reproduced from [61]). (e) The schematic of the bilayer CrI3 -based
magnetic tunnel junction. (f) The tunneling conductance as a function of the external magnetic
field that is perpendicular to the CrI3 plane. (Reproduced from [66])
Besides the extremely large magnetoresistance, the large area growth, electrical
manipulation via electrical field and spin-orbit torque, and read-out of the magneti-
zation in 2D van der Waals magnets have also been investigated intensively in the
last 2 years, i.e., see the recent review article [59]. These important progresses of
2D van der Waals magnets might pave an alternative route to achieve high-density
magnetic memories.
Magnetic Logic
Modern electronics rely on the use of CMOS technology for computing. For
the quick growth demand of emerging computing paradigms such as artificial
intelligence, new computing technologies are needed as a workaround to the von
Neumann bottleneck, decrease switching energy, and improve device interconnec-
tion and provide a complete logic and memory family. Nonvolatile logic-in-memory
architecture, where nonvolatile memory elements are distributed over a logic-circuit
plane, is expected to realize both ultra-low-power and reduced interconnection
1574 W. Han
delay. For the operation of complete logic devices (Table 1), a complete minimal
set is composed of a basic binary operator like logical AND or logical OR and
the unary operator NOT. Recent progresses of logic devices using nano-magnetic
elements and tunneling junctions have been made toward the logic memory in
a single device. This section will discuss the magnetic logic based on the nano-
magnetic dots, magnetic domain walls, and magnetic tunneling junctions as follows.
Nanomagnet Logic
is the logical AND of the input dot with the oscillating field as one input and the
elongated dot as the other input. In principle, magnetic solitons carry information
through the networks without loss and so should be able to mediate a logic switch
without dissipation at room temperature.
The magnetic quantum dot cellular automata arrays have been properly struc-
tured to perform the three-input majority gate NAND and NOR logic operations
[70]. The multiple magnetic quantum dots have single-domain state and couple to
each other through dipole-dipole interactions due to the stray fields close the outside
of the magnets. The dipole-dipole interaction gives rise to either ferromagnetically
ordered state (collinear along the axes) or antiferromagnetically ordered state (side
by side in parallel). For the configuration of a central nanomagnet surrounded by
four other nanomagnets, three of them can be used as inputs driven by additional
driver nanomagnets oriented in the x-direction, along the clock-field, and the last
one of them (to the right of the central magnet) is the output (Fig. 14a). After
applying a horizontal clock-field, switching inside the gate begins at the input
magnets and ends at the output magnet. After applying a right-oriented clock-field
of 500 Oe with 30 s rise and fall times, inputs (100), (101), (110), and (111) are
written by the driver magnets. On the other hand, with left-oriented clock-field,
inputs (000), (001), (010), and (011) are written by the driver magnets. The three-
input majority gate can be viewed as a programmable NAND or NOR gate in terms
of the central magnet (Fig. 14b, c).
1576 W. Han
Fig. 14 The majority logic gates using magnetic quantum cellular automata. (a) The functioning
majority gates characterized by magnetic force microscopy. The location of the magnets is drawn
superimposed on the magnetic force microscopy results. Top panel from A to D: Clock-field
applied horizontally to the right. Bottom panel from E to H: Clock-field applied horizontally to
the left. The black insets show alignment of magnetic dipoles, accounting for antiferromagnetic
and ferromagnetic coupling, and demonstrate majority logic gate functionality. (b) NAND gate
truth table. (c) NOR gate truth table. The logic state of the central nanomagnet is determined
by the logical majority vote of its three-input neighbors, of which the ferromagnetically coupled
neighbors vote directly and the antiferromagnetically coupled neighbor votes inversely to its
magnetic state. (Reproduced from [70])
A magnetic domain wall is the interface region between two oppositely aligned
magnetic domains in ferromagnetic materials. The domain wall is highly mobile
and can propagate in a nanowire by spin-polarized current torque. Recently, the
magnetic domains have been constructed into logic circuits consisting of the logic
elements, such as NOT, AND, signal fan-out, and signal cross-over [71]. All these
elements in the logic architecture can be built using planar magnetic nanowires
and domains (Fig. 15a). A single global magnetic field rotates in the plane of the
device and acts as both the clock and the power supply to operate with major logic
functions.
Figure 15b shows a typical integrated logic device consisting of one NOT gate,
one AND gate, two fan-out junctions, and one cross-over junction, which are made
of various domain structures. The magnetic optical Kerr signal at position I exhibits
32 Magnetic Memory and Logic 1577
Fig. 15 Magnetic domain wall logic. (a) Schematic drawing of the optimized magnetic domain
wall logic elements for the typical logic gates and junctions. (b) The magnetic domain wall network
containing one NOT gate, one AND gate, two fan-out junctions, and one cross-over junction. (c)
The magnetic optical Kerr effect measurements from the positions (I–IV shown in (b)) that describe
the operation of the magnetic logic within a counterclockwise rotating field. Traces II and III are
inferred from trace I and show the magnetization state of the AND gate’s input wires. (Reproduced
from [71])
a switching period of three field cycles, indicating the correction operation of the
NOT gate and sequential fan-out elements (Fig. 15c). For the AND gate, the logic
inputs are the magnetization states of the positions II and III, and the output is
the magnetization state at the position IV. The magnetic optical Kerr signal at the
position IV shows a high value, which corresponds to logic “1,” showing the correct
operation of the AND gate.
1578 W. Han
Magnetic tunnel junction logic devices have been constructed based on the tunneling
magnetoresistance effect in magnetic tunnel junctions [72]. For this purpose,
MgO-barrier-based magnetic tunnel junctions are used due to the large tunnel
magnetoresistance ratio at room temperature [11, 12]. The logic value of “1” uses
the low-resistance states when the magnetization of two magnetic layers is parallel
(Fig. 16a). On the other hand, the logic value of “0” uses the high-resistance states
when the magnetization of two magnetic layers is antiparallel. These two states can
be switchable using spin-transfer torque (Fig. 16b).
The ADD and CARRY logic-in-memory circuits using magnetic tunnel junctions
and metal oxide semiconductor transistors have been constructed (Fig. 16c). Since
the inputs are stored using the magnetic tunnel junctions, the logic operation is
nonvolatile, and the supply voltage can be cut off with maintaining stored data
in a standby state. This eliminates the static power dissipation of the logic circuit
with stored inputs. Furthermore, a single pinned magnetic tunnel junction-based
logic device can operate the six logic functions AND, OR, NAND, NOR, XOR, and
XNOR by introducing a current input line passing through MTJ as one of the input
[73]. The current input (“1” for current and “0” without current), the Joule heat
raises the temperature of the magnetic tunnel junction to the pinned layer blocking
temperature, and pinned layer magnetization direction can be reversed under the
magnetic field. The logic is read out using a Wheatstone bridge (Fig. 16d), and
the XOR and OR gate logic can be operated after gate SET steps (Fig. 16e). After
the XOR gate SET, the resistance state of logic-active magnetic tunnel junction
corresponds to the logic “1”; the XOR gate logic is operated. When inputs are 1,
1, and 1, the magnetization directions of the free layer and pinned layer become
parallel. On the other hand, the OR gate SET leads to the antiparallel states of the
pinned layer and free layer.
In this section, we discuss the spin current logic, which uses ferromagnetic
electrodes and spin current to carry the information, communicate, and perform
the logic. For the spin current, the angular momentum can be carried by electrons
conducting metals, semiconductors, and magnons/spin waves in ferromagnetic
materials. The following discusses the several recent important progresses of spin
current logic, including all spin logic, graphene spin logic, magnetoelectric spin-
orbit logic, and spin wave logic.
The all spin logic devices use nanomagnets as digital spin capacitors to store
information and spin currents in the spin channel/interconnect to communicate
32 Magnetic Memory and Logic 1579
Fig. 16 Magnetic logic based on magnetic tunnel junction devices. (a) Schematic for low-
resistance (“1”) and high-resistance (“0”) states that correspond to the parallel and antiparallel
configurations of the two magnetic layers across the MgO tunnel barrier, respectively. (b) Current-
induced magnetization switching in a typical magnetic tunnel junction. (c) Nonvolatile full
adder based on logic-in-memory architecture. The magnetic tunneling junctions (B and B ) are
merged into logic-circuit planes (surrounded by dotted lines). ((a–c) Reproduced from [72]). (d)
Schematics of Wheatstone bridge-type spin logic based on magnetic tunnel junction devices. (e)
The experimental results of the XOR and OR logic gate operations. ((d, e) Reproduced from [73])
Fig. 17 (continued)
W. Han
32 Magnetic Memory and Logic 1581
geometry spin valves [75]. The spin interconnect could be either a conducting
metal or a semiconductor [76–78]. The efficient spin injection into semiconductors
could be realized using tunneling spin injection via either tunnel or Schottky
barriers [78–80].
The nonlocal pure spin-transfer torque could be used to switch the magnetization
of the output nanomagnet, which has already been experimentally realized in the
metal spin valves [81]. This process could change the output magnetization to
be the same as the input magnetization and thus can also be viewed as a COPY
logic operation (Fig. 17b). Changing the polarity of the voltage bias to the input
transfers the COPY to a NOT logic operation. An example of the logic gate
operation with three nanomagnets as the inputs and one output is shown in Fig. 17c.
The superposition of the spin currents injected from the three inputs flowing in
the channel determines the final magnetization state of the output. Such gate can
function as an AND/OR gate. Flipping the magnetization direction of the middle
fixed input magnet toggles the functionality between OR and AND. With the applied
voltage bias onto all the three inputs, the transferred signals in the channel change
from COPY to NOT of the input, so that the gate A can work as NAND/NOR gate.
Importantly, the operation of gate logic A does not affect gate B that is in the idle
state.
For all the spin logic applications, a major challenge is to develop a suitable
spin transport channel with long spin lifetime and long spin propagation length.
Graphene is a single layer of carbon sheet, which has low intrinsic spin-orbit
coupling and has attracted a lot interest for this purpose. The electrical spin injection
and detection in graphene spin valves were first achieved at room temperature in
2007 [82], and the spin injection efficiency was enhanced to ∼30% with a large
nonlocal magnetoresistance of ∼130 ohms using MgO tunnel barriers in 2010 [83].
These room temperature spin-dependent physical properties, including long spin
diffusion length, large spin signal, and long spin lifetime, make graphene one of
the most promising material candidates for spin channel material in spin logic
applications [84, 85].
For graphene spin logic device [86], the building block is a magneto-logic gate
consisting of a graphene sheet contacted by five ferromagnetic electrodes (Fig. 18a),
Fig. 17 All spin logic. (a) Schematic for an all spin logic with built-in memory. The information
is stored in the bistable states of magnets. The corresponding inputs and outputs communicate with
each other via spin current flowing in the spin channel. (b) Schematic of input/output magnets for
a COPY process. The spin current torque switches the magnetization of the output magnet. (c)
The schematic for the bistable gates. For gate A, the state of the output is determined by the spin
currents injected into the channel by the three inputs (“Send” magnets). This gate can function as
a NAND/NOR gate or AND/OR gate. For gate B, it is in the idle state. (Reproduced from [74])
1582 W. Han
Fig. 18 Graphene spin logic. (a) Schematic drawing of graphene-based spin logic gate consisting
of a graphene sheet contacted by five ferromagnetic electrodes. Two electrodes (A and D) define
the input states, two electrodes (B and C) define the operation of the gate, and one electrode (M) is
utilized for read-out; Vdd drives the steady-state current, and IM (t) is the transient current response,
which gives the output; CM is a capacitor; IW is the writing current to manipulate the magnetization
direction of each ferromagnetic electrode; Ir (t) is the current used to perturb the magnetization of
the electrode M. (Reproduced from [84]). (b) Illustration of XOR logic device and measurement
geometry. A, B, and M are ferromagnetic electrodes (Co/MgO). R is a nonmagnetic electrode
(Ti/Au) used as ground point. Iout and Vout are the measured current and voltage, respectively.
Rsen is a variable resistor, and Voffs is an AC voltage source. (c) Experimental demonstration
of XOR operation: Iout as a function of in-plane magnetic field. Black (red) curve indicates the
magnetic field (H) sweeps upward (downward). Vertical arrows indicate the magnetization states
of electrodes A and B. Top left inset: truth table of XOR logic operation. ((b, c) Reproduced
from [87])
working as the inputs (A and D), the gates (B and C), and the output (M). These
magnetic electrodes consist of MgO/Py as the tunneling spin injection source and
two nanomagnets of CoFe that can switch the magnetization of Py via spin-transfer
torque. The read-out from M is highly dependent on the magnetization states of B
and C, which can extract the spin current that is injected from A and D and diffuses
to M. For example, if B and C electrodes are under the state “0,” the majority gate
logic of the inputs from A and D will be OR gate. Different gate logic operations
can be achieved by switching the magnetization of the Py layer via spin-transfer
torque from CoFe. Experimentally, XOR logic application has been demonstrated
on a graphene spin valve at room temperature [87]. Three ferromagnetic tunneling
contacts and one nonmagnetic Ti/Au contact were fabricated on the graphene
(Fig. 18b). The output voltage Vout (AC voltage) was measured using standard low-
frequency lock-in techniques, and output current Iout (=Vout /Rsen , Rsen is a sensing
resistor) was determined using a current detection. The experimental demonstration
of the XOR logic operation on the graphene spin valve is shown in Fig. 18c. During
32 Magnetic Memory and Logic 1583
the sweeping of the magnetic field, the magnetization of the two input electrodes
A and B changes, while the magnetization direction of the M electrode is kept
downward. The outcoming current is a logic operation output of the two information
of “0” and “1,” as defined by the inputs of A and B.
In the all spin logic devices, a large current density is usually required since the
magnetization switching requires the enough spin-transfer torque. The inefficiency
of switching a magnet with spin currents can be an intrinsic limitation. In contrast,
the number of electrons required to form an electrostatic energy barrier of 1 eV is
low, allowing for low-energy magnetization reversal.
Recently, a new spin logic, namely, magnetoelectric spin-orbit logic, has been
proposed, which is expected to compete with current complementary metal-oxide-
semiconductor technology in terms of switching energy and logic density [88].
In such a spin logic device, the input charge information is first converted to
magnetism/spin information via magnetoelectric effect [89], and then the spin infor-
mation is transformed to a charge output via spin-to-charge conversion (Fig. 19a),
such as inverse spin Hall and Rashba-Edelstein effects [29, 30, 90]. The proposed
interconnect wire transfers the charge output of the left magnetoelectric spin-orbit
logic to the current that can be used to switch the input of the next one (Fig. 19b).
The operation mechanism via the interconnect is as follows: The first step is the
injection of spin-polarized electrons from a ferromagnetic electrode into the material
with large spin-orbit coupling (Fig. 19c), which converts the spin current into a
charge current (Ic (output)) that flows in the interconnect. Then the second step that
is the charge current/voltage switches the magnetization of the ferromagnet layer
that is coupled to the magnetoelectric layer via exchange coupling and exchange
bias (Fig. 19d). The magnetization switching in the right magnetoelectric spin-orbit
logic results in the change of the Ic (out) of the right magnetoelectric spin-orbit
logic. The charge current in the interconnect also alleviates the spin signal decay in
the spin interconnects in all spin logic devices [74]. The one-stage magnetoelectric
spin-orbit logic with three input bits and one output bit is shown in Fig. 19e. The
state of the output is determined by the interconnects with three inputs, similar to
all spin logic gate (Fig. 17c) [74].
Compared to complementary metal-oxide-semiconductor technology, the mag-
netic spin-orbit logic device was reported to have superior switching energy (by
a factor of 10 to 30), lower switching voltage (by a factor of 5), and enhanced
logic density (by a factor of 5) [91]. The progress of the magnetic spin-orbit
logic gates requires further advances in the fields of the magnetoelectric and
spin-orbit effects, including the magnetoelectric switching stability, writing time,
spin-to-charge conversion efficiency, spin state reading, the interconnects and the
complexity, etc. [91].
1584 W. Han
Fig. 19 Magnetoelectric spin-orbit logic. (a) Transduction of state variables for a castable charge-
input and charge-output logic device via magnetoelectric and spin-orbit effects. (b) Schematic for
magnetoelectric spin-orbit logic interconnect with cascaded logic gates. Arrows on the ferromagnet
(red color) show the directions of the input and output currents of the device. (c) Illustration for
the spin injection from a ferromagnetic electrode and spin to charge conversion in a material with
large spin-orbit coupling. (d) Illustration for magnetoelectric effect that couples the charge voltage
with the magnetization of the FM layer. m is the FM magnetization, and HEB and HEC are the
exchange bias and the exchange coupling from the magnetoelectric material to the ferromagnetic
layer, respectively. (e) Schematic for one-stage magnetoelectric spin-orbit logic for majority gates.
(Reproduced from [88])
Besides the electrons that mediated spin current, spin wave, the collective excita-
tions of the magnetization perturbations in ferromagnetic materials (Fig. 20a), can
also carry spin current during the spin wave propagation. One advantage of spin
wave logic is the possibility of Joule-heat-free spin information transfer over long
distance [92].
The spin waves can be excited in ferromagnetic materials by many means. One
common way is utilizing the inductive microwave technique via an alternating
Oersted field induced around the microwave antennas. For the spin wave logic,
32 Magnetic Memory and Logic 1585
Fig. 20 Ferromagnetic spin wave logic. (a) Schematic for spin wave in a ferromagnet. (b) The
long-distance propagation of spin wave in a ferromagnetic insulator yttrium-iron-garnet. The spin
wave is excited by the microwave pulse and detected via inverse spin Hall effect of the Pt strip that
is 3 mm away from the input antenna. (Reproduced from [93]). (c) Conceptual design of spin wave
logic gates based on a Mach-Zehnder-type spin wave interferometer. (Reproduced from [94]). (d)
All spin wave chip proposed for XOR logic operation. The spin wave densities sent to the transistor
sources S1 and S2 are controlled by the input magnon signals I1 and I2 applied to the gates G1 and
G2 . (Reproduced from [95])
low Gilbert damping materials are favored, such as ferrimagnetic insulator yttrium-
iron-garnet (∼ 10−5 at room temperature). For example, it has been shown that
the spin waves can propagate over 3 mm at room temperature [93]. The spin
waves are excited by a microwave antenna and detected by charge voltage signal
on the Pt electrode via inverse spin Hall effect (Fig. 20b). Mach-Zehnder spin
wave interferometer equipped with current-controlled phase shifters has been used
to construct logic gates (Fig. 20c) [94]. The currents applied to the two inputs
control the phases of the two spin waves from sources. The logic output is defined
by the interference of microwave currents induced by the spin waves; a small
amplitude level due to the destructive interference corresponds to logic “0,” and
a high amplitude level due to the constructive interference defines logic “1.” The
change in the magnitude of the output pulsed signal corresponds to the XNOR logic
functionality. The drawback of the Mach-Zehnder interferometer logic gates is that
it is impossible to combine two logic gates without additional magnon-to-voltage
converters. To build all spin wave logic, the control of the spin wave via another
spin wave current is necessary. Recently, it has been demonstrated that such control
is possible owing to nonlinear magnon-magnon scattering [95]. An XOR gate could
be built in the form of a spin wave interferometer with two magnon transistors
embedded into its arms without any external antennas (Fig. 20d).
1586 W. Han
Fig. 21 Antiferromagnetic
spin wave logic. (a)
Schematic for the spin wave
modes in an antiferromagnet.
The red and blue arrows
represent the two sub-lattice
spins in an antiferromagnet
unit cell. (Reproduced from
[96]). (b) The universal logic
gate using antiferromagnetic
spin waves with the fixed 90◦
spin wave injection. The
instructions (I, J, and K),
inputs (A and B), and outputs
(U and L) are made of the
synthetic antiferromagnetic
domain racetracks. The blue
and red regimes represent the
opposite magnetic domains.
(Reproduced from [97])
Compared to single spin wave mode in ferromagnetic materials, the spin wave
dynamics of a collinear easy-axis antiferromagnet admits two degenerate modes
with opposite circular polarization (Fig. 21a) [98]. Similar to optical light, these
two modes can be recombined into an equivalently orthogonal but linearly polarized
basis. These two modes, distinguished by their opposite polarization, can give
rise to a novel degree of freedom to encode and process information. Recently,
a universal logic has been proposed for logic operations using the polarized spin
wave and the antiferromagnetic domain walls [97]. The physical mechanism relies
on the magnetic gating effect that can modulate the spin wave dispersions in an
antiferromagnet. The universal logic gate (Fig. 21b) consists of three instruction
tracks, two inputs, and one output that are made of ferromagnetic domain wall
racetracks and antiferromagnetic spin wave conducting channel. The outputs “U”
and “L” are synthetic antiferromagnetic coupled domain racetracks, which have
been experimentally achieved already [40]. The universal magnetic logic gate can
realize all unary and binary logic gates with the fixed 90◦ spin wave polarization
injection, which can be pre-processed into the desired polarization degrees of 32◦ ,
77◦ , and 120◦ for the performing all types of majority logic operations [97].
In summary, there have been enormous progresses using magnetic materials for
memory and logic applications in the last 30 years. The biggest success toward
commercial product is the use of the giant magnetoresistance and tunneling magne-
32 Magnetic Memory and Logic 1587
toresistance as magnetic sensors in magnetic hard drive disks, which have increased
the storage density more than thousandfold. Recently, the delivery of spin-transfer
torque magnetic random-access memory into the market could be considered as
the second success of spintronic devices that use magnetic tunnel junctions as the
memory cells. Looking forward in the next decades, the dream toward higher-
performance magnetic memories will continue to simulate the discovery of new
physical mechanisms and materials. The domain wall racetrack memory, skyrmion
racetrack memory, antiferromagnetic memory, and 2D van der Waals magnets
memory might hold the promise for the future magnetic memory applications.
Regarding magnetic logic applications, many logic-built-in-memory devices
have been proposed and realized for logic operations in research laboratories.
Although the success of magnetic and spin logic devices as commercial products
might need much more time and effort compared to the magnetic hard drives, the
quick growth demand of new computing technologies will make the research on
magnetic and spin current logic definitely a quite crowded and highly competitive
field. Looking forward, magnetic and spin logic devices will be quickly developed
and might be used in our daily lives in the near future.
Acknowledgments The author acknowledges the funding support of the National Basic Research
Programs of China (Grants 2015CB921104 and 2019YFA0308401), National Natural Science
Foundation of China (NSFC Grants 11574006 and 11974025), and Strategic Priority Research
Program of the Chinese Academy of Sciences (No. XDB28000000).
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Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1594
Magnetic Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1594
Magnetic Susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1595
Magnetic Susceptibility of Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1598
Pascal’s Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1598
Magnetic Field Effects in Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1599
Magnetoelectrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1601
Electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1602
Magnetic Forces in a Uniform Magnetic Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1605
Magnetic Forces in a Non-uniform Magnetic Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1610
Magnetic Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1614
Magnetic Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1616
High-Gradient Magnetic Separation (HGMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1618
Magnetic Carriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1618
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1621
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1623
Abstract
P. Dunne ()
Institut de Physique et de Chimie des Matériaux de Stasbourg, Strasbourg, France
e-mail: [email protected]
Introduction
The ability of magnets and magnetic fields to exert force and induce motion is
probably their most striking property. The forces may be exerted on currents of
moving electric charges or on preexisting or induced magnetic moments. Much of
this handbook is concerned with electronic currents in solid conductors. Here the
focus is on currents associated with chemical ions or free radicals. These are often
in solution, which leads us into the areas of electrochemistry and hydrodynamics.
In the early nineteenth century, both types of currents were being explored,
and the contributions of Michael Faraday were preeminent. He visualized the
magnetic field by lines of force and demonstrated the principle of the electric motor
with a current-carrying conductor. He also pioneered electrochemistry and in 1832
launched the field of magnetohydrodynamics (MHD) when he tried to measure the
potential difference across the Thames induced by its motion through the Earth’s
magnetic field. The attempt failed because his equipment was not sensitive enough;
the river was not sufficiently conductive, and the river bed short-circuited the
signal [1].
Our other topic, magnetic separation, has a longer history, dating from the first
patent in 1792, by William Fullerton, for the separation of iron minerals by means of
a magnet [2]. Between then and the start of the twentieth century, there was a gradual
flowering of the technique, with more than 300 patents awarded in the United States
by the end of the nineteenth century [2], for a huge variety of different types of
industrial magnetic separators. We first recall, how magnetic fields are produced
and how materials, especially liquids, respond to them.
Magnetic Fields
Magnetic fields have two sources; the first is the motion of electric charges, as
described by Ampère’s law
∇ × B = μj (1)
where μ is material permeability and j is the current density, which leads to the
generation of a magnetic field B. The second source of magnetic fields is the
intrinsic magnetism of elementary particles, especially the electron in condensed
matter. The magnetic moment of an electron is
where gS is the spin g-factor ≈2, μB is the Bohr magneton, and S is the spin angular
momentum of the electron. For an atom, the spin angular momentum S is the sum of
33 Magnetochemistry and Magnetic Separation 1595
all individual spin momenta; likewise the atomic orbital angular momentum L is the
sum of individual orbital momenta, and the total angular momentum is J = L + S.
Then the magnitude of the dipole moment of a free atom in space is
matom = gJ μB J (J + 1) (3)
J (J + 1) − L(L + 1) + S(S + 1)
gJ ≈ 1 + (4)
2J (J + 1)
The contribution of the spin and orbital angular momenta of the atom combine to
give the magnetization M, which is measured in some direction (conventionally the
z-direction). M is then defined as
N
M= mz (6)
V
where N is the number of atomic magnetic moments m of the sample and V is the
sample volume. Finally in the Sommerfeld convention, a third field, the auxiliary
field H , is related to the other two by
B = μ0 (H + M) (7)
where μ0 is the permeability of free space and M is the volume magnetization. In the
absence of an external magnetic medium, the H -field lines are identical to B-field
lines outside a magnet (the stray field) and only differ by a factor μ0 , (B = μ0 H );
but inside they point in a different direction. B is solenoidal (∇ · B = 0), meaning
that its field lines always form closed loops, or extend to infinity, whereas H is
conservative and irrotational (∇ × H = 0), provided no electric currents j are
present. Only in this case can H be represented by sources and sinks similar to the
electric field E (Fig. 1).
Magnetic Susceptibility
Fig. 1 H , M, and B fields for a uniformly magnetized material in the absence of an external
magnetic field. (Adapted from [3])
nets and ferrimagnets, the intensity of the field may be increased a millionfold.
Paramagnetic materials commonly contain transition metal elements or lanthanides.
Diamagnetism, however, is a universal property of matter. All condensed matter has
an underlying diamagnetism which may be masked if paramagnetism is also present.
For most substances, except ferromagnets, their initial response (i.e., magnetization
M) is proportional to the externally applied magnetic field H
χ = M/H (8)
C
χ= (9)
T
33 Magnetochemistry and Magnetic Separation 1597
where C = μ0 μ2B ng 2 J (J + 1) /3kB is the Curie constant, n is the number
density of magnetic moments, g is the Landé g-factor, μB is the Bohr magneton,
and kB is Boltzmann’s constant. Two frequently used quantities are the mass
susceptibility χmass = χ /ρ with units m3 kg−1 where ρ is density; and the molar
susceptibility χmol = MW χmass = MW χ /ρ with units m3 mol−1 where MW is
molecular density. Rewriting the molar Curie law susceptibility for non-interacting
spin-only moments, it becomes [3] (see Table 1)
μ0 NA g 2 μ2B S(S + 1)
χm = (10)
3kB T
where NA is Avogadro’s number, g is the g-factor (=2 for a spin only moment),
S is the ion spin angular momentum, and kB is Boltzmann’s constant. This can be
simplified to
Table 2 Molar susceptibility and susceptibility of one molar solution of selected paramagnetic
4f ions in water. (Adapted from [12])
exp exp exp
4fn ion S L J gJ p0 peff peff χm × χsoln
10−9 ( m3 mol−1 ) 10−6 (1 mol)
1 Ce3+ 1/2 3 5/2 6/7 2.14 2.54 2.5 32.9 23.9
2 Pr3+ 1 5 4 4/5 3.2 3.58 3.5 64.6 55.5
3 Nd3+ 3/2 6 9/2 8/11 3.27 3.52 3.4 60.9 51.9
4 Pm3+ 2 6 4 3/5 2.4 2.68 - - -
5 Sm3+ 5/2 5 5/2 2/7 0.71 0.85 1.7 15.2 6.2
6 Eu3+ 3 3 0 0 0 0 3.4 60.9 51.9
7 Gd3+ 7/2 0 7/2 2 7 7.94 8.9 417.6 408.5
8 Tb3+ 3 3 6 3/2 9 9.72 9.8 506.3 497.3
9 Dy3+ 5/2 5 15/2 4/3 10 10.65 10.6 592.3 583.3
10 Ho3+ 2 6 8 5/4 10 10.61 10.4 570.2 561.1
11 Er3+ 3/2 6 15/2 6/5 9 9.58 9.5 475.8 466.7
12 Tm3+ 1 5 6 7/6 7 7.56 7.6 304.5 295.4
13 Yb3+ 1/2 3 7/2 8/7 4 4.53 4.5 106.8 97.7
χ = χ water + χm c (12)
Pascal’s Constants
Pascal was able to conclude from a vast number of measurements that the
diamagnetic susceptibility of a molecule, χD , could be determined by summing the
susceptibility of every constituent atom, χDi , and bond, λi [13, 14]:
χD = ni χDi + λi (13)
i i
This is only an empirical law, yet its success at estimating χD remains unchallenged,
allowing the determination of susceptibilities where no other method is available,
such as in triarylmethyl radicals which have significant diamagnetic susceptibilities,
but without a direct method to determine them [13]. These constants are tabulated
in [14].
Since the 1970s, weak magnetic fields have been known to strongly influence certain
chemical reactions [15], which was surprising because the energies involved are
<0.1 meV. The reactions in question involve the simultaneous production of two
intermediate, short-lived radicals. Each radical has at least one unpaired spin, but
because they are produced simultaneously, spin multiplicity is conserved, and their
spin states are correlated in an antiparallel S = 0 singlet state ‘S’, or parallel S = 1
triplet state ‘T’. There are three ways to arrange the triplet state
1
|T0 = | √ (↑ + ↓)
2
|T+1 = |↑↑
|T−1 = |↓↓ (14)
1
|S = | √ (↑ − ↓) (15)
2
The unpaired electrons tend to be delocalized [16, 17] and interact with many
nuclei in the radicals. Nuclei with odd numbers of protons, neutrons, or both are
weakly paramagnetic, having magnetic moments which generate local hyperfine
magnetic fields. Most isotopes with paramagnetic nuclei are rare, but two, 1H and
14N, have almost 100% natural abundance and are common in organic radicals [16].
For radical pairs which have these hyperfine fields, their spin states are not static,
rather a fraction of radicals oscillate between singlet and triplet states at frequencies
dependent on the hyperfine field strengths found in the radical and can be of order
1 mT for 14N containing radicals [16]. This singlet-triplet (S-T) interconversion
can be driven not only by these nuclear spin states but additionally by an external
1600 P. Dunne
magnetic field. Due to the Zeeman interaction, the electron spin precesses at the
Larmor frequency around the external field, which is about 1.4 MHz in the Earth’s
magnetic field (50 μT) [16].
Figure 2b is a schematic of the simplest radical pair scheme. Radicals are
commonly formed by photochemical excitation, where the absorption of a photon
results in the transfer of an electron from a molecule A to molecule B in close
proximity, or to different parts of a single molecule. After this, an applied magnetic
field μ0 H can regulate the interconversion between S and T states, which then
decay to their singlet or triplet products. The simplest examples being a return to
the neutral AB reactants for the singlet state and different product, C, for the triplet
state. If the external magnetic field favors interconversion of S to T, then more C will
be produced, while if the field suppresses interconversion, less C will be produced,
and more radical pairs can recombine to AB.
a)
Electron
spins European Robin
Retina
B
Nuclear
spin
b)
– Singlet
N products
hO S ●+ ●–
[AB] [A B ]
Singlet AB
+ μ 0H
T
[A●+ B●–]
Triplets
T+ T–
Electron spin Triplet
N products
Nuclear spin T0 + C
Fig. 2 Schematic of radical pair production and how it is used to explain avian magnetoreception.
(Adapted from [18])
33 Magnetochemistry and Magnetic Separation 1601
Magnetoelectrochemistry
shown in Fig. 5 [40, 41]. These are the classical papers for the often surprising
science of magnetoelectrochemistry.
Electrochemistry
We first summarize some basic ideas in the absence of a magnetic field. In the
space of a few microns, electron kinetics, diffusion, and hydrodynamics combine
at the electrode-solution interface to determine much of what is important in
electrochemistry. The are two distinct interfacial regions, the diffusion layer and
the double layer [42]. The former is a zone 1–100 μm thick, where ion diffusion is
driven by a concentration gradient ∇c that is influenced by convection. The latter is
a layer a thousand times thinner where huge electrostatic fields control the electrode
kinetics in a region that is sensitive to surface tension and the structure of the local
charge distribution. The double layer is further divided into a compact charged layer
usually 0.5–10 nm thick coupled to a broader diffuse layer.
Even for simple one-electron transfer reactions, a number of steps are required
to oxidize or reduce an ion from solution at the electrode, requiring classical or
quantum mechanical descriptions [43,44,45,46] (see [47] for a rigorous description
of electron transfer including second-order effects). First, the ion must be driven
to the electrode surface by mass transport, which must be at a thermodynamically
favorable potential for the reaction to take place and have reasonably fast kinetics to
sustain it (Fig. 3). The charge transfer current is strongly dependent on the electrode
potential and the concentration of relevant species at the electrode surface, being
described by the Butler-Volmer equation when under kinetic control [42]
αc zFη αa nFη
j = j0 exp − − exp (16)
RT RT
ne
Red´ads
Desorption
Chemical
Adsosption reactions
Red´ Redsurf Redbulk
where αc and αc are the cathodic and anodic charge transfer coefficients, z is the
number of electrons involved in the reaction, F is Faraday’s constant, R is the gas
constant, η is the overpotential, and j0 is the exchange current density. In more
detail, η = E − Eq is the potential difference between the measured electrode
potential E and the thermodynamically determined potential of the reaction Eq ;
and the exchange current density j0 is the current when there is no net electrolysis
and the electrode is at equilibrium, i.e., ja + jc = 0.
Three processes govern the mass transport of ions, diffusion – movement of
a species due to a concentration gradient; migration, the movement of a charged
species in an electric field; and advection, stirring or other bulk hydrodynamic
transport of the medium, through density gradients or external forces. Confusingly,
convection is sometimes used as a synonym for advection, but convection is actually
defined as the collective motion of all particles in a fluid.
Mass transport can be described by the Nernst-Planck equation [42]
zi F
J i = −Di ∇ci − Di ci ∇φ + ci v (17)
RT
where J i is the flux of species i ( mol s−1 m−2 ) at a given position from the
surface, Di is the diffusion coefficient m2 s−1 , ∇ci is the concentration gradient,
zi and ci are the charge (dimensionless) and concentration (mol m−3 ) of species
i, ∇φ is the potential gradient, and v is the fluid velocity of a volume element in
solution. Migration is typically insignificant in electrode currents so long as an inert
supporting electrolyte is introduced to the solution, which can carry the migration
part of the current, without making any contribution to the reaction current, while
convection is the motion of a fluid under the action of a force. There are two
kinds of convection: the first is natural convection which arises from thermal and
density gradients and is common to all solutions. The second is forced convection
which is due to an external force, such as provided by mechanical stirring or
magnetohydrodynamic stirring. The velocity field in a fluid can be described by
the Navier-Stokes equation, where ρ is the fluid density
Divergence of stress
∂v
ρ + v ·
∇v = −∇p + μ∇ 2 v + f (18)
∂t
Convective Pressure Viscosity Other
Unsteady acceleration gradient body
acceleration forces
Two kinds of fluid flows most relevant to electrochemistry are laminar flow and
turbulent flow. In a laminar flow, the fluid velocity is smooth and steady and occurs
in separate layers or laminae. A flow is turbulent when the fluid motion is chaotic
and unsteady, with only an average net velocity in one direction. The most important
dimensionless numbers used in fluid dynamics are listed in Table 3 (Fig. 4).
1604 P. Dunne
Table 3 Characteristic dimensionless numbers used in fluid dynamics, where v is the fluid
velocity (m s−1 ), l is the characteristic length scale (m), e.g., pipe length, ν is the kinematic
viscosity (m2 s−1 ), D is the diffusion coefficient (m2 s−1 ), kd the convective mass transfer
coefficient (m2 s−1 ), and δ is the diffusion layer thickness (m). Note that convection is the total
collective motion of a fluid advection is fluid transport by bulk motion only
Number Formula Description
Reynolds number Re = vl/ν Measure of the ratio of inertial to
viscous forces. For small Re, flows
are laminar, and for large Re, flows
become turbulent
Schmidt number Sc = ν/D Ratio of momentum diffusivity (vis-
cosity) to mass diffusivity. Relates
δH and mass boundary layer
Peclet number Pe = lν/D(= Re.Sc) Ratio of advection of a physical
quantity of a fluid, e.g., mass or heat
transfer by flow to its rate of diffusion
Sherwood number Sh = kd l/D = 1/δ Ratio of convective mass transport to
diffusive mass transport
Hydrodynamic layer thickness δH = (ν/D)1/3 δ A characteristic length which con-
tains most of the fluid velocity gra-
dient between a bulk flow and fluid-
solid interface
Fig. 4 A three-electrode
electrochemical cell, I
- +
consisting of a working
electrode (WE), reference
electrode (RE), and counter
electrode (CE) Vcell
WE
RE CE
F = μ0 [∇ · (H + Hd )]H (19)
where H d is the demagnetizing field. However, the applied field H is uniform, and
as long as the demagnetizing field is negligible, there is no net force, which is true
for aqueous electrochemical systems, but not in ferrofluids (see section “Magnetic
Forces in a Non-uniform Magnetic Field”). There is also a weak stress in elec-
trolytes, known as the Maxwell stress, which in tensor form for an applied magnetic
field B is [1]
1 1 2
σij = Bi Bj − B δij (20)
μ0 2μ0
where 0 is the permittivity of free space and δij is Kronecker’s delta, or simply σ =
MB where the units are N m−2 [49]. This is known to deform volumes containing
paramagnetic ions, such as paramagnetic tubes [50].
Lorentz Force
In aqueous solutions, moving charges interact with a magnetic field through the
Lorentz force
FL = j × B (21)
Acting as a driving force, the Lorentz force induces convection in a bulk solution
[40, 41]. An example is the Aogaki cell (Fig. 5) which consists of two parallel plate
electrodes embedded in the wall of a tube, with a perpendicularly applied magnetic
field which induces a flow in the tube. The limiting current densities are described
by
γ
jl = j0 + αB β c0 (22)
Z X a
Y b
f d
e
B
f
i
f e
d
c
x
0 x1 x2 l
Rm = ul/λ (23)
and in Earth’s liquid outer core (Rm ≈ 103 ), and whose motion is sufficient to
sustain a magnetic field against dissipation [1]. In aqueous solutions, which are poor
conductors, Rm is small (≤1) and the magnetic field induced by motion of the liquid
is negligible compared to the imposed field. The generation of a magnetic field due
to the motion of a conductive liquid has only been achieved in large experiments
involving liquid sodium or mercury [54]. The second commonly used dimensionless
number is called the interaction parameter
which squared (Ha2 ) represents the ratio of Lorentz forces to shear forces. Previ-
ously MHD effects in solution were observed to have a dominant role and were
the focus of a number of reviews, which mostly concentrate on either deposition or
dissolution of metals [55, 56, 57, 58]. When the magnetic field is parallel to the
electrode surface, i.e., nominally perpendicular to the current, the Lorentz force
acts parallel to the electrode surface, generating a fluid flow orthogonal to both the
current and magnetic field (Fig. 6a). If the magnetic field is perpendicular to the
surface (Fig. 6b), and parallel to the current, there can still be a Lorentz force due
to non-collinear current lines at the edge. This can generate vortices at an electrode
unless care is taken to minimize edge effects. A further development to this case is
when secondary micro-MHD vortices appear at an electrode (Fig. 6c). These arise
from protuberances on the electrode surface, causing symmetric and asymmetric
concentration fluctuations close to the electrode surface [53]. Asymmetric fluctua-
tions are triggered in the double layer, and determine the reaction rate, yielding 2D
nuclei, and symmetric fluctuations are triggered in the diffusion layer, determining
the reaction rate of each crystal/grain and forming 3D nuclei [59].
Deposition
During metal electrodeposition, applied magnetic fields have been shown to influ-
ence the surface morphology [39, 55, 56, 61, 62, 63, 57, 64, 65, 66, 67, 68, 69, 70,
71, 72, 73, 74, 75, 76, 77, 78], crystal structure and orientation [79, 64, 80, 81, 82, 83],
deposition rate [84,85,86,87,88,89,90,65,91,92,66,67,69,73,93], alloy composition
(NiCu [72], CoNi [94, 95], NiRe [96]), magnetic properties [97, 64, 72], surface
adhesion [98], mechanical hardness [99], deposit crack density [100], and improved
corrosion resistance [101]. The surface morphology and crystal orientation depend
not only on the magnitude of the magnetic field but also its orientation, as set
out in Fig. 6. Due to the different local MHD flows, the surface of metal deposits
such as CoFe can be smoother with B parallel to the electrode surface, or rougher
for B perpendicular to the electrode [102, 78], or also with compounds like
1608 P. Dunne
Fig. 6 Hydrodynamic flow at an electrode in a uniform magnetic field. (a) Field applied parallel
to the electrode surface. The primary MHD flow is parallel to the surface. (b, c) Field applied
perpendicular to the electrode surface. In (b) the primary MHD flow is a vortex around the rim but
in (c) secondary micro-MHD vortices arise around protuberances on the surface. (From [60])
Fig. 7 SEM images of Cu2 O crystals grown under magnetic fields A1–A3: 0 T; B1–B3: 6 T;
C1–C3: 12 T. (From [111])
Fig. 8 Zinc electrodeposits grown from 0.1 M ZnSO4 at 10 V in a flat horizontal cell in the
presence of a 0.35 T magnetic field applied (a) vertically upward and (b) vertically downward.
(From [68])
magnetic fields. When the Lorentz and buoyancy forces sum, the mechanical effect
of the Lorentz force, whether it is to sweep the surface or apply torque to the bubbles,
will tend to dislodge the bubbles sooner than would otherwise be the case [121].
Whereas the magnetic field can have a stabilizing effect on the bubbles when the
Lorentz force opposes buoyancy. The average bubble size should be reduced by
the field in the former case and increased in the latter. This is indeed observed
during the deposition of CoFe or Cu [122,123,124,125] and has also been observed
during the direct electrolysis of water [126,127,128,129,130]. This effect is already
1610 P. Dunne
Corrosion
Previously mentioned was the fact that the very first magnetic field effects were
observed for the corrosion of iron. Until relatively recently it was assumed that only
ferromagnetic or paramagnetic electrodes exhibited a change in corrosion activity
under applied magnetic fields [136, 137, 138, 139, 140]. One figure of merit for cor-
rosion activity, the rest potential, is the potential difference between the immersed
surface of interest and a reference electrode. A cathodic shift of the rest potential
means an increase in corrosion, while an anodic shift means the reverse, and it is
only in the last decade that it was recognized that rest potential shift during corrosion
is due to micro-MHD effects acting on local currents [35, 36, 141, 37, 142, 143].
Interestingly, micro-MHD theory was originally developed to account for copper
corrosion patterns and behavior in uniform magnetic fields [53, 144, 145, 146].
Nevertheless, the effect can be magnified for ferromagnetic electrodes such as
Fe [147, 148, 149, 150] where the dissolved species (i.e., iron ions) remain close
to the electrode, displacing H + , thus inducing a cathodic shift of the rest potential
and a suppression of the corrosion current that can be enhanced even further by
magnetic field gradients (see the section below). Typical rest potential shifts are on
the order of −100 mV/T [37].
F = μ0 (M · ∇)H (26)
33 Magnetochemistry and Magnetic Separation 1611
It must be noted that the Kelvin force is only valid for linear media where the
susceptibility is linear in density, χ = αρ, where α is a proportionality constant
[151], and where we have assumed ∇ × M = 0. This is not true if we cannot
neglect the demagnetizing field H d = Nχsoln H , which is the case in ferrofluids of
order 10−1 times the applied field, in contrast to solutions used in electrochemistry
with much lower susceptibilities and demagnetizing fields of order 10−4 to 10−5 .
The correct description of the force in the absence of currents is then the Helmholtz
force rather than the Kelvin force [152, p. 127]
μ0 ∂χ μ0 2
F = ∇ H ρ
2
− H ∇χ (28)
2 ∂ρ T ,P 2
μ0 g 2 μB S(S + 1)B 2
E= = 7 · 10−7 eV
2kB T
1612 P. Dunne
which is considerably less than the thermal energy driving diffusion (kB T ∼
1/40 eV). Unlike the Lorentz force, the field gradient force is normally conserved,
meaning it cannot generate convection. However, it is not conserved if (i) there is a
non-uniform distribution of paramagnetic species and (ii) the concentration gradient
and field gradient are non-collinear allowing convection to develop [174,175]. These
two criteria can be summed up by taking the curl of the magnetic field gradient force,
which must be nonzero if it is to induce convection:
∇ × F ∇B = (1/2μ0 ) ∇c × ∇B 2 (29)
d = 10−2 m,ω = 102 rad s−1 , Δρ = 10 kg m−3 , η = 10−3 N s m−2 , v = 10−1 m s−1 , B = 1 T,
χm = 10−8 m3 mol−1 , ∇B = 10 T m−1 , j = 103 A m−2 , and σ = 102 Ω −1 m−1
Fig. 10 Normal deposits obtained from a Cu 2+ bath and inverse deposits obtained from a
Zn 2+ /Dy 3+ bath, using parallel (top) or alternating (bottom) hexagonal magnet arrays, compared
with the contours of B 2 produced by the underlying arrays. (From [197])
and buoyancy forces [195]. The second interpretation is that of a fluid flow driven
by the vorticity of the Kelvin force acting on a paramagnetic species in regions of
high magnetic fields. Both models capture the essence of the phenomena and are
equivalent interpretations [198, 197].
Even in the absence of a current, paramagnetic ions such as Cr 3+ , Mn 2+ ,
Co 2+ , Ni 2+ , and Cu 2+ can move along magnetic field gradient contours in silica
gels [199]. Using Mach-Zehnder interferometry, this concentration change can also
be measured directly for Mn 2+ , Dy 3+ , Gd 3+ , or Er 3+ in solutions [200, 201, 202].
Placing a magnet close to a solution containing Mn 2+ (Fig. 11), there is an
enrichment of Mn close to the magnet, which then decays after the removal of the
magnet, clearly showing the existence of a magnetophoresis effect on the solvated
ions. This implies that the ions are not acting independently but respond coherently
to the magnetic field.
Here we focus on the effects of magnetic fields on water itself. Since the 1950s, there
have been a profusion of permanent magnet devices on the market claiming to have
an effect on the formation of limescale from hard of water [203]. Claimed benefits
include being able to remove old scale and prevent new scale from forming in water
pipes or water boilers if the water passed through a magnetic field created by the
permanent magnet device. Later reports, such as by Kronenberg [204], reported
a change in the morphology of crystals grown from the mineral content in water
33 Magnetochemistry and Magnetic Separation 1615
a 1200 s b 1206 s
0 0 15
10 10
5 5
z (mm)
z (mm)
5 0 5 0
−5 −5
−10 −10
10 −15 10
0 5 10
−15
0 5 10
x (mm)
x (mm)
c 1206 s
x 10
−4
8
2
7
6
4
z (mm)
4
6
3
2
8
1
0
2 4 6 8
x (mm)
Fig. 11 (a) Enrichment of Mn 2+ in a magnetic gradient field 1200 s after the magnet was applied
on top of the cell. (b) and (c) show the concentration contour plot and the velocity vector plot
associated with the downward flow after the magnet was removed. The concentration changes in
(a) and (b) are in mM. (From [200])
which could be changed from dendrites into disk-shaped crystals with treatment of
the water, and other reported a change in the properties of calcite and aragonite in
this scale. Some of the conflicting theoretical and experimental reports include both
a decrease [205,206] and increase of surface tension [207] after magnetic treatment,
and a change in conductivity [208, 209], along with a time-dependent change of the
zeta potential and viscosity of calcium carbonate-containing water [210]. One of the
more puzzling aspects has been the report of a memory effect, with the change in
physical properties lasting for hours after the magnetic treatment [211,212,213,206,
214, 210]. The validity and reproducibility of many experimental results have been
strongly challenged [215, 216], not least because no physical mechanism could be
envisaged whereby fleeting exposure to a magnetic field gradient could influence the
nucleation of calcium carbonate from a saturated solution hours later. The situation
changed with the discovery that much of the calcium carbonate in equilibrium in
1616 P. Dunne
water was not in the form of isolated hydrated calcium cations and bicarbonate
anions but in shapeless nanometric hydrated prenucleation clusters [217, 218]. It
has been proposed that the field exposure facilitates singlet-triplet interchange of
proton dimers, which facilitates a long-term chemical modification of the clusters,
that influences subsequent carbonate nucleation [219]. The theory predicts the
design of the successful water treatment devices. Monte Carlo molecular dynamics
simulations have been contradictory in nature, showing magnetic fields to weaken
hydrogen bonds in water [220], while also suggesting the structure of water becomes
more stable with an increased number of hydrogen bonds in magnetic fields [221].
Thus, there is no clear consensus on what effects, if any, magnetic treatment of this
kind has on water.
Magnetic Separation
χ
F ∇B = B∇B (31)
μ0
A classic example is that of a magnetic conveyor belt, dragging metal waste over a
series of magnets (Fig. 12), so that the trajectory of falling ferromagnetic material is
disturbed by the attractive force.
The effectiveness of magnetic separation is governed by the competition between
the magnetic field gradient and gravitational forces, particle-particle interactions,
and when in a fluid: buoyancy forces and particle-fluid interactions [223, 222, 224,
225]. Although the earliest magnetic separation applications were devoted to ore and
waste separation, since the 1960s, the development of high-gradient magnetic sepa-
rators (HGMS) has led to applications in a wide variety of industries. In the 1970s
Tramp iron
Adjustable
nonmagnetic
splitter
33 Magnetochemistry and Magnetic Separation 1617
and 1980s, research was primarily focused on water treatment [226], petroleum
and ore processing [227, 228], and magnetic separation for discrimination of air
pollutants [229]. While in the last three decades, magnetic separation has become of
great interest to wastewater treatment [230]. Traditionally, industrial separation has
been the source of the majority of interest, but since the 1970s [231], there has been a
realization that magnetic fields and magnetic carriers can be used in the life sciences
too [232], especially for the separation of cells and proteins [231, 233]. Thus
the application domains of magnetic separation can be categorized into a number
of resource management and bio-healthcare subdivisions. Resource management
primarily consists of industrial waste treatment and ore refinement [222, 234],
whereas bio-healthcare is concerned with clinical applications: biological matter
separation [231,233] and industrial separation and purification of pharmacologically
active drugs and industrially relevant bacteria. Within the resource management
domain, a number of general classifications for separator types have emerged over
the years, but the most commonly used one refers to the intensity of the magnetic
field gradients (high or low intensity), and to the separating medium (dry, wet),
along with a few other classifications (Table 5).
Ore refinement was one of the earliest applications of magnetic separation and
now includes the beneficiation and separation of iron and manganese, ores, ilmenite,
some non-ferrous ores, mineral sands, and coal [222,234]. Coal beneficiation (sulfur
removal) is one of the most crucial new areas of magnetic separation [235,236,237],
as rapidly developing countries such as China increase the global demand for coal.
Coal plays a predominant role in Chinese energy generation, accounting in 2011 for
77% [238, 239] of their primary energy production.
Recycling is the other major field of magnetic separation, which includes the
separation of scrap metal and electronic circuit boards from landfills [240, 241,
242]; recycling ferrous materials from slag, i.e., by-products from metallurgical
processes [243,244]; waste incineration, such as municipal waste [245]; and, finally
in the nuclear industry, the removal of solids from fuel dissolved liquids and soil
decontamination [228, 246, 234].
One of the key developments in industrial magnetic separation was high- gradient
separation in the 1960s and 1970s [247]. A suspension of ferromagnetic or
paramagnetic material in liquid flowed through a fine soft ferromagnetic mesh or
steel wool in a conduit inside a large electromagnet, or superconducting magnet
(Fig. 13). The fine magnetic wires distort the local field, generating magnetic field
gradients of the order 105 T m−1 , and forces 1012 N m−3 , trapping the magnetic
particles so long as the external magnetic field is applied. This is followed by a
purge-clean cycle with the magnetic field off (Fig. 13b), or alternatively the filter
material can be replaced after heavy use.
HGMS is most effective for particles of diameter >10 nm [248], and to date, the
most successful industrial application of HGMS is the removal of magnetic impu-
rities from kaolin, or china clay, a naturally white aluminosilicate Al2 Si2 O5 (OH)4
mineral [228, 234]. Other popular applications include purification of wastewater
from factories [249,250], paper mills [251], and the removal of martensite stainless
steel particles from viscous liquids [252]. However, there are problems with HGMS
systems, the two most important being, first, an uncertainty in magnetic field
distributions, leading to difficulties in optimizing process conditions [250, 248],
and, secondly, reduced performance due to permanent aggregation of particles in
the filtration unit. The Fe2 O3 nanoparticles used for arsenic removal, for example,
can’t be removed from steel wires [253].
Magnetic Carriers
The success of HGMS and open-gradient separation has driven the development
of separation using magnetic carriers. Here the goal is to specifically adsorb the
material of interest onto magnetic nanoparticles (carriers) and then remove the
magnetic carriers via magnetophoresis [224]. This is shown in Fig. 14, where a
33 Magnetochemistry and Magnetic Separation 1619
a) Filtered stream b)
(F small)
Canister Canister
Steel Mesh
Fig. 13 Cross-section schematic of a high gradient magnetic separation (HGSM) system and fluid
flow pattern in a cyclic HGMS system during (a) the filtration and (b) washing sequences
suspension of coated iron oxide nanoparticles are strongly attracted to the fringing
field of two NdFeB permanent magnets. This type of separation has a greater
specificity and higher efficiency compared to similar centrifugation or filtration
methods [254]. It is faster and has a lower energy consumption [230], reduced
costs, and less contamination produced [255, 256], and for reusable nanoparticles
acting as catalysts, separation is carried out under controlled environments, avoiding
exposure of the catalysts to air [230]. However, magnetic forces scale with volume,
so larger magnetic nanoparticles are desirable for permanent capture [234, 225];
with magnetite particles, the minimum size for permanent capture was 40 nm for
uncoated and 70 nm for coated nanoparticles [249].
Wastewater Treatment
In terms of wastewater treatment, most of the research emphasis has been on
the removal of heavy metals and organic dyes from solution. Heavy metal waste
products are produced in a large number of industrial processes such as metal ore
mining and refinement, metal finishing, painting, printing, and pesticide and fertil-
izer manufacturing [258, 259, 260]. They are toxic, carcinogenic, and mutagenic,
even at relatively low concentration [260, 261], and are non-biodegradable and
tend to accumulate in living tissues [262]. So their separation and purification from
1620 P. Dunne
Fig. 14 Magnetic separation of oleic acid (OA)-Pluronic-coated iron oxide magnetic nanoparti-
cles. (From [257])
Biological Separation
The other domain where magnetic carriers are of interest is in biology and medicine.
This includes separation of proteins [273] and DNA [274], pre-concentration of
biomaterials for assays [275], and cell separation [231]. This involves surface func-
tionalization to bind or capture specific targets [276], as outlined in Fig. 15. There
are already some biotech commercial applications involving protein purification and
cell sorting [277], and magnetic separation has been recently used in the processing
of bacteria for biofuel production [278]. See Chap. 34, “Magnetism and Biology”
for further details.
Conclusions
Fig. 15 A generalized procedure for magnetic separation for biological assays including carrier preparation. (From [279])
P. Dunne
33 Magnetochemistry and Magnetic Separation 1623
a b Stable Emulsion
Field Coil
Bubble
Solids
backmixing
Grid
Flow Flow
Fig. 16 Sketch comparing standard fluidized solids with magnetically stabilized ones in a
fluidized bed reactor. (a) The condition of a normal fluidized reactor at the minimum fluidization
velocity, containing a large number of voids and non-collinear local fluid velocities. (b) Magneti-
cally stabilized emulsion expands homogeneously to accommodate a higher throughflow. (Adapted
from [280])
Acknowledgments The author wishes to thank J.M.D. Coey for helpful comments and critiques
of this work.
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Contents
Biomagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1634
Magnetic Navigation in Living Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1634
Magnetic Fields Produced by the Body . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1639
Iron in the Body . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1642
Magnetobiology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1643
Magnetic Nanoparticles for Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1644
Magnetic Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1646
Magnetic Fixation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1650
Magnetic Actuation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1652
Magnetic Heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1664
Effects of Magnetic Fields on Biological Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1665
Transcranial Magnetic Stimulation (TMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1667
Recommended Magnetic Field Exposure Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1667
Conclusions and Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1670
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1670
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1671
Abstract
There are many links between magnetism and biology. One way to classify
them is according to whether they are naturally occurring or whether they
concern the exploitation of magnetism in biology and medicine. Here we refer
to the former as “biomagnetism” and the latter as “magnetobiology.” Examples
of biomagnetism discussed here are magnetic navigation in animals, magnetic
signals generated by animals, and the presence of iron in the body. The field of
magnetobiology may be subdivided into imaging, fixation, actuation, heating, or
N. M. Dempsey ()
Institut Néel, CNRS & Université Grenoble Alpes, Grenoble, France
e-mail: [email protected]
Biomagnetism
The study of naturally occurring magnetic phenomena in humans and animals has
a checkered past. Mesmer’s claim to harness a biophysical force he termed “animal
magnetism” to heal the so-called nervous diseases was discredited by a Royal
Commission in 1784. Nevertheless, many practitioners of alternative medicine still
claim to exploit biomagnetic energy in the treatment of a range of conditions.
Here we discuss three fields of study of naturally occurring magnetic phenomena
which have a solid scientific basis and which benefit from recent and ongoing
developments in magnetic and structural characterization tools and protocols.
Magnetotactic Bacteria
Certain bacteria, referred to as magnetotactic bacteria [1, 2], move along the
geomagnetic field lines. This “magnetotaxis” was discovered when bacteria on
a microscope slide in Italy were observed to swim northward along the Earth’s
magnetic field lines [3]. Many types of magnetotactic bacteria have been found
throughout the world, in both fresh- and saltwater environments. They have been
shown to contain intracellular structures known as magnetosomes, which consist
of iron-containing crystals encapsulated in a membrane. The crystals, which are
synthesized by the bacteria, typically form intracellular chains (Fig. 1), though
clusters have also been observed. The vast majority of freshwater magnetotactic
bacteria contain nanocrystals of magnetite (Fe3 O4 ), while marine, estuarine, and
salt marsh species have been shown to contain the ferrimagnetic sulfospinel greigite
(Fe3 S4 ). The size of the crystals typically varies from 35 nm to 120 nm, which is
within the single-domain particle size range. Thus, magnetotactic bacteria naturally
produce permanently magnetized linear arrays of fully magnetized crystalites, and
it is the dipolar interaction that causes neighboring crystals in a chain to align
their moments along the chain axis, so as to minimize the magnetostatic energy
and maximize the magnetic moment of the organism. Coercivities of the order of
20–50 mT have been measured on cultured strains containing magnetite crystals.
The torque produced by the geomagnetic field on a magnetosome serves to align
the bacterial cell body parallel to the field, while movement along the field line is
produced by rotation of propeller-like helical flagella protruding from the bacteria.
The effect of the field is thus passive, and dead magnetotactic bacteria align with
the field but don’t move along it. The direction of motion of live bacteria is
switched when the direction of rotation of the flagella changes from clockwise
to counterclockwise, and vice versa. There is a predominance of north-seeking
Magnetite-Based Magnetoreception
In analogy to magnetotactic bacteria, the magnetite hypothesis assumes a special-
ized sensory neuron containing magnetite particles. Based on magnetite-containing
structures found in the beak of homing pigeons [10], a model of dipolar interactions
between neighboring superparamagnetic particles was suggested that could account
for how the direction of the geomagnetic field could transmit physiological signals
through interactions with mechanoreceptors in neighboring nerve cells or through
the opening of ion channels in these cells [11]. However, more recent studies suggest
that the magnetite-containing structures in the beak are not sensory neurons, but
macrophages, which are specialized cells involved in the detection and destruction
of bacteria and other harmful organisms [12]. Thus, despite the physical viability
of the mechanism, a structural candidate for a magnetite-based magnetoreceptor is
still missing.
Radical-Pair-Based Magnetoreception
The fact that avian magnetic navigation is light-sensitive led Schulten to propose a
chemical magnetoreception pathway based on the radical-pair mechanism, in which
a photo-induced chemical reaction occurring in a bird’s eye can be influenced by
the direction of the geomagnetic field [13]. Absorption of a photon by a molecule
and its subsequent (photo)reduction by an electron donor molecule nearby produces
a spin-correlated radical pair, with each radical carrying an unpaired electron
with a magnetic spin. Before conversion to a reaction product, the short-lived
radical pair oscillates between singlet and triplet spin states, because of hyperfine
interactions between nuclear spins in at least one of the radicals and the electron
spins. Application of an external magnetic field modulates these oscillations and
influences the reaction product (Fig. 2). The anisotropic shape of the molecules
leads to anisotropic hyperfine interactions, which in turn are the source of magnetic
anisotropy resulting in the reaction product being influenced by the direction of
an externally applied magnetic field. A proof-of-principle laboratory experiment on
an immobilized (frozen) synthetic radical-pair model has shown that radical-pair
recombination time can indeed be influenced by an applied static magnetic field as
weak as the geomagnetic field and that the magnetic field effects are orientation-
sensitive [14]. What is more, the influence of a static field can be modified by the
application of an additional time-varying magnetic field that matches the frequency
of the aforementioned oscillations between singlet and triplet states. Indeed, the fact
that birds were magnetically disoriented when subject to weak radiofrequency fields
speaks for the radical-pair mechanism underlying the inclination compass. The
molecular identity of the radical-pair mechanism in birds has not been elucidated
yet, although members of the cryptochrome protein family (discovered in 1993 by
Ahmad and Cashmore [15] and proposed by Schulten and coworkers [16] to have
a role in the radical-pair mechanism) are currently considered the best molecular
candidates. A comprehensive treatment of the subject is provided in the review by
Hore and Mouitsen [17].
While it is accepted that the radical-pair mechanism is the most probable
explanation for how birds exploit the geomagnetic field during long-distance
1638 N. M. Dempsey
Fig. 2 Illustration of the radical-pair mechanism. The plots are simulations for a simple model
radical pair showing the probability that the radical pair is in its singlet state and how the spin
dynamics are affected by the presence and direction of an Earth-strength magnetic field. The fast
oscillations come from the hyperfine interactions and the slower modulation, most clearly seen in
the red trace, comes from the interactions of the electron spins with the magnetic field. (Courtesy
of P. Hore)
migration (in combination with other cues which exploit their sense of sight, smell,
and hearing), this does not exclude magnetic-particle-based magnetoreception in
birds and other animals. Indeed, the application of a relatively strong magnetic
field pulse, which could reorient the direction of magnetization of single-domain
magnetite particles, was shown to lead to deflected orientation in adult migratory
birds (experienced birds which have an internalized “map” of the regions they
cover during migration). Magnetic-particle-based magnetoreception could explain
the apparent use of local magnetic map information in the late homing phase of
bird migration and also in the behavior of nonmigratory birds and other animals.
For example, some animals, such as the mole rat, build their nests in a direction
determined by the orientation of the geomagnetic field.
Despite significant progress made in studies of how a wide range of animals
are influenced by the geomagnetic field, there is no direct experimental proof
of either the radical-pair mechanism or the magnetic-particle-based mechanism
34 Magnetism and Biology 1639
for magnetoreception. This is also the case for the electromagnetic induction
mechanism proposed to explain magnetoreception in certain fish (sharks, skates,
and rays) known to have highly sensitive electroreceptors. Further advances in the
study of magnetoreception in animals will require a multidisciplinary approach
combining expertise in the fields of (bio)physics and (bio)chemistry, molecular- and
neurobiology, and genetics [18].
Electrical currents circulating in the bodies of humans and animals create very weak
magnetic fields. These currents are produced in muscle cells during contraction and
in nerve cells during signal transmission. All organs with muscle and nerve cells thus
produce fluctuating magnetic fields, and the largest are associated with synchronous
depolarization of muscle cells in the heart. The largest magnetic fields associated
with nerve cells are produced in the brain, where assemblies of neurons show
synchronous behavior. Typical magnetic field values associated with the human
body are shown in Fig. 3, together with data for the Earth’s magnetic field and
for electromagnetic fields produced by human activity (e.g., power transmission,
wireless communication, etc.), referred to as electromagnetic smog. The maximum
field values produced by various other magnetic field sources, some of which are
used in magnetobiology, are also included in the figure.
The electrical and magnetic signals produced by circulating currents are linked
through the laws of electromagnetism. The well-established techniques to measure
the electrical signals of the heart and brain, electrocardiography (ECG) and elec-
troencephalography (EEG), have their magnetic counterparts, magnetocardiography
(MCG) and magnetoencephalography (MEG). Seeing that the magnetic fields
produced by the body can be orders of magnitude lower than the Earth’s field
and electromagnetic smog, it is not surprising that measuring biomagnetic fields is
very challenging and has lagged far behind electrical measurements. Luigi Galvani
first recorded electrical activity in dissected muscles in 1786, while in 1842 Carlo
Matteucci demonstrated that electrical current pulses accompanied the heartbeat
of a frog. Thirty-five years later, Augustus Waller published the first human
electrocardiogram. Electrical measurement of brain activity was first reported in
1875, when Richard Caton measured electrical currents in the brains of monkeys
and rabbits, and he associated changes in current levels with functional activities
(rotation of the head and mastication) [19]. Fifty-four years later, Hans Berger
published the first EEG which demonstrated electrical potential oscillations in the
human brain at frequencies in the range 8–13 Hz, known as α-waves [20]. But it was
not until 1963 that the first magnetic signals from the human heart were measured
by Baule and McFee, using two coils with ferrite cores and two million windings
each, connected in series [21]. By winding the coils in opposition, they produced a
gradiometer that was able to cancel the background magnetic signals and measure
temporal variations in the magnetic field gradient produced by the heart. Four
years later, David Cohen addressed the background noise problem by carrying out
1640
10 20 30 40 50 60 70 80 90 100
Human brain Electromagnetic
smog (EMS) Hybrid coils
Muscle Earth’s magnetic field
Heart Pulsed electromagnets
(destructive)
Fig. 3 Typical magnetic field values associated with the human body compared to the Earth’s magnetic field and to a range of man-made fields
N. M. Dempsey
34 Magnetism and Biology 1641
EEG and MEG are large-scale sensing techniques, measuring the electrical and
magnetic signals produced by ionic currents in large assemblies of neurons. More
localized measurements using miniaturized sensors or sensor arrays can be used to
measure the signatures of intracellular and extracellular ionic currents from single
neurons or small groups of neurons adjacent to the sensor. Localized measurements
should lead to a better understanding of large-scale measurements and help to
shed light on how the brain works. Various techniques have been developed for
electrophysiological measurements using micro-scaled metallic electrodes or glass
pipettes filled with ionic solution. As with their large-scale counterparts, com-
plementary information can be achieved with micro-scaled magnetophysiological
measurements. The magnetic field sensors should be compact and highly sensitive
and operate at body temperature. A wound toroidal coil has been used to measure the
magnetic field associated with a single giant nerve axon from a dissected crayfish,
threaded through the coil [27]. Nitrogen-vacancy center diamond sensors have been
used to measure the magnetic fields produced by single neurons extracted from
marine worms and squids and from single neurons inside intact worms [28]. GMR
sensors mounted on a needle-like support to create a “magnetrode” have been used
for the in vivo magnetic recording of the neuronal activity of a cat [29].
Iron is an essential trace element for most living organisms, ranging from bacteria
to humans. A healthy adult body contains roughly 4 g of iron and requires a daily
dietary intake of 10 or 20 mg for men and women, respectively, only 10% of which is
absorbed by the body. While iron plays a critical role in oxygen transport and redox
processes, its ability to produce free radicals renders it potentially toxic, and a series
34 Magnetism and Biology 1643
of complex processes have evolved to maintain body iron levels at a healthy level.
Iron is bound to various proteins within the body (Table 3). The role of hemoglobin
is to transport oxygen in the blood, while that of myoglobin is to carry oxygen to
muscle tissue. Ferritin is a spherical protein cage, which serves to oxidize and store
iron in the form of ferrihydrite nanoparticles (9H2 O.5Fe2 O3 ) of diameter up to 8 nm.
Transferrin serves to transport iron through the blood.
In 1936, Linus Pauling and Charles Coryell measured the magnetic suscepti-
bility of oxygenated and deoxygenated hemoglobin, as well as other hemoglobin
derivatives [31]. They confirmed earlier reports that oxygenated hemoglobin was
diamagnetic and discovered that deoxygenated hemoglobin is paramagnetic and
estimated a magnetic moment of 5.46 μB per iron atom. The paramagnetism is due
to the presence of high-spin Fe2+ ions. While there is still debate about the elec-
tronic structure of iron–oxygen bonds in hemoglobin [32], these bonds play a key
role in oxygen binding and release in red blood cells which transport oxygen from
the lungs to tissue throughout the body. The magnetic susceptibility of red blood
cells is determined by its components, the major ones being diamagnetic water,
diamagnetic oxygenated hemoglobin, and paramagnetic deoxygenated hemoglobin.
The susceptibility difference between completely deoxygenated and completely
oxygenated red blood cells is 2.7 10−7 . When a person is infected by malaria, the
parasite feeds on hemoglobin, converting it to paramagnetic hemozoin crystals [33].
The number and size of hemozoin crystals, which have a distinctive brown color
resulting in hemozoin being known as malaria pigment, depend on the stage of
parasite development. The natural occurrence of iron in the human body is exploited
in a number of applications, as will be detailed below.
Magnetobiology
Fig. 5 Iron-oxide nanoparticle (IONP) biodegradation and general iron transport and metabolism
pathway in the body (MPS mononuclear phagocytic system) [30]. (With kind permission from
Royal Society of Chemistry)
pharmacokinetics [30]. Very fine particles (<10–15 nm) get filtered through the
kidney, while larger particles (>100 nm) are typically trapped in the liver and spleen.
The time taken for the concentration of nanoparticles injected into the blood to
decrease to half its initial value is known as the blood half-life. It can be lengthened
by modifying the surface of the nanoparticles so as to hide them from the immune
system, by attaching them to red blood cells, or by tricking the immune system by
injecting decoy particles. Blood half-life times vary from minutes to several days in
rodents and from 1 h to 1 day in humans.
Once trapped, exposure of the nanoparticles to acidic environments and biochem-
ical reactions leads to their biodegradation (Fig. 5). Degradation rates depend on the
particles’ location, their coatings, and their initial dosage. Iron from nanoparticles
can be stored in the iron protein complexes ferritin and transferrin, and transferrin
1646 N. M. Dempsey
Magnetic Imaging
Fig. 6 Image of an MRI suite with a whole-body MRI system based on a closed-bore supercon-
ducting coil together with an MRI image of a human head. (© Halkin Mason Photography)
34 Magnetism and Biology 1649
MRI static field sources are compared in Table 5. In all cases, shimming (passive or
active) is used to increase the field homogeneity, and shielding is used to limit the
stray field produced by the magnet.
Whole-body systems with 7–9.4 T fields are being used for f-MRI in neuro-
science studies in a few research laboratories and university hospitals, while systems
with even higher field values are being developed in very specialized laboratories
[48, 49]. The increase in field strength and field gradient applied during imaging
leads to increased sensitivity and spatial, temporal, and spectral resolution and
allows imaging of a range of nuclei (e.g., 13 C, 17 O, 31 P, 23 Na, 35 CI, and 39 K)
to study energy metabolism and electrolyte physiology in the brain. However, the
very high installation and running costs associated with mid- and high-field whole-
body MRI systems limit their use to well-funded hospitals, clinics, and institutes.
Furthermore, the large size of such systems and the need for cryogenic liquids
to cool the superconducting coils restricts their use to very specific environments.
Small-bore systems based on permanent magnets and resistive or superconducting
coils are being used for imaging human limbs in doctors’ surgeries [50], as well as
primates and small animal models (mice, rats) in research laboratories. MRI systems
with fields of just a few tens of mT are being developed with the aim to expand
the use of MRI to in-field use (doctors’ surgeries, sports grounds, battlefields, etc.)
and to resource-poor environments. Approaches to compensate for the very low
signal-to-noise ratio achieved with such low fields include the application of a strong
inhomogeneous magnetic field pulse to polarize the sample followed by readout in a
low field (pre-polarized MRI) and the use of very fast imaging techniques combined
with sparse sampling strategies [51].
Both time-varying and static magnetic fields are used during MPI (Fig. 7) [52].
An oscillating magnetic field is used to flip the direction of magnetization of the
magnetic nanoparticles, and pickup coils are used to record their M(t) response. As
the magnetization curves are nonlinear, a Fourier transform of the induced signal is
characterized by the excitation frequency and its higher harmonics. The presence of
these harmonics allows us to distinguish between the tracer signal and the excitation
field signal. To restrict the region in which magnetic nanoparticles are excited, a
static magnetic field of sufficient intensity, with either a field free point (FFP) or
a field free line (FFL), is superimposed on the oscillating magnetic field [53]. The
static field serves to magnetically saturate all magnetic nanoparticles outside the
FFP or FFL, so that they do not respond to the oscillating magnetic field. The
position of the FFP or the FFL is scanned over the total area to be imaged, to
build up a 3D picture of the concentration distribution of magnetic nanoparticles.
Scanning of the FFP or FFL can be achieved either mechanically or with the use
of additional magnetic field coils. The typical magnetic field frequencies applied
in MPI systems are in the range of 10–100 kHz, while their peak amplitudes are
in the range 10–100 mT. The sensitivity of the technique depends on the magnetic
moment of the nanoparticles, while the spatial resolution depends on their magnetic
susceptibility as well as the gradient of the static field. MPI offers exceptional
spatial (mm) and temporal (ms) resolution. While magnetic nanoparticles developed
as MRI contrast agents have been used as MPI tracer agents, the optimum
properties are not the same for both techniques, and much effort is going into
developing magnetic nanoparticles specifically for MPI. Progress is also being
made in image reconstruction and scanner design, with the aim to further improve
sensitivity and time resolution and to upscale to full-body systems for clinical
use. MPI is used to image the flow of blood containing magnetic nanoparticles in
cardiovascular studies, to track specific cells labeled with magnetic nanoparticles,
and to monitor the position of interventional instruments coated with magnetic
nanoparticles [53, 54].
Magnetic Fixation
Fig. 7 Schematic of the basic principles of MPI: (a) An oscillating magnetic field (modulation
field, H, green curve) is applied to the magnetic material at a given frequency f1 . As the
magnetization curve (M, black curve) is nonlinear, the resulting time-dependent magnetization (red
curve) exhibits higher harmonics, as shown in the Fourier transformed signal (S, red bars). (b) A
time-independent field is added to the modulation field. The oscillating field does not significantly
change the magnetization of the material, as it is always in saturation. In this state, harmonics of
the oscillating field are almost nonexistent. The gray box indicates those harmonics used for image
formation [52]. (With kind permission from Springer Nature)
1652 N. M. Dempsey
Magnetic Actuation
Magnetic fields can be used to move objects. A homogeneous field B can be used to
apply a torque (τ ) to an object of magnetic moment (m), oriented at an angle to the
field, causing it to rotate. The torque is given by
τ = m × B (1)
Units of m are Am2 , and units of τ are Nm. An inhomogeneous magnetic field
can pull or push the object via the field gradient force,
f = ∇ (m . B) (2)
where ∇B is the magnetic field gradient. Usually, the object does not have a
permanent magnetic moment; the moment is induced by the applied field. When
the response is linear, m = χvB/μ0 , where χ is the dimensionless susceptibility of
the object and v is its volume. Units of f are N. Since the magnetization M = m/ v,
the force density F in Nm−3 can be written as
F = (1/2 μ0 ) χ ∇B 2 (3)
Table 6 Examples of the use of magnetically induced actuation in fundamental studies in biology
and biomedical applications
Actuation Application
Magnetic trapping (non-lab-on-a-chip) Diagnostics and therapeutics
Magnetic trapping, transportation, mixing of Chemical and biological analysis diagnostics
cells in lab-on-a-chip devices
Magnetic tweezers Measurement of physical properties,
mechanical stimulation
Magnetically induced cell destruction Cancer treatment
Magnetoporation Payload delivery to cells
Magnetic orientation Tissue engineering
the target. Levitation can be achieved when the magnetic force compensates
gravity:
F = ρg (4)
where ρ is the density of the target. A Bitter coil producing a magnetic field of 16
Tesla was used to levitate a living frog [57], while Nd-Fe-B micromagnets producing
a maximum field gradient of 106 T/m were used to levitate living cells [58].
Deoxygenated red blood cells are paramagnetic and have been manipulated directly,
without being magnetically labeled. Finally, some biological targets naturally con-
tain ferrimagnetic iron-oxide nanoparticles (e.g., magnetotactic bacteria, splenic red
pulp macrophages, etc.), which renders them easy to manipulate by a magnetic field.
As the magnetic field source used to achieve actuation, one can use current-
carrying wires and coils or permanent magnets (Fig. 3). The field strengths
achievable with resistive wires and coils operated in continuous mode are typically
restricted to values of the order of tens to hundreds of mT because of Joule heating,
while fields of the order of 1–10 T can be achieved in pulsed mode. Superconducting
coils can produce fields of this strength in continuous mode, but they require cooling
and are both cumbersome and expensive, and thus they are impractical for benchtop
magnetic actuation in biology laboratories. Permanent magnets based on hard ferrite
(e.g., Ba2 Fe12 O19 , Sr2 Fe12 O19 ) and rare earth transition metal (e.g., Nd2 Fe14 B,
SmCo5 ) phases produce stray fields of the order of a few hundred mT and 1 T,
respectively.
Miniaturization of the magnetic field source may be desirable for two reasons.
Firstly, it allows to locally address and manipulate small-scale biotargets. Secondly,
reducing the size of the field source while maintaining its intensity leads to an
increase in the magnetic field gradient it produces and thus increases the force it can
apply on a biotarget. When scaling down the size of a coil, it is usually necessary
to reduce the current and thus the field intensity, because of increased heating.
Nevertheless, planar coils suffer this less than wire coils, as their high surface-to-
volume ratio allows for improved cooling [59]. Micro-scaled permanent magnet
1654 N. M. Dempsey
field sources can be fabricated using hard magnetic powders [60, 61] or by micro-
patterning hard magnetic films using topographic [62] or thermomagnetic [63]
techniques. When miniaturized field sources are required, it is also possible to use
micro-scaled soft magnets based on Fe, Ni, or Co and their alloys and to magnetize
them using larger coils or permanent magnets. The choice of field source depends
on the specific application. Micro-coils and soft micromagnets are very suitable
when easy control of the force intensity is required, while hard micromagnets are
particularly well adapted when space is limited.
Magnetic Hemofiltration
High-gradient magnetic separation has been proposed for hemofiltration, in which
an extracorporeal device is used to remove targeted entities from whole blood in
a reservoir [67] or directly from blood drawn from and repumped into the body
[68] (Fig. 8). This approach could be used to eliminate undesirable entities such as
pathogens responsible for sepsis, toxins due to kidney or renal failure, circulating
tumor cells, viruses, and radionuclides or to harvest desirable entities such as stem
cells, for therapeutic use. A magnetic trap has been added to a dialysis circuit to
perform magnetically assisted hemodialysis [69]. While much work is going into
developing biofunctionalized magnetic particles suitable for binding to a wide range
of specific blood-borne targets [68], malaria-infected paramagnetic red blood cells
do not require labeling with magnetic particles to be magnetically extracted from
blood [70].
of the chemotherapy agent killing healthy cells, by trapping them at a specific site on
a tumor. Efficient trapping allows the overall drug dose administered to the patient
to be reduced. A range of biocompatible magnetic carriers have been developed
using both nano- and micro-sized magnetic particles coated by or embedded in
polymer or silica. The carriers are typically administered by injection in the form
of a ferrofluid into the bloodstream. Magnetic targeting is achieved using external
electromagnets, external or implanted bulk permanent magnets, implanted soft
magnetic microwires or microrods magnetized by an external field [71], or so-called
magnetic resonance navigation (MRN). In the latter technique, the static field of a
clinical MRI scanner is used to magnetize the magnetic carriers, and the software-
controllable magnetic gradient fields of the system are used to navigate the carriers
in real time along a pre-planned trajectory from their injection site to the targeted
area [72]. Payload release may be activated by changes in pH or temperature in
the targeted area or through thermal, electrical, or magnetic stimulation [73]. The
general approach has also been proposed for targeted delivery of radionuclides and
therapeutic genes [74]. Magnetic drug delivery trials have been carried out on many
animal models, but very few trials have been carried out on humans. Challenges
faced for clinical implementation include the risk of blocking blood vessels through
the accumulation of magnetic carriers, potential toxicity of the magnetic carriers
themselves, and the limited spatial extension of the magnetic field produced by non-
MRN external field sources, which restricts potential applications of such sources
to shallow targets.
Fig. 9 Schematic image of a microfluidic chip with an integrated array of permanent micromag-
nets used to separate magnetically labeled cells from non-labeled cells [81] With kind permission
from Elsevier (A). Schematic image of a free-flow magnetophoresis chamber used to separate
magnetic particles from nonmagnetic material, according to their size and magnetic susceptibility.
(Reprinted with permission from [82]. Copyright (2004) American Chemical Society (B))
34 Magnetism and Biology 1657
Magnetic Transportation
In most microfluidic systems, fluid flow is used to transport objects within the
channel, but when the objects to be moved are magnetic, then magnetic forces can be
used to help control their transportation [76]. This was first demonstrated by simply
moving an external permanent magnet below a channel containing magnetic beads.
Arrays of sequentially excited electromagnets positioned along a channel can also
be used to drag magnetic beads along, and more complex arrays of independently
addressed current-carrying wires can be used for magnetically controlled transport.
Application of an external magnetic field to further magnetize the beads can
significantly increase the magnetic forces. The risk of heating potentially limits
the use of current induced magnetic fields for magnetic transportation. Arrays of
micromagnets can produce a periodic potential energy landscape in which magnetic
beads are trapped. Superposition of a rotating external magnetic field on such an
array can then be used to translate the energy landscape and thus transport magnetic
beads in a process known as travelling wave magnetophoresis. This process can
be used to separate beads of different sizes. Advances made in the sequential and
parallel, timed magnetically induced movement of an ensemble of single particles
and cells hold great potential for a wide range of applications in cellular biology and
biotechnology [85].
Magnetic Mixing
Magnetic mixing in microfluidic channels of dyes and buffer solutions has been
achieved using bar-shaped stirrers made of permalloy or chains of magnetic particles
rotated under the influence of an external rotating magnetic field [75]. Pumping and
mixing of ionic fluids has been demonstrated using magnetohydrodynamic micro-
pumps in which an electric field and a magnetic field are applied perpendicular to
each other across the height and width of a microchannel. Coupling between the
electric force produced on ions by the electric field and the Lorentz force produced
by the magnetic field results in movement of the liquid along the channel.
Magnetic Tweezers
Magnetic tweezers are tools used by biologists to apply a mechanical force on a
target object. The basic idea is to apply an external magnetic field to a magnetic
particle within or attached to the biological target. Originally developed to measure
the mechanical properties of cells and molecules, the approach is now also used to
study the biological response to mechanical stress.
that the cytoplasm has viscous properties and the order of magnitude of the modulus
of rigidity could be estimated. In a twist of fate, the approach was later adapted to
directly measure the elastic properties of DNA molecules! One end of a molecule
was chemically attached to a glass slide, the other to a superparamagnetic bead, and
the ensemble was placed in a microfluidic chamber with external movable magnets
(Fig. 10). By recording the movement of the tethered beads as a function of the
magnetic and applied hydrodynamic forces in the range 10−14 –10−11 N, it was
possible to establish force versus extension, stress–strain curves characteristic of
the DNA molecule. The approach was further refined to measure the elasticity of
a single supercoiled DNA molecule, by using permanent magnets [87] and later
on an array of electromagnets [88] to precisely translate or rotate a bead attached
to the end of a molecule anchored to a glass slide. The fact that a torque can be
applied to a superparamagnetic bead indicates some magnetic anisotropy, which is
attributed to a nonuniform distribution of superparamagnetic nanoparticles within
the bead [89]. Magnetic tweezers have two specific advantages compared to optical
tweezers: the first is that the angular position of the target can be controlled,
and the second is that the biomaterial being manipulated is not exposed to
photodamage.
Magnetic tweezers have also been used to measure the rate of dissociation
of ligand–receptor bonds [90], notably the prototypical ligand–receptor pair,
streptavidin–biotin, commonly used to attach magnetic nano- and microparticles to
biotargets. Magnetic beads were functionalized with streptavidin, and biotinylated
proteins were adsorbed to the surface of a plastic slide. The beads were allowed to
contact the surface so that ligand–receptor binding occurred and then a permanent
magnet was used to pull the receptors away from the ligands. Massively parallel
(100–1000) measurements were made on large batches of single complexes
perturbed by constant forces. Technical advances made in the magnetic beads,
field sources, and force characterization protocols now allow the characterization
of the mechanical properties of a large number of biological samples, from
34 Magnetism and Biology 1659
Mechanical Stimulation
Living cells are able to feel, respond, and adapt to the mechanical properties of their
environment; the process by which cells convert mechanical signals into biochemi-
cal signals is called mechanotransduction. Cells are sensitive to both the spatial and
temporal signatures of mechanical stimuli, and thus to study mechanotransduction,
it is essential to stimulate cells with mechanical cues controlled both spatially and
temporally. Mechanical stimuli have been applied to cells using both direct methods
such as atomic force microscopy and indirect methods including optical or magnetic
[92] tweezer manipulation of beads attached to the cell. The magnetic tweezer-based
approach has the advantage of being minimally invasive and relatively simple to
implement. Nevertheless, attachment of a magnetic bead to the surface of a cell
can potentially perturb the cell due to direct mechanical interactions between it
and the stiff bead. Substrates made of micropillars that can be actuated with a
magnetic field were used to apply local and dynamic mechanical stimuli on cells
adhering to the surface (Fig. 11a) [93]. When an external magnetic field is applied,
pillars containing magnetic nanowires apply a force on cells, while nonmagnetic
posts deflect in response to, and therefore measure, traction forces of the cells.
To overcome the fact that the topology of such discrete surfaces can affect the
cellular behavior, flat soft elastomer substrates containing iron micropillars have
been developed (Fig. 11b) [94]. These can be locally and dynamically deformed
in a magnetic field, and localized deformation can be quantified by measuring the
displacement of fluorescent markers encrusted under the surface of the elastomer
using traction force microscopy. Cells spread on such magneto-active substrates
can be mechanically stimulated both in tension and in compression.
Magnetic actuation of magnetic particles on the surface of cells can be used
to activate mechanically sensitive ion channels, which control the passage of ions
through the cell membrane [95]. Specific binding of magnetic nanoparticles can be
used to activate specific ion channels. Such nanomagnetic actuation can be used to
study biochemical pathways associated with mechanical activation and to evaluate
ion-channel kinetics, and it has potential applications in tissue engineering and
regenerative medicine [95].
Magnetic forces can also be used to study mechanotransduction at the embryo
level. The role of mechanical forces during a specific stage in embryo development
known as gastrulation, during which the first coordinated movement of cells occurs,
has been studied in zebra fish and fruit flies [96, 97]. Magnetic nanoparticles
encapsulated in liposomes, a type of carrier vessel, were injected into specific
regions of embryos that had been genetically modified to arrest development at
the pre-gastrulation stage. Static magnetic forces produced by a ring of hard
magnetic particles and dynamic magnetic forces produced by an array of Fe
micromagnets magnetized by an external electromagnet were used to mechanically
initiate gastrulation in the zebra fish and fruit flies, respectively [96, 97]. These
results demonstrate the mechanosensitivity of biochemical pathways active during
gastrulation.
1660 N. M. Dempsey
Fig. 11 Schematic diagrams of microfabricated magnetically active polymer substrates used for
mechanotransduction studies at the cellular level [93]. (With kind permission “Copyright (2007)
National Academy of Sciences, U.S.A.” [94], Creative Commons CC BY license)
2 R
3α
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Surface
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membrane DNA damage
Magnetoporation
Just as magnetic fields can be used for targeted drug delivery at the macroscale, they
can also be used for delivery at the cell scale in a process known as magnetoporation.
A specific form of magnetoporation which is used to deliver nucleic acids attached
to magnetic nanoparticle vectors into cells is known as transfection. Both static and
time-varying magnetic fields have been used for in vitro and in vivo transfection
of various cell types [105, 106]. The application of static inhomogeneous fields,
typically produced by bulk magnets with a maximum applied field of about 0.5 T,
is believed to increase transfection by rapidly accumulating nucleic acid–magnetic
nanoparticle complexes on the surface of target cells. The higher efficiency of time-
varying magnetic fields, produced by pulsed electromagnets delivering a maximum
applied field in the range of 30–300 mT or vibrating arrays of permanent magnets,
is attributed to the influence of magneto-mechanical forces on cellular uptake
processes. Rotating magnetic fields of a few tens of mT have been used to increase
the uptake of iron-doped carbon nanotubes by cancer cells [102]. A benchtop
compact pulsed field system capable of producing fields of up to 10 T has been used
to deliver magnetic nanoparticles into cells that do not internalize nanoparticles by
phagocytosis [107].
1662 N. M. Dempsey
Magnetic Orientation
Homogeneous magnetic fields can apply a torque to orient macromolecules and
cells, which has potential applications in tissue engineering. The direction of
orientation depends on the molecule or cell type, due to anisotropy in susceptibility
(Fig. 13) [108]. A number of studies of magnetic orientation concerned the
polymerization of fibrous extracellular matrix proteins (fibrin, involved in blood
clotting, and collagen, found in connective tissue such as tendons, ligaments, skin,
etc.) in magnetic fields of the order of a few Tesla. While fibrin aligns parallel
to the field lines, collagen aligns perpendicular to the field lines. Magnetic fields
in the range of 1–8 T were also used to align red blood cells in gelatine. Normal
red blood cells, which have a donut-like shape, tend to align with their disk plane
parallel to the field. The degree of alignment depends on the field strength but is
independent of the oxidation state of the constituent hemoglobin, suggesting that
Fig. 13 Photographs of cells aligned either parallel or perpendicular to an applied magnetic field
[108]. (With kind permission from Elsevier)
34 Magnetism and Biology 1663
the torque acts on the diamagnetic cell membrane. In some people, polymerization
of deoxygenated hemoglobin deforms the shape of red blood cells from donut-
like to sickle-like and leads to cell rigidification. Blockage of these deformed cells
in small blood vessels leads to sickle cell anemia. When exposed to a magnetic
field, sickle cells align perpendicular to the field axis, owing to their anisotropic
paramagnetic susceptibility. Adherent cells such as osteoblasts that form bones,
endothelial cells that line the interior surface of blood vessels and lymphatic vessels,
smooth muscle cells, and Schwann cells, which are the principal nonneuronal cells
of the peripheral nervous system, have all been shown to align parallel to magnetic
field lines. The directional control of osteoblastic cells is studied because of its
potential use in bone fracture treatment [109]. Another application of magnetic
orientation in a homogeneous field concerns nerve regeneration [110]. Neurite
outgrowth from neurons was shown to be significantly greater on magnetically
aligned collagen gel than on nonaligned control gel and was found to depend on
the magnetic field strength. Such nerve regeneration could be exploited in tissue
engineering and regenerative medicine. In a complementary magnetic approach to
nerve regeneration, the field gradient force exerted by an inhomogeneous magnetic
field on magnetic nanoparticles attached to nerves has been used to induce tensile
forces which give rise to oriented neurite outgrowth [111] (Fig. 14).
Magnetic Heating
Heat is known to have healing power, and whole-body or localized heating is used
in the treatment of a variety of medical conditions. An area of particular interest
is cancer treatment. Cancer cells stop growing at about 42 ◦ C, while normal cells
can tolerate higher temperatures. Heating to temperatures in the range of 42–45 ◦ C
is referred to as hyperthermia. When combined with irradiation or chemotherapy,
hyperthermia can efficiently damage cancer cells. Heating to temperatures above
50 ◦ C is referred to as thermoablation, and this leads to necrosis, coagulation, and
carbonization of tissue. The major challenge with cancer treatment by hyperthermia
is to restrict the temperature increase to the targeted region, i.e., the tumor. Localized
heating methods used in clinical settings for the treatment of superficial tumors
include ultrasound, microwave, and near-infrared irradiation. Alternating magnetic
fields can also be used to heat tissue, and most importantly deep tissue, through three
different mechanisms: dielectric loss in poorly conducting materials, eddy current
losses in conducting materials, and hysteresis losses in magnetic materials. The first
two mechanisms can give rise to direct heating of the tissue, while the third can lead
to highly localized heating of magnetic materials that then transfer heat through
conduction to the tissue. In 1957, Gilchrist used magnetic particle hyperthermia to
selectively heat the lymph nodes of dogs into which iron-oxide particles of size in
the range 20–100 nm had been injected [112]. Following this, ferromagnetic needles
were studied as thermal seeds, which could act as constant temperature seeds if
the material passes through its Curie temperature, or constant power seeds, if used
far below their Curie temperature [113, 114]. However, these fell out of favor as
they needed to be surgically implanted and aligned with the axis of the applied RF
field to be efficiently heated. A range of other magnetic powders were then studied
(Fe2 O3 /Fe3 O4 , Fe3 Co, Ni, ferrites, etc.), with by far the greatest number of studies
done on Fe2 O3 /Fe3 O4 nanoparticles.
Heating of magnetic nanoparticles exposed to an alternating magnetic field
occurs because of magnetization reversal and/or particle rotation in a fluid suspen-
sion. The physics behind magnetic particle hyperthermia is detailed in the chapter
of this handbook on magnetic nanoparticles. Here we recall that the most important
figure of merit is the specific absorption rate (SAR), which corresponds to the power
absorbed per mass of magnetic nanoparticles. While SAR depends on the intensity
and frequency of the magnetic field, the magnetic particle size and size distribution
have been found to be crucial parameters [115]. In vitro studies have been carried
out on cell cultures, to test the biocompatibility of the magnetic nanoparticles used.
Such studies serve to distinguish between thermal effects due to power absorption
from the alternating magnetic field and toxicity of the particles themselves.
When using an alternating magnetic field to produce heating through hysteresis
losses in magnetic materials within cancerous tissue, it is essential to minimize
heating due to eddy current losses in healthy tissue. Modeling is used to estimate
heating due to exposure to an alternating magnetic field. In the case of eddy
currents, the rate of heat production per unit volume of tissue of cylindrical shape is
given by.
34 Magnetism and Biology 1665
P = σ (π μo )2 (H0 f )2 r 2 (5)
In the preceding sections, we have described how magnetic fields are used in a range
of biomedical applications. It is important to ask what are the potential effects of
these fields on living organisms and what are the risks associated with using them.
This question is particularly relevant to MRI, as millions of patients are exposed
to high static magnetic fields, time-varying low-frequency gradient magnetic fields,
and high-frequency RF magnetic fields. Besides, thousands of healthcare workers
that operate and maintain MRI systems are repeatedly exposed to the stray static
fields produced by MRI systems.
Static magnetic fields may affect the human body through the Lorentz force felt
by moving charged particles in the bloodstream. Changes observed in electrocardio-
grams of animals in the presence and absence of a static magnetic field have been
attributed to electrical potentials induced by the Lorentz force. Electric fields and
currents can also be induced in bodies that are moving in a static magnetic field.
A static homogeneous field can produce a torque on objects such as paramagnetic
molecules showing anisotropic susceptibility and cause them to rotate, while a static
inhomogeneous field can displace magnetized objects through the field gradient
force. A number of studies have been carried out to assess the potential impact
1666 N. M. Dempsey
of static magnetic fields [110, 117]. For example, in vitro exposure of certain cells
to static fields (8 T during 3 h) was reported to result in increased levels of reactive
oxygen species, while genotoxic effects were reported in other cells exposed to 3 T
fields. Swelling and the formation of reactive oxygen species in cells positioned
close to arrays of permanent micromagnets were attributed to the very-high-gradient
static magnetic fields produced by such field sources (106 T/m at the surface of the
micromagnets) [118]. The potential effects of high-gradient static magnetic fields
on intracellular processes have been assessed from a theoretical point of view [119].
Following analysis of a large number of studies, the World Health Organization
(WHO) reported that both positive and negative effects were claimed on a range of
aspects studied (cell metabolic activity, cell membrane physiology, gene expression,
cell growth, genotoxicity) but that most data was not replicated. A WHO analysis
of literature related to the effects of static magnetic fields on animals concluded that
the movement of rodents in fields of 4 T or greater induced aversive responses and
conditioned avoidance related to discomfort. The observed effects were attributed
to the influence of the magnetic field on fluid in the inner ear. Some humans moving
in static fields produced by MRI machines reported experiencing vertigo, nausea,
poorer hand–eye coordination, and a metallic taste. The WHO concluded that there
is inadequate data to assess the health risks related to human exposure to static
magnetic fields.
Exposure to time-varying magnetic fields induces time-varying electric fields
and currents in the body. The intensities of the induced electric fields and currents
depend on the orientation of the time-varying magnetic field with respect to the
body, and they vary depending on the conductivity of the organs and tissue affected.
Induced currents are known to stimulate nerve and muscle cells, which can cause
discomfort. The onset of discomfort due to peripheral nerve stimulation is used to
set the upper limit for field exposure in terms of field amplitude and frequency.
Reports of people exposed to time-varying magnetic fields seeing flashes of light,
known as magnetophosphenes, are attributed to induced currents within the retina or
visual cortex. The International Agency for Research on Cancer (IARC) classified
the time-varying magnetic field associated with electricity transmission at 50–60 Hz
as possibly carcinogenic, based on epidemiological studies that reported increased
risk of childhood leukemia for magnetic field amplitudes greater than 0.4 μT.
However, there is no supporting evidence that such fields, referred to as extremely
low-frequency (EFL) fields, have an effect on cells or animals.
When a high-frequency RF electromagnetic field impacts upon tissue, the
induced electric field it produces in the tissue exerts forces on polarized molecules,
electrons, and ions, causing them to move, which leads to heating of the tissue.
This has to be considered when choosing field amplitude and frequency for
selective localized heating of magnetic nanoparticles during magnetic hyperthermia.
Exposure to RF fields may also influence the outcome of radical-pair biochemical
reactions within the body and could explain why magnetic navigation in birds is
disturbed by RF fields. The IARC classified RF fields as possibly carcinogenic to
humans, though evidence from experimental studies on animals and humans is very
limited.
34 Magnetism and Biology 1667
Fig. 15 Transcranial magnetic stimulation: Top, head models with different types of coils: double-cone coil (a), H-coil(b), halo-circular assembly coil, (c) and
figure-of-eight coil(d); bottom, corresponding simulated distribution of B-field (Tesla) with the contour outline of scalp and gray matter [122]. (Copyright:
© 2017 Lu, Ueno)
N. M. Dempsey
34 Magnetism and Biology 1669
Fig. 16 ICNIRP exposure guidelines for low-frequency (1 Hz–100 kHz) magnetic fields [126].
(With kind permission from Wolters Kluwer Health, Inc.)
This chapter has given an overview of many, though certainly not all, links between
magnetism and biology. Advancing the study of magnetic fields produced by the
brain, through the improvement of existing and the development of new macro-
scopic and microscopic field detection tools and data analysis protocols, will help
us to progress in our understanding of how the brain works. This in turn should guide
the use of magnetic fields in the treatment of a range of brain disorders. The exploita-
tion of magnetic fields for other therapeutic applications requires validation through
systematic studies under very well-defined experimental conditions. A number of
biomedical applications involving the introduction of magnetic nanoparticles (e.g.,
magnetic particle-based imaging, hyperthermia, targeted drug delivery) or small
magnets (e.g., magnetically guided medical devices) into the human body are still at
the developmental stage and will require extensive animal and human clinical trials
before approval for clinical use. The further development of magnetic resonance
imaging in very high fields will lead to unprecedented resolution and access to
complex physiological processes, while at the low field end it will expand the use of
the technique to beyond hi-tech, high-cost environments. Developments in material
and device fabrication (e.g., microfabrication of magnetoelectric composites, 3D
printing of complex magnetic structures, etc.) should lead to advances in the
detection and exploitation of magnetic fields in biology and medicine. Fulfilling the
enormous potential at the interface between magnetism on one side and biology and
medicine on the other requires truly interdisciplinary research between physicists,
engineers, chemists, biologists, and medical doctors.
Further Reading
Acknowledgments The author is very grateful to Michael Winklhofer for very fruitful discussions
and feedback, to Kieron Ranno for artwork and to Mario Fratzl for assistance in putting the chapter
together.
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34 Magnetism and Biology 1677
Curie temperature, 23, 33, 34, 69, 83–84, Diffuse magnetic scattering, 1276
92, 130, 223, 354, 439, 443, 448, Diffusion, 1603
552, 627, 648, 929, 950–952, equation, 1442
961–963, 1392 layer, 1602
Curie-Weiss law, 20, 247, 687 Difluorides, 890
Current sensing, 1545 Dilute ferromagnetic semiconductors (DFSs),
Current-in-plane (CIP), 446, 449 928–929, 957–960
Current-perpendicular-to-plane (CPP), 446, Dilute magnetic materials (DMMs), 928
449, 465 band and localized spins, exchange
Curvature measurement, 572 interactions, 936–938
Cycloidal spin spiral, 601, 602, 604 dilute ferromagnetic insulators and
Cyclotron motion, 1127 topological insulators, 960–963
dilute magnetic semiconductors,
929–930
D dilute magnetic topological materials, 930
Damon-Eshbach spin-wave mode, 283, 294 dominant spin–spin interactions,
DC magnets, 1094 946–952
high-field resistive magnets, energy states of magnetic dopants, in
1095–1098 solids, 931–936
hybrid magnets, 1098 heterogenous magnetic semiconductors and
DC servomotor, 1422 oxides, 930, 964–967
Dc sputtering, 907 p-type dilute ferromagnetic
de Gennes factor, 69, 85, 86, 130 semiconductors, 928–929,
de-Gennes polymer analogy, 92 957–960
Dead layers, 910–911 sp-d( f ) exchange interactions, effects of,
Debye model, 1450 938–946
Decoherence, 265–268, 274, 275 spin-glass systems, 952–957
Decomposition, 1156 Dilute magnetic oxides, 911–914
Decoration methods, 1140 Dilute magnetic semiconductors (DMSs), 221,
Degenerate Fermi-surface crossing 912, 929–930, 938, 939, 945–947,
(DFSC), 152 953
3d elements, 1394 with rare earth metals, 948
Demagnetization factor, 15, 1377 with transition metals, 948
Demagnetization tensor, 1377, 1390 Dilute magnetic topological materials, 930
Demagnetization time, 506 Dimensionless numbers
Demagnetizing field, 14, 15, 358–361, 401, fluidic, 1603
1376, 1377 MHD, 1606
Demand for Nd-Fe-B, 1409 Dioxides, 877–878
Dense stripe domains, 412 Dipolar interaction, 1314
Density functional theory (DFT), 78, 79, 81, Dipolar nets, 268–271
95, 154, 155, 190, 574, 639 Dipole fields, 358–359
Density of states (DOS), 73, 76, 77, 193, Dipole selection rule, 485
195, 196, 200, 208, 211, 662, 663, Dipole-dipole interaction, 225, 946
678–680, 934, 942, 952 Dirac, Paul, 22
Deoxygenated red blood cells, 1653 Dirac and Weyl semimetals, 1173, 1175
Deposition, 1607, 1608, 1610 Dirac equation, 188, 201, 202, 227
Diamagnetic susceptibilities, 1596 Dirac Hamiltonian, 201
Diamagnetism, 105, 1596, 1598 Dirac matrices, 201
Dichroic bleaching, 507 Direct coupling, 996–999
Die-upset melt-spun Nd-Fe-B, 1399 Direct magnetoelectric effects, 609
Dielectric targets, 1186 Direct spin-spin interactions, 946
Dielectric tensor, 481, 485, 486 Disordered local moment (DLM), 201,
Differential phase contrast microscopy, 240, 245
1210–1212 Dispersion relation, 193
Index 1685
Hall effect, 188, 438, 440, 458–461, 959, Hemoglobin, 1643, 1646, 1647, 1662
1335, 1563 Hendrika van Leeuwen, 21
sensors, 1534, 1535 Herrings-Kittel formula, 285
Hall probe, 1218 Heteroepitaxial templates, 1160, 1161
Hall resistance measurement, 1568 Heteroepitaxy, 1160
Hall voltage, 458, 465, 1116 Heusler alloys, 88, 213–217, 508, 520,
Hard disk, 1537 559, 1412
Hard ferrite, 1389, 1392–1393 Heusler compounds, 1178, 1506, 1508
Hard steels, 666–667, 1390 Heusler families, 33
Hardness parameter, 1375 Hexagonal ferrites, 30, 873–875, 1392
Hartmann number, 1607 Hexagonal point symmetry, 113
Hartree-Fock approximation, 644 H-field, 13
Hauerite, 893 Hibonite, 873
Hausmannite, 878 High frequency losses, soft
H-coils, 1667, 1668 magnets, 1449
HD-AOS, 505 insulators, 1450–1451
Heat assisted magnetic recording metals, 1450
(HAMR), 1030 High gradient magnetic separation
Heat treatment process, 703, 1394 (HGMS), 1655
Heavy d-shell elements, 689 High magnetic fields, 42
Heavy f-shell elements, 690 High-field magnet facilities
Heavy fermions, 83 DC-magnets and facilities, 1094–1099
Heavy p-shell elements, 689 Megagauss magnetic fields, 1102–1104
Heavy-fermion compounds performance limitations and magnet
basic properties, 776 classification, 1091–1095
electron mass, 771 pulsed magnets and facilities, 1099–1102
energy scale, 773 High-field resistive magnets, 1095
fermi level, 772 High-gradient magnetic separators (HGMS),
fermi-liquid, 771 1616, 1618
groups, 778 High-harmonic generation (HHG), 496
Kondo effect, 772 High-resolution transmission electron
Kondo-lattice compounds, 773 microscope (HRTEM), 816
magnetic interactions, 778 High-spin low-spin transitions, 69
microscopic level, 772 High-temperature superconductivity (HTSC),
non-superconducting, 775 94, 95
Quantum phase transition, 773 High-temperature superconductors (HTC),
Sommerfeld coefficient, 771 1175, 1176
unconventional superconductivity, 778 Highly-oriented pyrolytic graphite (HOPG),
uranium/cerium intermetallics, 774 689, 1170
vegetable, 774 History of magnetism, 4–10
Hedenbergite, 898, 901 compass, 5–7
Heisenberg exchange, 1055, 1335 Lucretius, 5
interaction, 1265 magnetic attraction to Thales, 5
Heisenberg hamiltonian, 22, 220, 221, 862 modern science, 7
Heisenberg model, 34, 63–65, 92, 97, 105, Holding components, 1419
165, 349 Holding magnet, 1419
Heisenberg picture, 520 Homoepitaxy, 1158
Heisenberg, Werner, 22 Hopping (interatomic), 56, 58, 72–74, 82,
Heitler-London approximation, 56 93, 95
Helicity-dependent multiple-pulse Horseshoe magnets, 1391
mechanism, 524 Horseshoes, 4, 8, 15
Helimagnetism, 87 Hot deformation, 1388, 1399, 1400
Helmholtz coils, 1090 Hot extrusion, 1412
Hematite (α-Fe2 O3 ), 87, 864–865, 1374 Hot isostatic pressing (HIP), 703
Index 1691
Micromagnetism, 25, 43, 349, 1374, 1375, precise beam flux control, 1178
1383, 1386 pseudo-binary compounds, 1178
basics, 349–350 slow growth rate, 1178
Brown’s micromagnetic equation, 376–381 substrate temperature, 1167, 1168
characteristic length scales, 372–376 UHV environment, 1164, 1165, 1167
magnetic Gibbs free energy, 350–371 Molecular beam(s), 1165
magnetization dynamics, 382 fluxes, 1165, 1167, 1168
Microphones, 1391, 1421 Molecular field, 20
Microscopic, 392 Molecular quantum spintronics, 995, 996
equation of motion, 1299–1301 direct coupling, 996–999
Microscopic three-temperature model indirect coupling, 999–1001
(M3TM), 514, 516, 519, 520 quantum algorithms, 1001–1002
MicroSQUID, 990 Molecules, 1023
Microstructure, 1393, 1395, 1396, 1412 Molybdenum permalloy powders cores, 1483
images, 702 Moment
Microwave absorption, 1479 dipole, 1595
Microwave ferrites, 1478–1480 electron, 1594
Microwave materials, 105 spin-only, 1595, 1597
Microwave power tubes, 1419 Momentum
Microwave resonator, 1322 canonical, 1105
Microwave signal, 1327 kinetic, 1105
Mineral and metal separation, 1420 Monatomic spin-chain model, 151, 152
Miniaturised sensors, 1642 Monoxides, 876
Minnesotaite, 898, 899 Monte Carlo simulation, 839, 1276
Minor loops, 1403 MO recording, 478
Mixed-valence compounds, 862 Morin transition, 865
Mixed-valence manganites, 879, 881, 884 MO spectroscopy, 495–496
Mixed-valence oxides, 878 Mössbauer spectroscopy, 744, 754, 1034
Mn dimers, 87, 965 Motors, 1391
Mn3 (Cu(1−x) Gex )N, 553 Mott detector, 1215, 1351
Mn/GaAs (001), 814–816 Mott insulator, 860
Mn2 Ga, 76 Mott-Hubbard insulators, 66
MnAl, 76 Mott-Hubbard transition, 935
MnAs precipitation, 966 Mott-Ioffe-Regel limit, 438
MnBi, 56, 76 Mott’s two-current model, 443, 444
MnF2 , 84 Multicore particles, 1644
MnFeP1-x Asx alloys, 767 Multiferroic(s), 880, 915
MnO, 84 evolving terminology, 599
MnSi, 87 ferroelectric antiferromagnets, 601–604
Mobility edge, 438 ferroelectric ferrimagnets, 602, 604
μT −model, 517 ferroelectric ferromagnets, 599, 600
Modulation technique, 1109 ferroic crystal, 598
Molar susceptibility, 1597 ferroic properties, 598
Molecular beam epitaxy (MBE), 810, 907 as primary ferroics, 599
application, 1165 single-phase multiferroics, 599
chamber, 1165, 1166 spin filter, 458
development, 1165 Multigrain particles, 1400
drawback, 1178 Multilayer heterostructures, 1556
features, 1165 Multi-phase branching, 413
Heusler compounds, 1178 Multiple-pulse AOS mechanism, 525
history, 1165 Multiple scattering theory, 199, 226
in-situ monitoring of thin film growth, Multi-pole magnetization, 1388
1168, 1169 Multi-spin Hamiltonian, 987
molecular beam fluxes, 1167, 1168 Mumetal, 580, 1465
Index 1703
Y
W YCo5 , 148, 157
Wagner-Mermin theorem, 94 Young’s modulus, 554, 578
Walker breakdown, 424 Yttrium iron garnet (YIG), 30, 871,
Wannier functions, 58 916, 1480
Waste-water treatment, 1619
Weak localization, 439
Weak skin effect approximation, 1440 Z
Weiss, Pierre, 20, 1436, 1461 Zeeman effect, 634
Weiss field, 240 Zeeman energy, 26, 350, 357, 360, 400, 407,
Weiss model, 514 421, 452, 635
Weiss’ molecular field, see Mean-field Zeeman interaction, 55, 64, 68, 83
approximation (MFA) Zeeman splitting, 631
Whole-body MRI, 1648, 1649 Zeeman torque, 423, 424
Wide-field Kerr microscopy, 497 Zero bias anomaly (ZBA), 1068
Wiedemann effect, 556, 557, 571 Zero field resistivity, 450
Wiggler, 1418, 1419 Zero field splitting (ZFS), 983, 984,
Wind turbines, 1423 988, 1308
Working point, 1412 Zero-magnetostriction alloys, 580–582
World Health Organisation (WHO), 1666 Zhang-Rice polaron, 932
Wüstite, 867–868, 876 Zinc ferrite, 870
Zn bonding, 1404
X Zone plate, 1232
X-ray absorption (XAS), 1263 Z-phase, 1395
X-ray diffraction (XRD), 966 ZrZn2 , 56, 74