See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/8542501

Electric Polarization Reversal and Memory in a

Multiferroic Material Induced by Magnetic Fields

Article in Nature · June 2004

DOI: 10.1038/nature02572 · Source: PubMed

CITATIONS READS

1,516 881

6 authors, including:

Soonyong Park Peter Anand Sharma

Chung-Ang University Sandia National Laboratories
42 PUBLICATIONS 3,519 CITATIONS 82 PUBLICATIONS 3,225 CITATIONS

SEE PROFILE SEE PROFILE

Jai Sang Ahn Shaili Guha

Kumoh National Institute of Technology Manav Rachna International University
220 PUBLICATIONS 3,764 CITATIONS 119 PUBLICATIONS 3,800 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Quantum Critical Phenomena in Heavy Fermion Systems View project

Physics of manganites View project

All content following this page was uploaded by Peter Anand Sharma on 06 June 2014.

The user has requested enhancement of the downloaded file.

NATURE 2572—12/5/2004—VBICKNELL—104170
letters to nature
.............................................................. plane at ,25 K. Below ,4.2 K, the Mn and Tb moments are believed
to be amplitude-modulated at fixed angles to the ab plane21,22. In
Electric polarization reversal and addition, the Tb ordering transition was indirectly suggested
memory in a multiferroic material through alternating-current magnetoelectric measurements18.
A delicate balance between various exchange interactions among
induced by magnetic fields the Tb3þ, Mn3þ and Mn4þ spins and the lattice polarization
induces a number of phase transitions in TbMn2O5. Figure 1a
N. Hur, S. Park, P. A. Sharma, J. S. Ahn*, S. Guha & S-W. Cheong shows the temperature (T) dependence of the magnetic suscepti-
bility, x ¼ M/H as well as the magnetic field (H) dependence of the
Department of Physics & Astronomy, Rutgers University, Piscataway, New Jersey magnetization of a TbMn2O5 crystal along the three principal
08854, USA crystallographic directions. (Single crystals of TbMn2O5 were
* Present address: Department of Physics, Pusan National University, Pusan 609-735, Korea grown using B2O3/PbO/PbF2 flux in a Pt crucible. The flux was
............................................................................................................................................................................. held at 1,280 8C for 15 hours and slowly cooled down to 950 8C at a
Ferroelectric and magnetic materials are a time-honoured sub- rate of 1 8C per hour. Crystals grew in the form of black platelets as
ject of study and have led to some of the most important well as cubes with a typical size of ,10 mm3.) A large magnetic
technological advances to date. Magnetism and ferroelectricity anisotropy, primarily originating from the large spin-orbit coupling
are involved with local spins and off-centre structural distor- of the Tb moment, was clearly observed. M(H) curves at 2 K in
tions, respectively. These two seemingly unrelated phenomena the inset of Fig. 1a show that the magnetic ‘easy’ direction is along
can coexist in certain unusual materials, termed multiferroics1–11. the a axis, that the magnetization saturates for H . 2T applied
Despite the possible coexistence of ferroelectricity and magnet- along the a axis, and that the corresponding saturation moment is
ism, a pronounced interplay between these properties has rarely 8.2 mB per formula unit, consistent with earlier studies18. Several
been observed6,12. This has prevented the realization of multi- distinct features occur in x(T) at ,24 K, ,38 K and ,43 K, more
ferroic devices offering such functionality13. Here, we report a clearly displayed in Fig. 1b. All three crystallographic directions
striking interplay between ferroelectricity and magnetism in the show this behaviour, although it is more apparent along the b and c
multiferroic TbMn2O5, demonstrated by a highly reproducible axes. Long-range antiferromagnetic order of the Mn3þ/Mn4þ spins
electric polarization reversal and permanent polarization
imprint that are both actuated by an applied magnetic field.
Our results point to new device applications such as magnetically
recorded ferroelectric memory.
Multiferroics, sometimes called magnetoelectrics, possess two or
more switchable states such as polarization, magnetization or
strain1,2. Although there are a number of materials that possess
both ferroelectricity and magnetism, it may be surprising that there
need not necessarily be a large coupling between them. The non-
trivial spin-lattice coupling in these multiferroics has been mani-
fested through various forms, such as linear and bilinear magneto-
electric effects14,15, polarization change through field-induced
phase transition16,17, magneto-dielectric effect5,7, and dielectric
anomalies at magnetic transition temperatures8,9. Arguably, mag-
netoelectric effects have been studied the most in multiferroics such
as perovskite-type BiFeO3 (refs 3, 4) or BiMnO3 (ref. 5), the boracite
family6,7, and the families of BaMF4 (M, divalent transition metal
ion)8, hexagonal RMnO3 (R, rare earths)9,10, and the rare-earth
molybdates11. In general, the applied magnetic field results in a small
modulation in the spontaneous polarization. However, the com-
plete (non-reversible) rotation of ferroelectric domains by magnetic
fields has rarely been observed6,11. Why and under what circum-
stances a large coupling should come about is a major open
question, but this problem has proved difficult to tackle owing to
the lack of materials that show such large coupling.
Here we report that the multiferroic TbMn2O5 exhibits a pro-
found interplay between electrical polarization and the applied
magnetic field. This is demonstrated by two discoveries: the highly
reversible switching of electrical polarization using relatively low
magnetic fields of 0–2 T; and the combined application of electric Figure 1 Coupled dielectric and magnetic properties at phase transitions. a, Temperature
and magnetic fields, which leaves a permanent imprint in the dependence of magnetic susceptibility of a TbMn2O5 crystal along three crystallographic
polarization. This ‘reversible’ polarization switching and memory directions, measured in 2 kOe. The inset shows magnetization versus magnetic field up to
effect are distinct from the ‘non-reversible’ rotation of ferroelectric 4 T. b, The temperature derivative of the magnetic susceptibility along the three
domains by magnetic fields6,11. crystallographic directions as well as the temperature dependence of specific heat exhibit
Very little is actually known about the ferroelectricity and various low-temperature features, signalling a number of phase transitions. c, Dielectric
magnetism of TbMn2O5, primarily owing to its chemical and constant versus temperature. The features of the dielectric constant along the b axis
structural complexity18–20. The structure at room temperature is closely match those in Fig. 1b. For the dielectric measurement at 1 kHz, we used thin
orthorhombic (space group, Pbam). The Mn4þ ions are octahed- rectangular specimens with a cross-sectional area of 1–2 mm2 and a thickness of
rally coordinated by oxygen, whereas Mn3þ ions are at the base 0.2–0.5 mm. The dielectric constants along the a and c directions show negligible
centre of a square pyramid. Neutron diffraction studies have anomaly. Certainly, this material is highly anisotropic in magnetic and dielectric
suggested a helical distribution of Mn moments rotating in the ab properties.
NATURE | doi:10.1038/nature02572 | www.nature.com/nature 1
NATURE 2572—12/5/2004—VBICKNELL—104170
letters to nature
is known to occur at about 40 K. The 24 K feature has been identified spin ordering at 43 K, suggesting a close relationship to the
as a Mn spin reorientation19. The structural complexity of this subsequent appearance of ferroelectricity along this direction. It
material allows for a number of magnetic exchange paths of has been suggested that the long-range magnetic ordering of Mn3þ
comparable magnitude that can cause such a transition. Although and Mn4þ induces the ferroelectric transition through an additional
there is no clear evidence in our x(T) data, Tb magnetic ordering is distortion of the Jahn–Teller-distorted Mn3þ neighbours19. A pro-
suspected to occur below ,10 K (refs 18, 21, 22). nounced ‘step’ in the e(T) at 24 K appears simultaneously with
The specific heat, C (Fig. 1b), and dielectric constant, e (Fig. 1c), respect to the Mn3þ/Mn4þ spin reorientation. Although a detailed
also exhibit features that closely match those in x. The large peak in study of the magnetic ordering and accompanying polar atomic
e along the b axis at 38 K signals the onset of ferroelectricity, just displacements has not yet been performed, these dielectric features
below the magnetic-ordering temperature. Earlier studies have at the magnetic transition temperatures signal non-trivial spin–
shown a much-less-pronounced peak and a lower ferroelectric lattice coupling. Note that the significant C rise below 10 K on
transition T (T C), probably resulting from lower crystal quality18. cooling may suggest the slow onset of Tb magnetic order.
There are no clear dielectric signatures along the a and c directions, We attempted to observe how the dielectric behaviour evolves
indicating the dominant orientation of polarization, P, along the b with H along the a axis; H induces a drastic increase of magnetiza-
axis. Intriguingly, the rise of the b-axis e starts upon Mn3þ/Mn4þ tion at low temperatures. The magnetic field had a strong influence
on e along the b axis, whereas little change was observed along the a
and c axes, as depicted in Fig. 2a. As evident in the figure, the 38-K
ferroelectric transition gradually decreases in T with increasing H,
whereas the ‘step’ anomaly dramatically increases in T with increas-
ing H.
To observe the influence of H on P directly, we measured the

Pn

Pn

Figure 2 Magnetic-field dependence of ferroelectricity and memory effect.

a, Temperature dependence of 1-kHz dielectric constants along the b axis in various
magnetic fields applied along the a axis. For clarity, only warming data are displayed.
b, Temperature dependence of the total electric polarization along the b axis in magnetic
fields. The polarization was calculated by integrating the measured pyroelectric current23.
Before each measurement, the sample was cooled from 120 K to 3 K in a static electric
field, E pole ¼ 4 kV cm21 and zero magnetic field (ZFC); the pyroelectric current was Figure 3 Reproducible polarization reversal by magnetic fields. a, Dielectric constant
measured while heating the sample at a rate of 4 K min21. Inset, the measured versus applied magnetic field at 3 and 28 K. b, Change of total electric polarization by
polarization may be the sum of a positive component (P1 ) and a negative component (P2 ). applied magnetic fields at 3 and 28 K. The magnetic-field dependence of the total electric
The inset shows a diagram of the proposed temperature dependence of P1 and P2 in polarization was obtained by measuring the magnetoelectric current as a function of
H ¼ 0 T and 9 T. c, Total electric polarization in various magnetic fields, measured after magnetic field, which was varied linearly with time at the uniform rate of 100 Oe s21. The
cooling in a magnetic field (FC) along the a axis as well as an electric field E pole along the magnetoelectric current was measured after cooling with E pole along the þb axis without
þb axis. d, Total electric polarization measured in zero magnetic field after cooling under magnetic field. The total polarization was obtained by adding the spontaneous polarization
four different conditions: E pole along the þb axis without magnetic field; E pole along the to the field-induced polarization, which was calculated from the magnetoelectric current.
2b axis without magnetic field; E pole along the þb axis with a magnetic field of 9 T; and The cartoon shows the orientation of the net polarization (P n ¼ P 1 þ P 2) in zero field
E pole along the þb axis without magnetic field followed by an application of 9 T at 3 K, and high fields .2 T. c, Polarization flipping at 3 K by linearly varying magnetic field from
which is again followed by removing E pole before removing the magnetic field of 9 T. The 0 to 2 T. These results clearly display highly reproducible polarization switching by
applied magnetic field leaves a permanent imprint in the polarization. magnetic fields.
2 NATURE | doi:10.1038/nature02572 | www.nature.com/nature
NATURE 2572—12/5/2004—VBICKNELL—104170
letters to nature
temperature-dependent pyroelectric current and magnetic-field- e(H) at 3 and 28 K. The dielectric constant exhibits a maximum
dependent magnetoelectric current along the b axis. Magnetic change of 13% at 3 K and 20% at 28 K. At 3 K, a broad peak occurs in
field was always applied along the a axis; curiously, only fields e at around 1 T, with a small amount of hysteresis, corroborating the
along this direction appeared to have any effect at all. Figure 2b and c behaviour of P(H) in Fig. 3b. This peak rapidly smears out as T
displays the total P(T), the sum of the spontaneous P and the increases and diminishes at ,10 K, suggesting a relation to Tb
H-induced P, in various magnetic fields. All measurements were magnetic ordering. At 28 K, e exhibits a field-induced ‘step’
performed by poling the sample along the b axis in a static electric anomaly with a larger hysteresis rather than a peak, consistent
field, E pole ¼ 4 kV cm21. At H ¼ 0, P starts to increase at 38 K, with the H dependence of the step feature in e(T) shown in Fig. 2a as
confirming the onset of ferroelectricity signalled by the peak in e(T). well as P(H) in Fig. 3b.
The lower-temperature ‘step’ in e(T) correlates with a sudden The electric polarization shows a startling magnetic-field-
decrease in P on cooling, both of which behave systematically induced reversal at low T, shown in Fig. 3b. At 3 K, the direction
with increasing H. In general, an anomaly in e(T,H) indicates a of P is completely reversed with a rather low H, corresponding to a
sudden change of P (for example, rotation or onset). As is evident in change in P of ,80 nC cm22 at 2 T. This change in P for H below 2 T
Fig. 2b, even modest fields as low as 1 T had a surprisingly profound is considerably large and nonlinear, suggesting that this behaviour
effect on P. The direction of the P at low T could be completely stems from H-induced phase transitions16,17, possibly associated
switched with the application of only 2 T. This field effect can be with the H-induced change of Tb magnetism. However, the P
seen more dramatically by ‘poling’ the sample with magnetic field change for high H is rather linear with H, indicating that the linear
cooling (FC) in addition to applying E pole. As shown in Fig. 2c, the magnetoelectric effect14,27 becomes active above 2 T. These results
FC polarization at low temperatures initially decreases and becomes are certainly consistent with the behaviour of magnetization, which
negative with increasing H, but for H . 3 T, it increases again, and saturates for H along the a axis above 2 T. Note that the magnetic
eventually becomes positive. symmetry P 2am 0 c 0 21 (magnetic point group, m 0 m 0 2) in zero field
This seemingly quite complicated temperature and magnetic- proposed from a neutron diffraction study18,22 allows only non-zero
field dependence may be explained using the concept of ferrielec- diagonal elements of the linear magnetoelectric tensor14,15, but H
tricity23–26. The net polarization can be considered to be the sum of a along the a axis above 2 T appears to induce ferromagnetic Tb
few different components, each of which may have a different T and ordering, changing the magnetic symmetry and thus allowing a
H dependence. It is natural to consider such a model because of the large off-diagonal linear magnetoelectric coefficient, a 21, of about
structural complexity inherent in this material. From the shape of 221 ps m21. We also point out that the reversible P flip along the
the polarization data for H ¼ 0, we conjecture that the total P is ^b axis with H ¼ 0–2 T should be distinguished from the non-
composed of a positive component (P 1) which spontaneously reversible 1808 switching of the spontaneous polarization induced
appears at T C < 38 K and a negative component (P 2 ) at by the 908 rotation of magnetic field in Ni3B7O13I (ref. 6), the non-
T C < 24 K as shown in the inset of Fig. 2b. We emphasize that the reversible 1808 switching of the spontaneous polarization of a
absence of the a- and c-axes e(T) anomaly in magnetic fields portion of the ferroelectric domains in Tb2(MoO4)3 (ref. 11), and
indicates that P 1 and P 2 always lie along the ^b axis. Because the the 908 rotation of P by applied H < 5 T in TbMnO3 (ref. 12).
direction of P can be switched completely by an oppositely directed We performed a sequential flipping of P by slowly varying H
E pole as shown in Fig. 2d, we can assume that the direction of P 2 is linearly from 0 to 2 T. A strikingly reversible and reproducible
always opposite to that of P 1. Once E pole and H fix the direction of variation of the polarization was observed without any noticeable
P 1, P 2 always chooses the opposite direction. Judging from the decay in its magnitude, as displayed in Fig. 3c. By combining this
overall behaviour of the polarization in Fig. 2b, P 1 does not appear highly reproducible P reversal with the ability to leave a permanent
to be very sensitive to H, while P 2 changes considerably, particularly ‘imprint’ in the polarization with an applied magnetic field demon-
below ,15 K. strated in Fig. 3c and Fig. 2d, respectively, one can envision a
There is clearly a distinct difference between FC poling and poling ferroelectric memory that can be magnetically recorded. A
in zero magnetic field (ZFC), as shown by comparing Fig. 2b and c,
but this combined magnetic- and electric-field poling process can Received 5 November 2003; accepted 19 April 2004; doi:10.1038/nature02572.

also affect P even after removing H, as illustrated in Fig. 2d, for 1. Smolenski, G. A. & Chupis, I. E. Ferroelectromagnets. Usp. Fiz. Nauk. 137, 415–448 (1982); Sov. Phys.
which all measurements were taken in zero field. In this figure, Usp. 25, 475–493 (1982).
2. Schmid, H. Multi-ferroic magnetoelectrics. Ferroelectrics 162, 317–338 (1994).
applying E pole along the þb direction produces a net positive total P, 3. Wang, J. et al. Epitaxial BiFeO3 multiferroic thin film heterostructures. Science 299, 1719–1722
and reversing E pole to be along the 2b direction naturally produces (2003).
a net negative total P. However, poling with E pole along the þb 4. Smolenskii, G. A., Yudin, V. M., Sher, E. S. & Stolypin, Yu. E. Antiferromagnetic properties of some
perovskites. Sov. Phys. JETP 16, 622–624 (1963).
direction and H along the a direction surprisingly results in a net
5. Kimura, T. et al. Magnetocapacitance effect in multiferroic BiMnO3. Phys. Rev. B 67, 180401
negative total P measured at H ¼ 0. A net negative total P was also (2003).
obtained when a high magnetic field was applied at 3 K after ZFC 6. Ascher, E., Rieder, H., Schmid, H. & Stössel, H. Some properties of ferromagnetoelectric nickel-iodine
poling along the þb direction, but E pole was removed before boracite, Ni3B7O13I. J. Appl. Phys. 37, 1404–1405 (1966).
7. Baturov, L. N., Al’shin, B. I. & Yarmukhamedov, Yu. N. Nonlinear magnetoelectric and dielectric
removing H. This seemingly contradictory result can be understood
properties of Ni-I boracite. Fiz. Tverd. Tela 20, 2254–2259 (1978); Sov. Phys. Solid State 20, 1300–1303
with the scenario we have considered. At low enough T (,,20 K), (1978).
the negative P 2 state should become dominant in high applied 8. Scott, J. F. Phase transitions in BaMnF4. Rep. Prog. Phys. 12, 1056–1084 (1979).
magnetic fields, as evident in Fig. 2b. The simultaneous application 9. Katsufuji, T. et al. Dielectric and magnetic anomalies and spin frustration in hexagonal RMnO3
(R ¼ Y, Yb, and Lu). Phys. Rev. B 64, 104419 (2001).
of a high H and a positive E pole will align a large P 2 along the þb axis
10. Fiebig, M., Lottermoser, Th., Fröhlich, D., Goltsev, A. V. & Pisarev, R. V. Observation of coupled
and consequently, P 1 along the 2b axis (P 1 and P 2 always remain in magnetic and electric domains. Nature 419, 818–820 (2002).
opposite directions). After removing E pole and H, the P 1 state 11. Ponomarev, B. K., Ivanov, S. A., Popov, Yu. F., Negrii, V. D. & Red’kin, B. S. Magnetoelectric properties
should now become dominant, but P 1 is in the direction opposite of some rare earth molybdates. Ferroelectrics 161, 43–48 (1994).
12. Kimura, T. et al. Magnetic control of ferroelectric polarization. Nature 426, 55–58 (2003).
to E pole, consistent with the above experimental results. This 13. Hill, N. A. Why are there so few magnetic ferroelectrics? J. Phys. Chem. B 104, 6694–6709 (2000).
phenomenon is truly unique in the sense that a magnetic field 14. Rivera, J.-P. On definitions, units, measurements, tensor forms of the linear magnetoelectric effect and
can leave a permanent polarization imprint even after removing on a new dynamic method applied to Cr-Cl boracite. Ferroelectrics 161, 165–180 (1994).
H. Thus, the polarization state ‘remembers’ the applied electric as 15. Schmid, H. On a magnetoelectric classification of materials. Int. J. Magn. 4, 337–361 (1973).
16. Popov, Yu. F. et al. Low-temperature phase transition in EuMn2O5. Physica B 284–288, 1402–1403
well as magnetic field. (2000).
The aforementioned polarization switching by applied magnetic 17. Popov, Yu. F. et al. Features of the magnetoelectric properties of BiFeO3 in high magnetic fields. J. Low
field results in a giant magnetocapacitance effect5,7. Figure 3a shows Temp. Phys. 27, 478–479 (2001).

NATURE | doi:10.1038/nature02572 | www.nature.com/nature 3

NATURE 2572—12/5/2004—VBICKNELL—104170
letters to nature
18. Saito, K. & Kohn, K. Magnetoelectric effect and low-temperature phase transitions of TbMn2O5. 26. Maisonneuve, V., Cajipe, V. B., Simon, A., Von Der Muhll, R. & Ravez, J. Ferrielectric ordering in
J. Phys. Condens. Matter 7, 2855–2863 (1995). lamellar CuInP2S6. Phys. Rev. B 56, 10860–10868 (1997).
19. Golovenchits, E. I., Morozov, N. V., Sanina, V. A. & Sapozhnikova, L. M. Correlation of magnetic and 27. Nakamura, N. & Kohn, K. Magnetoelectric effect of rare earth manganese RMn2O5. Ferroelectrics 204,
dielectric properties in EuMn2O5 single crystals. Sov. Phys. Solid State 34, 56–59 (1992). 107–114 (1997).
20. Goshen, S., Mukamel, D., Shaked, H. & Shtrikman, S. Magnetic symmetry and ferroelectricity
induced by antiferromagnetic transitions. J. Appl. Phys. 40, 1590–1592 (1969).
Acknowledgements This work was supported by the National Science Foundation-MRSEC, and
21. Buisson, G. Structures magnétiques sinusoı̈dales et hélicoı̈dales de la terre rare dans TMn2O5. Phys.
J.S.A. was primarily supported by the Korea Science and Engineering Foundation through the
Status Solidi A 17, 191–198 (1973).
Center for Strongly Correlated Materials Research, Seoul National University.
22. Gardner, P. P., Wilkinson, C., Forsyth, J. B. & Wanklyn, B. M. The magnetic structures of the rare-earth
manganates ErMn2O5 and TbMn2O5. J. Phys. C 21, 5653–5661 (1998).
23. Inomata, A. & Kohn, K. Pyroelectric effect and possible ferroelectric transition of helimagnetic
GdMn2O5, TbMn2O5 and YMn2O5. J. Phys. Condens. Matter 8, 2673–2678 (1996).
Competing interests statement The authors declare that they have no competing financial
24. Sawada, A., Ohya, S., Ishibashi, Y. & Takagi, Y. Ferroelectric phase transition in (NH4)2SO4-K2SO4
interests.
mixed crystals. J. Phys. Soc. Jpn 38, 1408–1414 (1975).
25. Sawada, A. & Tomatsu, M. Ferrielectric behaviors in Li2Ge7O15 crystals. Ferroelectrics 137, 297–302 Correspondence and requests for materials should be addressed to N.H.
(1992). ([email protected]).

4 NATURE | doi:10.1038/nature02572 | www.nature.com/nature

View publication stats