Introduction

1. Transition Metal and rare earth Oxides

2. Ferroelectricity and Ferromagnetism

3. Multiferroics

4. Type-I and Type-II

5. Applications and latest research

6. Issues and Motivation of the present work

i. Delafossites- CuFeO2

CuCrO2

ii. Colossal dielectric constant,magnetism,relaxor ferroelectricty

iii. Orthoferrites- spin reorientation

7. Organization of the Thesis- Chapterwise

Introduction

Transition-metal (TM) and rare earth (RE) based oxides, which form an important
category of materials have been attracting intense attention from the condensed matter
community since exhibit a rich variety of electronic, structural, magnetic and
electrical properties []. Fascinating electronic and magnetic properties of TM oxides
are driven by the nature of outer d electrons, while those of RE oxides are governed
through interactions between valence d and f electrons. These oxides show diverse
electrical properties being good metals at one end [e.g. CrO 2, RuO2, NbO, TiO, NiO3,
LaNiO3] and strong, large-gap insulators at other end [e.g. MnO, NiO, La 2O3,
BaTiO3]. There are also oxides that exhibit metal–insulator transitions with some
external perturbations such as change of temperature, pressure, or composition (e.g.
V2O3, La1-xSrxVO3). Their magnetic properties are also very diverse; which is ranging
from the long range ferromagnetic e.g., Fe 2O3, EuO antiferromagnetic e.g. NiO,
Mn2O3, Co3O4 to ferrimagnetic (canted AFM) e.g. Fe3O4, Ni(Co)Fe2O4.
TM and RE based oxides exhibit interesting properties such as ferroelectricity[],
magnetism[], magnetoresistance[], strong electron correlations[], colossal dielectric
constant[], metal to insulator transitions[], superconductivity[], topological insulator[],
charge density waves covering a vast range of phenomena in solid-state physics.
These properties make them useful for various applications such as supercapacitors[],
spintronics, thermoelectrics, battiers [], catalyst[]. Oxide complexes of TMs (TM
surrounded by oxygen) exhibit variety of structures and properties due to unique
nature of their outer shell d-electrons.[]
The crystal structure plays an important role in the observed physical and chemical
properties of the material. Therefore, it becomes essential to develop the
understanding of structure-property correlation in order to investigate the microscopic
origin of the physical properties. This thesis deals with investigation of the structure-
property correlation in TM based delafossites (CuMO2, M = Fe and Cr) and RE based
orthoferrite (NdFeO3), which are known to be type-II multiferroic (MF) compounds.
Thus, it is essential to highlight some important aspects related to phase transition in
these TM and RE oxides, which is originating from the octahedral distributions along
with the possible spin ordering which actually governed through indirect exchange
mechanism. These indirect magnetic interactions in these Mn based oxides are
explained by super-exchange interactions. The other important phenomena crystal
field splitting, John-teller distortion, magnetic ordering and spin-phonon/ lattice
coupling are also arising in these systems and discussed below in detail.

Crystal field splitting

The crystal field is the internal electric field an ion experiences that originates from
neighbouring ions in a crystal. In this approach, the crystal field around a given ion is
modelled electrostatically by approximating neighbouring orbitals as point charges,
which in most cases provides a reasonable description in TMO. This effect is of
particular importance for TM ions in crystalline solids as it explains the splitting of
energy levels in the d subshell, and furthermore allows the prediction of the magnetic
moment from Hund's rules []. In most of the TMO, either six or four ligands (oxygen
ions) surround the cation, this gives the octahedral or tetrahedral structure. The
coordination of cation and the negative oxygen ions (octahedra and tetrahedral)
produces splitting of five d orbitals (dxy, dxz, dyz, dx2-y2, and dz2). The resultant lift in
degeneracy between orbitals is thus referred to as crystal field splitting, with the
energy difference between higher and lower energy levels being the crystal field
energy. (Fig. 1.2).In both these cases the field (repulsion) produced by the oxygen
ions are not spherically symmetrical. Thus, the five d orbitals are not all affected
equally by the surrounding oxygen. For an octahedral structure, the metal ion at the
centre of the octahedron and the oxygen ions (ligands) are at the six corners. In an
octahedral crystal field, the d orbitals get split into two groups (t2g and eg) of different
energies. The t2g orbitals are at the lower energy than the e g orbitals this is due to the
fact that the lobes of the eg orbitals (dx2-y2, dz2) point along the axis x, y and z
whereas the lobes of the t2g orbitals (dxy, dxz, dyz) point in between the axis. For the
tetrahedral field the above situation will be reverse.The d orbitals splitting in case of
octahedra crystal field is presented in Figure 1.1. Thus, following the Hund’s rule
[28], for e.g. in Cr3+ the electronic configuration is 3d3 in which the low lying t2g
levels are first filled according to Hund’s rule and e g levels remain empty, so
degeneracy is removed.
Colossal dielectric constant
The materials described above although having high dielectric constant are not robust
against the frequency and temperature. In 2000, Subramanian discovered a huge
dielectric constant (~104) independent of temperature and frequency over their large
ranges, in ceramic as well and in single crystal form of CaCu3Ti4O12 [10, 11]. The
crystal structure of CaCu3Ti4O12 at room temperature was determined to be
Perovskite cubic, with lattice parameter 7.39Å and space group Im3. [10].
CaCu3Ti4O12 unit cell size of 2×2×2 times the Perovskite ABO3 unit cell, and is
represented by the general formula A′A′′3B4O12 where A′-site is occupied by Ca, Sr,
and Ba, A′′- site is occupied by a magnetic active element Cu2+, and B-site is placed
by Ti4+ element. In CCTO, the Ti-O6 octahedra are largely tilted to form a square-
planer arrangement of Cu-O4 [10]. A typical picture of a complete unit cell is shown
in fig. (3).
In 2002 Homes [11] performed low-temperature dielectric and optical measurements
on CCTO and observed that the dielectric constant of CCTO reduces on cooling by
almost two orders of magnitude, without any ferroelectric or relaxor kind of
transition. However, the theoretically calculated/predicated value of the dielectric
constant is less than 100 [12], two orders of magnitude less than actually observed. In
the last decade, it was a controversial issue as to how CCTO has such a huge
dielectric constant and why it shows orders-of-magnitude drop on lowering the
temperature, without any electrical ordering. Various physical models were suggested
to explain this behavior e.g., internal barrier layer capacitance (IBLC)
model,nanoscale charge ordering electrode effect etc, with a brief discussion given
below.

Ferroelectrics
Ferroelectrics are the materials in which spontaneous electric polarization can be
reversed by the application of an external electric field. Ferroelectricity was
discovered for the first time for Rochelle salt having chemical formula
NaKC4H4O6H2O by Valasek et al. in 1921 [1]. The most famous ferroelectric BaTiO 3
was discovered in 1942 [4]. Subsequently, many other ferroelectric ceramics have
been developed, including perovskites and mixed perovskites such as KNbO3,
PbTiO3, PMN, and PZT etc. or more complex structures such as Aurivillius phases or
tungsten bronzes [].
Ferroelectric materials are identified by the occurrence of ferroelectric hysteresis-loop
in the polarization (P) vs electric field (E). The spontaneous polarization of a
ferroelectric material is called the remanent polarization (Pr), the electric field
required to decrease the polarization to zero is called the coercive field (Ec), and the
saturation polarization is denoted as Ps. This P-E hysteresis loop in ferroelectric
materials is a consequence of the energy barrier when switching from one polarization
direction to another. Regions of similar polarization directions in a ferroelectric
material are called ferroelectric domains which are separated by domain walls. The
thickness of the domain wall ranges typically from 1-10 lattice parameters across.The
domain walls are generally formed to reduce the energy of the system. The grain size,
crystal symmetry, magnitude of spontaneous polarization, defect structure, as well as
the sample geometry and the method of preparation contribute to the size and
structure of these domains.The application of an external electric field to a
ferroelectric material leads to the growth of the domains in which the polarization
orientation is parallel to the direction of application of the electric field. The growth
of the domains is followed by a domain wall movement.
Symmetry plays crucial role in the origin of ferroelectricity. Amongst the 32 crystal
classes, 11 cannot show ferroelectricity because they are centrosymmetric and the
application of an electric field; these materials are polarized linearly, exhibiting a
dielectric polarization. Remaining 21 crystal classes are piezoelectric crystals (with
the exception of one), which means that the application of a mechanical strain causes
an electric current to flow in a certain direction through these materials. Of the 20
piezoelectric classes, 10 have a single polar axis per unit cell and therefore these are
spontaneously polarized [39], which is temperature dependent (also called
pyroelectrics). A material can be ferroelectric only in certain temperature range
because of its crystal structure or symmetry, responsible for spontaneous polarization
(Pr). This high temperature paraelectric phase undergoes to a ferroelectric phase
through a phase transition below certain temperature called phase transition
temperature or Curie point (Tc). This transition is connected with a lowering of
crystal symmetry which leads to appearance of the spontaneous polarization.
BaTiO3 shows a series of ferroelectric phase transitions on cooling from high-
temperature paraelectric phase (>123°C) to low-temperatures.

t has the ABO3 type Perovskite structure; A-site is occupied by the Ba2+ ions and the
B-site is occupied by Ti4+ ions forming a TiO6 octahedra cage. It is a displacive
material in which ferroelectric state is formed due to the displacement of the Ti-ions
in the TiO6 octahedra cage, resulting in a net spontaneous polarization. Many
properties like lattice constant, polarization etc. exhibit discontinuities at the transition
temperatures, as shown in Figure (1). The dielectric permittivity (ε’) shows a sharp
peak at the Curie temperature (Tc) and follows the Curie-Weiss law (for T > Tc) given
as follows

where C is Curie constant, Tc is the Curie temperature; ε∞ is the dielectric

permittivity contribution due to electronic polarizability.

Figure: phase transitions in barium titanate single crystals observed through changes in the unit cell
parameters [32], spontaneous polarization [33], and dielectric constant [15], reproduced from the
respective sources.

Relaxor- ferroelectricity
Relaxor ferroelectrics exhibit outstanding dielectric, electromechanical, electro-
caloric, and pyroelectric properties []. The term ‘relaxor’ refers to its dielectric
maximum over a broad temperature range, rather than a sharp Curie–Weiss
divergence, and its frequency dependent dielectric response. Out of RFEs family, Pb-
based mixed perovskite structure having general formula Pb(B1B2)O3 (where B1 =
Mg2+, Zn2+, Ni2+, Co2+, In3+, Sc3+, Fe3+ etc. and B2 = Ti4+, Zr4+, Nb5+, Ta5+,
V5+, Te6+, W6+ etc.) are widely studied. Lead magnesium niobate (PMN) is the first
relaxor ferroelectric discovered in the late 1950s, has received special recognition due
to their extraordinary properties viz., high dielectric constant (~20,000) over a wide
temperature range near room temperature, inability to sustain a remnant polarization
until temperatures significantly below the dielectric constant maximum (ε'm),
hysteresis loss free polarization-electric field (P-E) loop at room temperature [3].PMN
has the ABO3 cubic perovskite structure with a mixed B-site. X-ray and neutron
diffraction studies confirm the cubic symmetry of PMN with space group Pm3m
down to 5 K [4]. However, at present widely accepted picture of PMN is unveiled by
local probes (e.g., diffused neutron scattering, TEM and Raman spectroscopy etc.);
where coexistence of chemical ordered regions (CORs) with a Fm3m symmetry and
polar nano regions (PNRs) with a rhombohedral R3m symmetry is observed in
paraelectric matrix with a cubic Pm3m.symmetry as shown in Fig. 1.1 [5-7]. It is
believed that the presence of PNRs is responsible for the high dielectric and
piezoelectric properties of relaxors. These PNRs are permanently correlated dipole
moments (giant dipoles) composed of many unit cells, which appear at a temperature
TB ~ 600 K (Burns temperature), which is characterized by deviation from its linear
temperature dependence in volume, inverse susceptibility and refractive index [8].
Microstructural evolution with temperature has revealed an increase in number and
size of the PNRs on cooling below the TB and these PNRs are reported to become
static around T* ≃400 K [9-11]. Finally PNRs collapse around the CORs into
elliptical shape with maximum size of ~10-20 nm near ~220 K, as measured by TEM
and diffused neutron scattering (Fig. 1.2) [10,11]. The interaction/coupling between
the PNRs is not sufficiently strong in order to get long range ordering.
Relaxor ferroelectrics were discovered by Smolensky group [6]. In contrast to the
usual ferroelectrics (e.g., BaTiO3), relaxors show unusually large dielectric constant
over a broad temperature range (∆T ~100K). Frequency-dependence is attributed to
the formation of the polar nano regions (PNR) [7] below a certain, Burns temperature
[7]. In PNR’s, a local polarization might be occurring and responsible for the huge
permittivity. PbMg1/3Nb2/3O3 (PMN) is a muchstudied relaxor ferroelectric [8]
whose real permittivity is given in figure (2). The dielectric constant shows
frequency-dependent maxima, whose value decreases with increasing frequency and
the maxima shift to higher temperatures [9]

Spin re-orientation transition

The process in which the direction of the easy axis of magnetization changes from one
crystallographic axis to another under the external field (magnetic field, temperature,
pressure, laser pulse etc.) is called a spin reorientation transition. In case of perovskite
oxides, it is most commonly shown by rare earth orthoferrites (RFeO3, R= rare earth
ion), orthochromites(RCrO3), Nd–Fe based intermetallic compounds such as Nd2Fe14B
[4], NdDyFe14B [5], Nd6Fe13Si [6], as well as in oxides NdFeO3 [7], SrNdFeO4 [8],
and CaNdFeO4 [9
In order to interpret the mechanism of the second-order spin reorientation transition,
Horner and Varma proposed a phenomenological treatment in Landau mean field
theory.[] In their report on the investigation of spin reorientation in RFeO 3
compounds [43], Levinson et al have proposed that the spin reorientation may occur
in two ways, (1) The spin easy axis rotates gradually by 90 degrees between a
temperature interval and (2) that the easy axis changes abruptly with a possibility of
thermal hysteresis. Researchers attempted to explain the spin reorientation by
considering a large magnetocrystalline anisotropy of the rare earth ions in RFeO 3 and
proposed that the interaction between the rare earth and transition metal moments
causes the moment direction in the transition metal sub-lattice to rotate by 90 degrees
at low temperatures [39,44,45].
Jacob et al in their report [38] made it clear that the presence of anisotropy is a must
for a material to show spin reorientation. T. Yamaguchi [46], later pointed out that the
explanations/theories given in ref [41,43] don’t explain properly the case where the
spin direction changes gradually with temperature, also, in most of the cases the spin
reorientation takes place at relatively high temperatures [39,47,48,49].
This suggest that contrary to the earlier explanations, the anisotropy of the rare earth
ion order does not play an important role in the spin reorientation. Yamaguchi has
studied the role of antisymmetric and anisotropic-symmetric exchange interactions
between transition metal and rare earth ion in spin reorientation and has explained the
mechanism of continuous and abrupt spin reorientation. The aforementioned
interactions create an effective field for the transition metal ion and as the temperature
is lowered, the increase in the rare earth moment causes the effective filed to increase
and the competition between the interaction energy of the transition metal spins with
effective fields and the anisotropy energy of the transition metal ion dictates the
dynamics of the spin reorientation.
The first neutron diffraction evidence of the spin reorientation process in NdFeO3
[25] has shown a gradual change of the ordered Fe 3+ magnetic moment from Gz type
to Gx type between 70 and 160 K. Further high-resolution neutron diffraction
measurements [7, 15] have confirmed a continuous spin reorientation process in the
range from 105 K up to 180 K and that the ordering below and above the reorientation
transition, i.e. at 200 and at 50 K, differs slightly from the pure Gx and Gz modes, as
shown in table 1. The spin reorientation transition in NdFeO3 has been also studied in
previous decades by several techniques including NMR [31, 32], Young’s modulus
[33] and magnetic susceptibility [30, 33, 34]. Other evidence of the spin reorientation
in NdFeO3 has been obtained by inelastic neutron scattering measurements [35]. The
ground-state doublet of Nd3+ ions in NdFeO3 is split by 0.49 meV due to the
molecular field. The inelastic neutron scattering peaks change their shape at
temperatures inside the spin reorientation region due to a change of the distribution of
molecular fields at Nd3+ sites in NdFeO3 [35]. Chen et al., studied theoretically based
on density functional theory calculations that the spin reorientation transition of Fe3+
spin sublattice can be ascribed to the exchange interaction between Nd-4f and Fe-3d
electrons, which are mediated by O2- state in Fe-O plane.
The spin reorientation transition can sometimes give rise to many astounding physical
properties. For example, in case of a continuous temperature dependent spin
reorientation, the magnetic structure during the spin reorientation is non-collinear
which allows local non-centrosymmetry and creates a possibility of polarization in an
otherwise centrosymmetric material which cannot have polarization.

Multiferroics
As defined by Schmid in 1994, multiferroics refer to a big class of materials which
exhibit simultaneously more than one primary ferroic order parameter in a single
phase [].
From application point of view, the coupling between these two ferroic orders is
more important. For example, possibility of controlling magnetization by applying
electric field or controlling polarization by applying magnetic field, in a single phase
materials, is of great technological importance.[41-45] Magnetism and ferroelectricity
(FE), as independent phenomena, are rather well studied in condensed matter physics.
The stabilization of FE and magnetism in a single phase is quite difficult due to
demand of two mutually exclusive requirements.[3,33] The magnetic ordering
requires localization of electrons into partially filled d shells and is usually seen in
TMs leading to the metallic behavior. Conversely, FE (and hence electrical
polarization) requires structural distortion of the lattice occurring usually from empty
d shells, and ferroelectric materials tend to be insulators.3,41 This is not the only
constraint, as simultaneous occurrence of magnetic and electric orders is also
prohibited from symmetry considerations. Electrical polarization needs the lack of the
inversion center whereas, magnetic order requires lack of time reversal.33,41
Although, the coexistence of FE with magnetism was initially considered as one of
the rarest of rare phenomena, the evolution of strongly cross-coupled response of
various materials with the spontaneous polarization and the spontaneous
magnetization in the absence of external field has changed the existing scenario
drastically.
Combining Ferroelectroicty nad ferromagnetism
Basically, magnetism and electricity are the two fundamental concepts in physics, and
they co-setup the unified framework of electromagnetism via the four Maxwell
equations.
Ferroelectricity and ferromagnetism (ferroic orderings) are two most important
phenomena, as these properties can be combined together in a single material to make
them functional.[] A compound having transition metal provides magnetic ordering.
But inducing FE in the same phase is not trivial.3,33,41 The path that MF community
adopts is to induce ferroelectricity in a compound (consisting of magnetic elements),
either by BIS or by using some other mechanism.3,41 On the basis of microscopic
mechanism for the origin of FE, the MF materials can be classified into two types, the
type I (proper) and type II (improper) MFs.
However, in crystals, magnetic moment and electric dipole are usually mutually
exclusive, namely only one or neither of them is available in one single
material.Similar physical phenomena in crystals include the mutual exclusion between
magnetism and superconductivity. However, the discovery of high-TC
superconductivity in doped cuprates and iron-based materials breaks through this
exclusion condition, in which the superconductivity always twists with magnetism.
Similarly, the discovery of multiferroicity breaks the principle of exclusion between
magnetic moment and dipole. Extensive research activities in the past decade have
been enabling a comprehensive theoretical framework of multiferroicity to be
gradually established, which can explain many existing experimental observations and
lead to new predictions and experimental findings. In this sense, the past decade of
multiferroicity can be considered as a successful example of exploring the physics of
correlated electronic materials.
Recent years have seen an increasing interest in multiferroics, materials with multiple
memory phenomena (“ferroic” phenomena), and specifically those which are both
magnetic and ferroelectric. This interest is especially due to a sub-family of materials
in which the electric polarization is caused by and is intrinsically coupled to the
magnetic order (type-II multiferroics).
Types of Multiferroics
Type-I
In this type of multiferroic materials there are two different origins for magnetization
and ferroelectricity. Generally, ferroelectricity appears at higher temperatures than
magnetization, and a week coupling of both is present. This group can be further
divided into subgroups on the basis of the mechanism of electric polarization as
follows.
1.6.1: Ferroelectricity due to Lone–Pair Electrons
In this kind of multiferroics, ferroelectricity originates from the unpaired outer 6s or
5s electrons which are stereo-chemically active and do not participate in any chemical
bonding; called the ‘lone-pair’ electrons. These unpaired electrons have large
polarizability, hybridized with the oxygen 2p orbitals, and originate ferroelectricity.
BiFeO3 [36], BiMnO3 [37, 38] and PbVO3 [39] are famous examples of this family.

1.6.2: Ferroelectricity due to Geometric Frustration

In this type of multiferroics, ferroelectricity originates from complex geometrical
frustration, and mostly hexagonal RMnO3-type (R=Y, Ho, Tm, Yb, Lu) multiferroics
belong to this class. A prototype example of this family is YMnO3 [40].
1.6.3: Ferroelectricity due to Charge-Ordering
In some multiferroics, a specific charge-ordering (both site- and bond-type) breaks the
inversion symmetry, leading to the appearance of a spontaneous electric polarization
and ferroelectricity. Most common examples of this type-I multiferroics are Pr1-
xCaxMnO3 and La1-xCaxMnO3 [41]. Another famous example of this kind of
material is LuFe2O4 [42, 43].

Type-II
Ferroelectricity in type-II multiferroics originates from magnetic ordering; and
therefore their strong magneto-electric coupling. Polarization from different magnetic
structures viz. collinear, cycloidal, spiral etc. can be easily understood by
Dzyaloshinskii-Moriya (D-M) interaction [44, 45]. The cycloidal-spiral magnetic
structure is formed due to the competing magnetic interactions of nearest and next
nearest neighbors. Ferroelectric polarization is orthogonal to both the spins’ rotation-
axis S and the magnetic modulation-vector Q. [46], as shown in figure (8).
Based on the type of spin-rotations, these multiferroics are further categorized as
follows.

1.7.1: Ferroelectricity due to Spiral Magnetic Structure

Famous examples of this kind of material are TbMnO3 [47], Ni3V2O6 [48], and
MnWO4 [49]. In TbMnO3 a spin-flop transition is also observed, providing a huge
magnetic control on associated electric polarization, along with the tilt-angle change
(90°) of spins [47].
1.7.2: Ferroelectricity due to Collinear Magnetic Structure
Ferroelectricity in these types of materials comes through the exchange-striction
induced by the collinear magnetic-ordering The distortion induced by different
configurations of up-up (downdown) or up-down and down-up bonds is different, and
responsible for the electrical dipolarordering. Ca3CoMnO6 [50] is a well-known
example of such multiferroic material. RMn2O5-type (R=Tb, Dy, Y, Er, and Ho)
manganites also belong to the same category [51]. Orthorhombic HoMnO3 is another
good example of this kind of multiferroic [52].

Issues and Motivation of the present work

The crystal structure plays an important role in the observed physical and chemical
properties of the material. Therefore, it becomes essential to develop the
understanding of structure-property correlation in order to investigate the microscopic
origin of the physical properties.
In present thesis an attempt has been made to understand correlation between
structural and physical properties of two class of compounds.
(i) Transition metal based delafossites : CuMO2, M = Fe and Cr
(ii) Rare earth based orthoferrite: NdFeO3

History and Current status

Delafossite oxides
The delafossite family of oxides gathers its name from the material CuFeO 2 which
1
was discovered in 1873 by Charles Friedel and is named after Gabriel Delafosse
However, several other ternary oxides with the general formula A 1+B3+O2 were also
shown to crystallize in the delafossite structure 2, and so this name has been used for
denoting compounds with the molecular formula of ABO 2. The A site of the
delafossite is typically a monovalent cation, such as Cu, Ag, Pt, and Pd, while the B
site comprises of a trivalent cation such Fe, Cr, Rh, Co, Al, Sc, Ga, In or even the rare
earth metals such as La. Depending on the orientation of each layer in stacking,
delafossites can crystallize either in rhombohedral (R3¯m) or in hexagonal (P6 3/mmc)
structures, both of which are centrosymmetric structures. It was shown by Huda that
delafossites with B-site elements belonging to group IIIA on the periodic table (Ga,
In) tend to form rhombohedral structures while structures with group IIIB elements
(Sc, Y) in the B-site settle into a hexagonal geometry3
These two structures are shown in Figure 1.1. Therefore, structures of these materials
consist of distorted edge shared BO 6 octahedral layers. The A cation is linearly
bonded to two oxygen atoms of upper and lower BO 6 layers, thus forming a linear O-
A-O dumbbell along the c-axis 1.

Figure 1.1: The two general ABO2 delafossite structure polytypes. (a) R3¯m symmetry group (b)
P63/mmc symmetry group. The lattice constants a and c are shown for both structures.

Delafossites are well known triangular-lattice antiferromagnets and have appeared as

the most typical example of geometrically frustrated spin systems. These materials
have recently attracted much interest because of their intriguing spin driven (type-II)
multiferroicity, which has been shown for CuFeO2 4, AgFeO2 5 CuCrO26 and AgCrO26
systems. Delafossites show ferroelectric polarization induced by the proper screw
helical magnetic orderings.
The neutron diffraction experiments on AgFeO2 demonstrated two successive
magnetostructural phase transitions at TN1 = 15 K, TN2 = 9 K and induced macroscopic
polarization in this system can be understood in terms of the inverse Dzyaloshinskii
Moriya effect 5. Copper based delafossites, CuFeO2 and CuCrO2 are frustrated
triangular lattice antiferromagnets derived from Fe3+ (S = 5/2, t2g3eg2) and Cr3+ (S =
3/2, t2g3eg0), respectively.

Figure : (a) Magnetic phase diagram for Figure: (a) Magnetic susceptibility (b) electric
CuFeO2 under H||[001]. (b) Magnetic field polarization, (c) real and (d) imaginary parts of
dependence of P perpendicular to the c axis. the dielectric constant of a powder sample of
AgFeO2 as a function of temperature. The inset in
(b) is the poling electric field dependence of the
polarization.
Figure: Temperature dependence of magnetic susceptibility, dielectric constant, and electric
polarization P for (a)–(c) CuCrO2 and (d)–(f) AgCrO2 with delafossite structure.

Neutron diffraction study suggests that CuFeO2 undergoes two successive AFM
transitions, one at 14 K and other at 11 K 7 . First it transforms to a partially disordered
phase at 14 K and then to a collinear ordered, four sublattices (↑↑↓↓) phase at 11 K 7 .
These AFM transitions are accompanied by two structural phase transitions, from
rhombohedral (R-3m) to the disordered phase and then to monoclinic (C2/m)
symmetry 8. In CuFeO2, ferroelectricity was discovered in the non collinear magnetic
phase under the application of magnetic field 4 and also by substituting nonmagnetic
trivalent ions for Fe3+ ions 9–12
. Applied magnetic field or non-magnetic impurity
induced helical magnetic order breaks the inversion symmetry and gives rise to
spontaneous polarization. In addition to this, H. Tamatsukuri et al.13 have discovered
ferroelectricity in CuFeO2 through the application of pressure and magnetic field.
Like CuFeO2, CuCrO2 is also type-II multiferroic. Seki et al. have shown that
CuCrO2 exhibits multiferroicity at magnetic ordering temperature (~24K) 6 .Around
this temperature, AFM interaction takes place between Cr 3+ ions that form a triangular
lattice in ab-plane. Because of the geometrical frustration of the antiferromagnetic
interaction, the 120 spin structure is realized at the ground state. Ferroelectricity in
this system has been observed in the magnetically ordered state without the
application of a magnetic field due to proper screw magnetic ordering below Neel’s
temperature6 .
In these improper multiferroics CuFeO2 and CuCrO2 the ferroelectric coupling cannot
be explained by the inverse Dzyaloshinskii-Moriya interaction (DMI) because the
electric polarization P is parallel to the spin14. In CuFeO2, proper screw type of
magnetic ordering was proposed to induce ferroelectricity through the variation in the
metal–ligand hybridization with spin–orbit coupling in this system 15. Kaplan and
16
Mahanti based on a local symmetry theory have shown that a pair of magnetic
atoms with canted spins Sa, Sb can give rise to an electric dipole moment P. Xiang et
al.17 developed a general theory for the FE polarization induced by spin-spiral order
where the coefficients needed to specify this theory are calculated on the basis of the
density functional theory (DFT).
18
The microscopic origin of the polarization of CuCrO2 was studied by Kimura et al.
Spin-polarized neutron study suggest that proper-screw magnetic structure of CuCrO2
induces electric polarization and can be explained by Arima’s theoretical prediction of
spin dependent d-p hybridization19,20. Although no structural transition at T N is
detected through neutron powder diffraction measurements, still a small
magnetocrystalline effect is observed21 Through high-resolution x-ray diffraction and
strain gauge thermal expansion measurements performed on single crystal, and a
slight deformation of the triangular lattice has also been observed 22.
Magnetoelectric (ME) multiferroicity is not the only exotic phenomenon exhibited by
this family of materials; these materials also have other specific applications as
thermoelectrics, catalysts, luminescent materials, p-type semiconductors used in solar
cells 23–29
Orthoferrites
Apart from delafossites, orthoferrites form another interesting class of type-II MF
materials showing fascinating magnetic, ferroelectric and optical properties, also with
potential technological applications as magnetocapacitors, ultrafast magneto-optical
sensors etc. [23]. These materials show various interesting phenomena such as spin-
reorientation, magnetization reversal as a result of interactions between two magnetic
sub-lattices of iron and rare earth ions e.g., Fe3+-O-Fe3+, R3+-O-Fe3+ and R3+-O-
R3+ [24]. Orthoferrites have gained a lot of interest after discovery of multiferroicity
in these compounds [25–27]. These materials show coexistence of weak
ferromagnetism and ferroelectricity. These materials are weak ferromagnets (canted
AFM), unusually exhibiting large antisymmetric exchange interactions.
Ferroelectricity in these materials arises via exchange striction or inverse
Dzyaloshinskii–Moriya (DM) interaction [25–27]. There are few reports about the
multiferroicity of NdFeO3 where ferroelectricity observed in centrosymmetric
structure (Pbnm) was attributed to inverse DM interaction [28,29]. There remains a
number of questions with respect to underlying physics of spin-reorientation,
especially the role of structure around spin-orientation transition (SRT) region, which
has rarely been discussed in literature [30]. Also, there is a lack of detailed study of
dielectric, magnetic and ferroelectric properties of NdFeO3. Motivated by this, we
have explored these properties and their structural correlation in multiferroic NdFeO3
system.

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Motivation of the present work

There are several issues, those needs to be discussed in order to understand the
microscopic origin of multiferroicity in these systems. Although there are few reports
available on structural phase transition in CuFeO2 associated with the AFM transition
in close proximity of ordering temperature [10,17], still there is a lack of detailed
structural study from room temperature (R-3m) down to the low temperature phase
(C2/m). It is imperative to find out the nature of phase transition through variation of
bond lengths and bond angles. Therefore, we have studied the phase transition
through detailed analysis of temperature dependent X-ray diffraction (XRD)
measurements. Apart from the average structure as probed by XRD measurements,
the roles of oxidation states of TM ions and local structure in driving structural and
magnetic phase transitions have also been explored using X-ray absorption near edge
spectroscopy (XANES) and extended X-ray absorption fine structure spectroscopy
(EXAFS) respectively, as has been studied for several TM oxides in the literature
[18,19]. Such studies are rare in the literature for CuFeO2 as well as for CuCrO2
systems. This has motivated us to investigate the local structure across structural and
magnetic transitions in these systems.

Recently there has been a great interest for materials showing large dielectric constant
due to their demand in the electronic industry for various applications, such as
memory devices, capacitors, and energy storage devices [20]. Dielectric properties of
CuFeO2 and CuCrO2 systems are reported only in the immediate vicinity of magnetic
transitions i.e. at very low temperatures of T < 30K [21,22]. The dielectric dispersion
mechanism could be important from basic physics as well as technological point of
view in the vicinity of room temperature. Such studies are yet to be performed in
these systems. This has motivated us to explore dielectric properties of CuFeO2 and
CuCrO2 near room temperature (85K-450K), i.e. well above the magnetic ordering
temperatures.
As mentioned earlier, both CuFeO2 and CuCrO2 exhibit the same crystal structure
(R-3m) at room temperature, however, their dielectric and magnetic properties are
different as these properties arise from different interactions. We have attempted to
couple these interactions by mixing Fe and Cr ions at B site. With this motivation we
have investigated structural and physical properties of intermediate compounds
CuCr1-xFexO2 with different compositions (x = 0.1 to x = 0.9) and have compared
the results with the parent compounds CuCrO2 (x = 0.0) and CuFeO2 (x = 1.0).