Multiferroics: An Introduction

R.N.P. Choudhary and S. K. Patri

Department of Physics and Meteorology, Indian Institute ofTechnology

Kharagpur - 721 302, India

Abstract. Multiferroics: the multifunctional materials exhibit the entwined nature between the
two distinct phenomena of ferroelectricity and ferromagnetism, which allow them to utilize for
novel device concepts that would not be attainable by either ferroelectric or ferromagnetic
materials. Magnetic and ferroelectric materials are time-honoured research subjects which have
led to new discoveries, both scientific and technological. Multiferroic compounds are the source
of magnetoelectric (ME) effects that are strong enough to induce magnetic or electric phase
transitions, thus exerting ME phase control. The giant response can be generated by the presence
of exceptionally large magnetic and/or electric fields in matter, which are the result of the long-
range ordering. In this sense the ME effect in multiferroics is 'large' if the ME contribution
corresponding to the free energy of the system is large. Due to their interesting physical,
chemical, and mechanical properties, these materials have been used to realize a vast number of
devices ranging from giant devices like electrical transformers to tiny devices like sensors, used
in integrated circuits or as storage devices. Furthermore, these materials are likely to offer new
kinds of devices and functionality, because of their size-dependent physical and chemical
properties, which have motivated a lot of current research activity in the area of ferroelectric and
magnetic materials. In particular, advances in atomic and nanoscale growth and characterization
techniques have led to the production of modern ferroelectromagnetic materials that reveal a
range of fascinating phenomena. These phenomena derived from the fact that electrons have spin
as well as charge, giving an extra level of complexity to the physics, and an extra degree of
freedom in device design. Magnetoelectric coupling between electric and magnetic order
parameters has been theoretically predicted, and there is intense interest in its implementation in
device architectures taking advantage of these properties. Multiferroics may be in the form of
single-phase, exhibit mulitferroicity generally at low temperatures and in a composite form as a
product property of a composite phase consisting of a magnetostrictive and a piezoelectric
material. Hence, the search continues for new single-phase and composite multiferroic materials
that exhibit high ordering temperatures, high coupling constant, low dielectric loss and low
leakage current.

Keywords: Magnetoacoustic effects. Transition-metal compounds. Composite materials,

antiferromagnetics
PACS: 72.55.+S, 72.80.Ga, 72.80.Tm, 75.50.Ee

INTRODUCTION

Multiferroics with multiple (charge, spin) order parameters; offer an exciting way of
coupling between electronic and magnetic ordering [1]. In these materials, a weak
magnetoelectric interaction can lead to spectacular cross-coupling effects when it
induces electric polarization in a magnetically ordered state. Most of the work on these

CPIOG^, Mesoscopic, Nanoscopic, and Macroscopic Materials, edited by S. M. Bose, S. N. Behera, andB. K. Roul
© 2008 American Institute of Physics 978-0-7354-0593-6/08/$23.00

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materials on control charges by applied magnetic fields and spins by apphed electric
field, are useful to construct new type of multifunctional devices. It was proved to be a
difficult problem towards bringing ferroelectricity and magnetism together; as these
two contrasting order parameters turned out to be mutually exclusive [2-5]. Further, it
was found that the simultaneous presence of electric and magnetic dipoles does not
guarantee strong coupling between the two, as microscopic mechanisms of
ferroelectricity and magnetism are quite different and do not strongly interfere with
each other [6, 7]. Thus, there are very few materials which display the multiferroic
properties [8-16]. The rareness of the ferroelectromagnets is ascribed to the fact that
ferroelectricity and ferromagnetism are incompatible (e.g. ferromagnetic perovskites
such as (La, Sr) MnOs and (La, Sr)Co03 are generally metalhc, while ferroelectric
perovskites are insulator). The scarcity of multiferroics has resulted in the various
obstacles for their utilization in multifaceted potential apphcations. Thus, some
challenges developed in order to have multiferroic at moderate temperature with high
coupling coefficient for potential device application. From the physical point of view
multiferroics present an extremely interesting class of systems and problems. There
are essentially two conditions for occurrence of this phenomenon: (i) microscopic
condition, which determines the possibility to combine in one system both magnetic
and ferroelectric properties, and (ii) the coupling between different degrees of freedom
or order parameters. Different techniques can be adopted for the design of
multiferroicity in materials; including doping of appropriate elements in a given host
material which results in inducing the functional properties. In this paper, we discuss
the origin and cause of multiferroicity, previous works on some well known family
and some recent development on some multiferroics.

REQUIREMENTS FOR MULTIFERROICITY

By definition, for a material to be a magnetoelectric multiferroic; it must be
simultaneously ferromagnetic and ferroelectric. Therefore, its allowed physical,
structural and electronic properties are restricted to those which occur both in
ferromagnetic and in ferroelectric materials. Basic requirement for the effect is the
coexistence of magnetic and electric dipoles. The exceedingly rare occurrence of
multiferroicity is due to the exclusiveness of partially filled atomic orbitals, for
magnetic dipoles or moments and the occurrence of local electric dipoles, which are
typically associated with the presence of either empty d-shells and/or an electron lone-
pair configuration. In fact, the materials exhibiting the ME effect can be classified as:
single phase and composites. Single phase materials will have an ordered structure.
The ME effect arises in this class of materials due to the local interaction between the
ordered magnetic and ferroelectric sublattices. The conditions for the occurrence of
ferroelectricity and magnetic order in the same material often accompanied by
ferroelasticity which implies (a) the presence of adequate structural building blocks
permitting ferroelectric-type ionic movements, (b) magnetic interaction pathways,
usually of the superexchange type, and (c) the fulfillment of symmetry conditions
[17]. In composite materials, a suitable combination of two phases can yield the

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desirable properties such as a combination of piezomagnetic and piezoelectric phases
or a combination of magnetostricitve and piezoelectric phases. The ME effect can also
be reahzed by couphng the thermal interaction in pyroelectric-pyromagnetic
composites. The ME coefficient of composites is more than a hundred times that of
single-phase (ME) materials [18].

PREVIOUS WORK
To achieve rich functionality; one of the very promising approaches to create novel
materials is to combine different physical properties in a single material. Two
independent events mark the birth of the ME effect: (i) in 1888 R'ontgen discovered
that a moving dielectric became magnetized when placed in an electric field [19],
which was followed by observation of the reverse polarization effect of a moving
dielectric in a magnetic field (17 years later) [20], and (ii) in 1894, Curie pointed out
that it would be possible for an asymmetric molecular body to polarize directionally
under the influence of a magnetic field [21]. The term 'magnetoelectric' was coined
for the first time by Debye |^22], a few years after the first (unsuccessful) attempt to
demonstrate the static ME effect experimentally [23, 24]. In spite of Curie's early
recognition of symmetry being a key issue in the search for ME behavior, many
decades passed until it was realized that the ME response is only allowed in time-
asymmetric media [25]. Such violation of time-reversal symmetry can extrinsically
occur through application of an external magnetic field or movement as in the historic
experiment conducted by R'ontgen, or intrinsically in the form of long-range magnetic
ordering. Dzyaloshinskii [26] was the first to show violation of time-reversal
symmetry explicitly for a particular system (antiferromagnetic Cr^O,), which was soon
followed by experimental confirmation of an electric-field-induced magnetization
[27] and a magnetic field- induced polarization [28, 29] in Cr^O,.
The search for ferromagnetism-ferroelectricity in the same material began in Russia
in the 1950s, with the replacement of some of the d° B cations in ferroelectric
perovskite oxides by magnetic d" cations [30, 31]. Later, Landau and Lifshitz [32]
showed from symmetry considerations that a linear ME can occur in magnetically
ordered crystals. Subsequently, Dzyaloshinskii [33], on the basis of theoretical
analysis, predicted the existence of the ME effect in antiferromagnetic Cr203. This
was confirmed by Astrov [34] by measuring the electric field induced magnetization
and later by Rado and Folen [28, 35] by detection of the magnetic field-induced
polarization. Smolenskii and Loffe [36] in 1958 synthesized the antiferromagnetic-
ferroelectric perovskite ceramic Pb(Fei/2Nbi/2)03 (PEN). The first synthetic
ferromagnetic ferroelectric material, (l-x)Pb(Fe2/3Wi/3)03 - x Pb(Mgi/2Wi/2)03, was
produced in the early 1960s using this approach. Here the Mg^^ and W^^ ions are
diamagnetic and cause the ferroelectricity, and the formally d^ Fe^^ ions are
responsible for the magnetic ordering. Other examples include (a) B-site ordered
Pb2(CoW)06 which is ferroelectric and ferromagnetic, (b) B-site disordered
Pb2(FeTa)06 [37] which is ferroelectric and antiferromagnetic [38, 39]. Because of
dilution of the magnetic ions, these materials have rather low Curie or N'eel

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temperatures. The attempts to combine in one system both the (ferro)magnetic and
ferroelectric (FE) properties started in 1960's, predominantly by two groups in then
the Soviet Union: (i) the group of Smolenskii in St.Petersburg (then Leningrad) [40,
41] and (ii) by Venevtsev in Moscow [42]. Materials combining these different
"ferroic" [43] properties were later on called "multiferroics" [44]. Since then the
probability of new techniques has been reahzed for such novel materials for very
promising applications in diverse fields. [45-48]. In composite materials, the ME
effect is realized by using the concept of product properties introduced by Van
Suchetelene [49]. In 1978, Boomgaard [50] outhned the conceptual points inherent to
the ME effect in composites. These can be summarized as follows: (i) two individual
phases should be in equilibrium, (ii) mismatching between grains should not be
present, (iii) magnitude of the magnetostriction coefficient of piezomagnetic or
magnetostrictive phase and magnitude of the piezoelectric coefficient of the
piezoelectric phase must be greater, (iv) accumulated charge must not leak through the
piezomagnetic or magnetostrictive phase and (v) deterministic strategy for poling of
the composites. The basic ideas underlying composite electroceramics can be
classified into three categories: (i) sum properties, (ii) product properties, (iii)
combination properties [49-53]. On the basis of point group symmetry, Aizu have
enlisted a number of possible species of ferroic crystals, their number of orientation
states, and their relationships to ferromagnetism, ferroelctricity, and ferroelasticity
[54]. In 1980, Ismailzade et al. [55] reported the presence of linear ME effect in
BiFeOs, a compound of antiferromagnetic-feroelctric nature. Its combination with
bismuth titanate and barium titanate forms a family with Aurrivilius structure (Bi4Bin,.
sTisFcmjOsm+s) show coexistence of ferroelectric and magnetic nature up to high
temperatures [56]. Schmid [57] has worked onboracites belonging to the large crystal
structure family with a general formula M3B7O13X, where M stands for a bivalent
cation of Mg^^, Cr^^, Mn^^, Fe^^, Co^^, Ni^^, Cu^^, Zn^^, etc. and X stands for a
monovalent anion like OH", F", CI', Br", I" or NO^'.

SOME RECENT WORKS

Since the discovery of multiferroic materials, several attempts were made to study
the magnetoelectric effect in different compounds of many structural families.
Unfortunately, because of some inherent properties (i.e., leakage current, small
coupling coefficient, low temperature phase transition, structural distortion and
stability), the industrial apphcations of these materials were very much limited, and
hence not much attention was paid. The strucutural classification of magnetoelectrics
include perovskies, hexagonal manganites, boracites, rare earth doped manganites,
layered perovskites etc. Though the existence of weak magnetoelectric (i.e., coupling
between magnetic and electric ordering in a monophase distorted structure) effects in
Pb-based complex perovskites, Pb (Fei/2Nbi/2)03, were known for few decades, recent
discovery of the effect in environmental friendly (i.e. free from Pb) rhombohedrally
distorted BiFeOs (BFO) much above room temperature (i.e., TN = 650 K, Tc=IIOOK)
has attracted much attention of researchers to design and develop new/modified

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magnetoelectric materials with high ME coefficients for multifunctional apphcations.
In view of the above, we have also designed and developed (ceramics and composites)
a few Pb/Bi based ferromagnetoelectrics for better understanding, and enhancement of
the ferroelectric/ferromagnetic and couphng properties of materials for possible
devices.

(a) Pb(Fei/2Nbi/2)03

Lead iron niobate Pb(Fei/2Nbi/2)03 [PFN] belongs to the series of complex

perovskite compounds discovered at the end of the 1950s [58]. It was considered to
be ferroelectrically and antiferromagnetically ordered below a certain temperature. Its
(dielectric) Curie temperature is around 383 K and the antiferromagnetic order begins
at about 143 K. In view of the importance of these materials, there have been intensive
studies both on single crystals [59-63] and ceramics synthesized using different
methods [64-72]. Due to their exceptionally high dielectric constant [73], PFN
ceramics are one of the most attractive candidates for making multilayer capacitors.
The presence of magnetic Fe^^ ions in octahedral (Bi) sites of (ABiBii)03 perovskite
lattice makes PFN an interesting single-phase multiferroic material. Majumdar et. al
[74] surprisingly have observed ferromagnetic ordering at room temperature in their
sol-gel-derived PFN powders. It was assumed that any other segregated phase such as
Fe304 is responsible for the observed room-temperature ferromagnetic ordering. In a
disorder perovskite system such as PFN, no cation ordering is expected in between
Fe^^ and Nb^^ cations. But again it was examined that Fe^^-0-Fe^^ spins are no longer
collinear and was concluded that the room temperature behavior is not due to
segregated phase, but as a result of small canting of spins to yield weak ferromagnetic
behavior.

b) Ba Modified Pb(Fei/2Nbi/2)03

Due to the presence of Fe^^, O^" ion vacancies, PFN and related materials (ME)
have high-leakage current which limits the materials for any meaningful devices with
higher sensitivity [75-77]. In order to obtain suitable materials for devices, several
attempts have been made to design and develop materials by substituting
isovalent/nonisovalent elements/atoms at the B-site [78] or fabricating composites of
2-3 components/oxides. In view of the above, the effect of Ba substitution at the Pb-
sites i.e., (i.e., (Pbi-xBax)(Fei/2Nbi/2)03 (PBFN) with x = 0, 0.05, 0.07) have been
synthesized by high-energy ball milhng with particles of nanometer size. A decrease
in phase transition temperature was observed in Ba modified PFN material in
comparison to PFN, which may be due to intergranular stresses, ferroelectric domain
sizes, compositional inhomogeneities, and Ba distribution at the Pb^^ site [79]. The
phase transition behavior in PFN provides a signature of a normal transition of the
paraelectric to the ferroelectric phase type. However on increasing Ba content to x =
70 wt%, a cross-over of phase transition from normal to relaxor ferroelectric was

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 100 200 300 400 SCO eoo rut) BOO
T(K)

100 150 JOO 250 300 350 400 450 500 550
T(K)

FIGURE 1. Temperature dependence of relative dielectric constantEjOf Pbi-jBa^fFeo.sNbosJOs with {a)x

= 0, (b) X = 0.05, and (c) jc = 0.07 at frequencies 100 kHz (n), 250 kHz (o), 500 kHz (A), IMHz (+) [Ref
79].

-P300K
Sf Ms (emu/g)
fa) 3

-2it10'

H(Oe)

0 BO 100 150 2 0 0 250 300

T(K)

FIGURE 2. Variation of (a) magnetization vs. magnetic field at 300 K, (b) magnetization vs.
temperature at 100 Oe, and (c) magnetization vs. magnetic field at 2K of Pbi-jBajfFeo.sNbo.sJOs {x = 0,
j<: = 0.07)[Ref 79]

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observed (Fig.l). It is indeed an interesting and new observation on PFN [20]. A weak
magnetization in PBFN (Fig. 2) is observed which may be largely related to structural
distortion of the parent structure, since the magnetization is crucially dependent on the
symmetry of the system [80, 81]. A stable antiferromagnetic G-type phase of PFN is
related to ferroelectric tetragonal distortion with large shift of the Pb atom [79].

(d) BiFeOs

Recent discovery of ferromagnetoelectricity in BiFeOs (BFO) at high temperature

(Tc = 1 lOOK and TN= 630K) has attracted much attention of researchers to design and
develop (single crystals, thin films and ceramic structure) eco-friendly, toxic free
modified BFO and/or the search of new materials with high magnetoelectric
coefficient above room temperature useful for multifunctional devices. Although
rhombohedral BFO has been studied extensively since 1960s, the electrical properties
of the pure BFO R-phase have been rarely reported due to its high leakage current,
which may be originated from uncertain oxygen stoichiometry, high defect density
and poor sample quality [82-84]. BFO is reported to exhibit eight structural transitions
and a weak ferromagnetic ordering [85-86]. However, it is an antiferromagnet with a
spatially modulated spin structure [87], which does not allow net magnetization and
also inhibits observation of the linear magnetoelectric effect. Spontaneous
magnetization in BFO can be induced by the substitution of Fe^^ by other transition
metal ions [88]. Again B-site ions substitution decreases magnetic ordering
temperature drastically [89] thus hampering their apphcation at room temperature.

(e) La substituted BiFeOs

In order to solve few inherent problems of multiferroics in general, and BFO in

particular, such as high leakage current, structural instability, formation of multiphase
system during synthesis, etc. [90], and to increase the dielectric constant, reduce the
leakage current, and hence to improve the ferroelectric polarization in BFO, some
attempts have been made including a small doping at the Bi/Fe sites. There are also
several reports on the synthesis of sohd solution of BFO with other perovskite
structures (with different concentrations), which has enhanced electrical and magnetic
properties of BFO. Several attempts have been made in recent years including (a)
fabrication of composites, (b) use of different synthesis process, and (c) preparation of
thin films and single crystals. Encouraging results have been obtained on substitution
of La at the Bi-site and/or some isovalent elements at the Fe-site of BiFeOs [91-94]. It
was observed that on La substitution at the Bi site (BFOL) ehminates the small
impurity phase of BiFeOs and stabilized the crystal structure into hexagonal
symmetry. However, the dielectric properties (Fig. 3 & 4) were not enhanced by La
substitution, but systematic increase in both the ferroelectric and ferromagnetic
properties (Fig.5) were achieved. With the increase in La concentration, the magnetic

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parameters increase and this may be due to the doping, which increase the magnetic
anisotropy and magnetization [95].

IJD
• HFD • BFO
4 0 BLFOID * ' BLFDII
• BLFDIi ^ • BLF01S A

a- • BLFOID • « BLfDII %
<i BLfO!
. BLFOI ' >
Frequency = 100 kHz JV OD Fnqueney = 1 MHz '^
c s- 5 04
n
4-1

» 1
n*-/ 0
0 »eHtt««e«ftftB»BDe9l£*Mw -• Oi) !!!'Siiiia*^
100 200 300 400 SDQ GOO 700 100 200 300 400 500 GOO TOO

Tempcratjrc (K) Temperature (K)

FIGURE 3. Variation of dielectric constant with temperature of BFO and BFOL ceramics at 100 kHz
and 1 MHz. [Ref 95]

FIGURE 4. Variation of loss tangent with temperature of BFO and BFOL ceramics at 100 kHz and 1
MHz. [Ref 95]

080 1SGn
- BFD > RF4
4-<
AM

g »)0
•
(
BFOLS
BFOLIO n 13S.
^
° BFOLt
a BFOLIir u
r
m '
»
9F0L1S
BFDLZD "• -.—
C 100
» HFOLH!
1 BFOL30 a
C 400
O
Frequency • 100 kHz • o
" 7S Frcquenef > 1 MHz 3
u
'C
-rt so-
o (j
0) •
O 100 • * "5 26
i5 „ tllHiifiHiliH
tDD 200 300 4DD SQD SOC 7DD
lAO iQD saa 4DQ saa GOO TOO
Temperature (K) Temperature [K}

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 0.4-1 0.01 T ' 1 '

_ 0.2
^•0.01
^
1 0 1
•5
P 00
BFO
T ^ XO K
= .0.2 /
-0.4
/
-iO -4D -20 0 10

H(kOe]
Q.E

a.3
3 '•n—j—]—i
»90ty
P
E Q.D
u •s> BFOLIS
•S'
T = 30D K
-0.3

</>'
-Q.E
-60 -40 20 0 20 40 60
H (kOe)
FIGURE 5. Magnetic hysteresis loops of BFO and BFOL samples. The insets show the details of the
loops for lower fields [Ref 95]

(g) Y Substituted BiFeOj

The orientation of magnetic moments, magnetic moment canting and the spiral spin
structure attributed to weak magnetic characteristics of BFO [96]. Bi substitution by
rare earth ions improves magnetic properties attributed to structural phase transition,
resulting in the release of latent magnetization [97-98]. Mishra et al [99] have
substituted Y at Bi site. Substitution of Y at the Bi site of BFO (BYFO) has caused
compositionally driven structural change and facilitates single-phase formation of the
material by suppressing the pyrochlore phase. This has led to a considerable change in
ferroelectric and magnetic properties of BFO. Up to 10% Y substitution there is a
significant reduction of low frequency dispersion in both permittivity and loss pattern,
indicating a considerable control of dc conductivity thereby enhancing ferroelectric
behavior. However, with Y substitution at the Bi site, a remarkable increase in
macroscopic magnetization and the switching behavior in low fields which are the
most interesting observation of the field dependence of magnetization of BYFO
samples, which makes them different from rare-earth substituted BFO. This unique
magnetic behavior along with the existence of ferroelectricity in these samples makes
them probable candidates for obtaining better magnetoelectric coupling.

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 (i) BiFe03-Bi4Ti30i2 Composites

Among the different ferroelectromagnetic compounds mentioned above, special

classes of bismuth layered structure ferroelectromagnetic (BLSFEM) compounds, of
Aurivillius family [100,101], are found to be interesting because of their
crystallographic anisotropy. From the earlier reports, the three-layered compound
Bi4Ti30i2 has monoclinic symmetry at room temperature with a ferroelectric transition
at 675°C [102], while BiFeOs is ferroelectric and also antiferromagnet with
rhombohedral symmetry at room temperature Combining Bi4Ti30i2 with n moles of
BiFeOs (BFTO), where n = integer, perovskite compounds with four, five, six, seven,
and eight layers (i.e. BisFeTisOis, Bi6Fe2Ti30i8, Bi7Fe3Ti302i, Bi8Fe4Ti3024 and
Bi9Fe5Ti3027) can be synthesized [103]. Rare-earth (Gd^^, La^^, Sm^^, Dy^^)
doping/substitution at the Bi site in these layered compounds have shown interesting
magnetic and ME properties [104-106].

CONCLUSIONS

In reviewing the growth, development and properties of multiferroics, it is worth

discussing the issues of creating new materials and understanding the origin of
multiferroism in them. The mechanisms of the coupling between ferroelectric and
magnetic orders are the most challenging aspects. Nowadays, multiferroic is a topic of
great interest, both in science and technology, because of their interesting properties
and dimensionality for novel advanced devices. Beginning with a brief summary of
the history of the ME effect since its prediction in 1894 by Curie, the paper focuses on
the approaches to ME effect, its chronological development and recent works with
possible future applications. At present the multiferroic and its related phenomena are
primarily interesting from the point of view of basic research rather than applications.
The number of multiferroic compounds is still small, and a continued research is going
on to know the fascinating intriguing features of these materials in different forms
(single crystals, composites and thin films) and only very few multiferroics with ME
behavior at room temperature are known yet. ME behavior in several multiferroics
have been understood and precise criteria for the search of new multiferroics have
been given and future research on their improvement and tuning of their ME
performance should drive multiferroics much closer to practical apphcations in the
near future. In addition, exploration of new classes of multiferroic materials is on
progress in our ongoing research.

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