Ferroelectrics

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A brief review on perovskite multiferroics

Hongbo Liu & Xue Yang

To cite this article: Hongbo Liu & Xue Yang (2017) A brief review on perovskite multiferroics,
Ferroelectrics, 507:1, 69-85, DOI: 10.1080/00150193.2017.1283171

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FERROELECTRICS
2017, VOL. 507, 69–85
http://dx.doi.org/10.1080/00150193.2017.1283171

A brief review on perovskite multiferroics

Hongbo Liua and Xue Yangb
a
School of Materials Engineering, Shanghai University of Engineering Science, Shanghai, PR China; bResearch
Center of Space Laser Information Technology, Shanghai Institute of Optics and Fine Mechanics, Chinese
Academy of Sciences, Shanghai, PR China

ABSTRACT ARTICLE HISTORY

The paper first introduces the basic physics behind perovskite multiferroics. Accepted 8 January 2017
Then the recent progress on simple, complex perovskites, and manganites
KEYWORDS
are briefly reviewed. The review discloses two important directions on Multiferroic; ferroelectricity;
achievement multiferrocity in perovskite: pay with strain engineering and magnetism; perovskite
adjust octahedral deformation. The authors also suggest that specific
issues like leakage current and characterization platforms are also very
important for the study of multiferroics.

1. Introduction
Multiferroics originally refers to a single phase material with two or more primary ferroic
order parameters, such as ferromagnetism, ferroelectricity and ferroelasticity [1]. The cur-
rent researches focus on materials exhibiting both magnetism and ferroelectricity simulta-
neously, which have attracted more attentions for interesting physics and potential
applications in the memory devices [2,3], especially after the discoverings of magnetic con-
trol polarization in TbMnO3 (TMO) [4] and large polarization in BiFeO3(BFO) [5]. Multi-
ferroics with strong magnetoelectric (ME) coupling at room temperature are the most
promising materials for data storage. Unfortunately, TMO has very low ordering tempera-
tures and BFO does not show strong direct ME coupling. Such disadvantages push further
more studies, which are clearly manifested by the exponential growth of publications in the
area [6].
From a structural view, both TMO and BFO coincidentally belong to perovskite structure,
which is perhaps the most adjustable structure model to induce fantastic properties like
superconductivity, ferroelectricity, and ferromagnetism. Nevertheless, in general the chance
to combine both ferroelectric and ferromagnetic in single perovskite is of scarcity [78].
Therefore, sophisticated strategies have been exploited to combine both magnetic and ferro-
electric properties in perovskite-type materials. The goal of the review is to pay attention to
the recent progress on single phase perovskite multiferroics, especially emphasizing on the
relations between the freedoms of structure and the possibilities of combining magnetization
and ferroelectricity in the same phase at room temperature with strong magnetoelectric
coupling. The paper is scheduled as followings. First, a brief physical basis of perovskite

CONTACT Hongbo Liu [email protected]

Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gfer.
© 2017 Taylor & Francis Group, LLC
70 H. LIU AND X. YANG

multiferroic will be introduced. Then, the recent progress on achieving multiferroicity in

perovskites will be given. Finally, the paper will close with a short summary and perspectives.

2. Physics of perovskite multiferroic materials

2.1. The origins of ferroelectric and magnetic orders in perovskite
The ideal perovskite crystallizes in Pm3m space group, which is simple primitive cubic
lattice without any deformation, as depicted in fig. 1. The chemical formula of perovskite is
commonly expressed as ABO3, where A and B are two cations of very different chemical
valences (2C and 4C correspondingly) and sizes, and O is oxygen anion that bonds to both
of them, note that both A and B could be mixed cations of different chemical valences. The
small cation B4C is surrounded by an octahedron of 6-nearest neighbor O2¡ (BO6) and the
large A2C is coordinated with maximum 12-nearest neighbor O2¡. Such coordination form
is stable if the sizes of A2C, B4C and O2¡ vary under the limitation of famous Goldshmidt
tolerance factor t [9]:

rA C rO
t D pffiffiffi (1)
2.rA C rO /

The t factor somehow decides the lattice types of perovskite [10,11] and the delicate
balance could be further influenced by temperature, pressure, electric field, and etc..
The origin of ferroelectricity in perovskite has long been well established by soft mode theory
[12]: the lowest-frequency polar-phonon mode becomes softer during cooling, and finally goes
to zero frequency at TC, which is the critical temperature that the material transforms from ideal
cubic to lower symmetrical ferroelectric structure. Obviously, such structural instability results in

Figure 1. Octahedral framework of ideal cubic perovskite structure, in which the red ball indicates A2C ion,
blue balls represents B4C ions, and oxygen ions are represented by green balls. The dashed lines show
cubic cell.
 FERROELECTRICS 71

Figure 2. The potential shifts of B-site cation (blue ball) in an octahedral framework of ideal cubic perov-
skite structure. The oxygen ions are represented by green balls and red lines show high symmetry axes
along which B-site cation moves.

broking of centrosymmetry and deformation of perovskite, commonly known as second-order

Jahn-Teller Effect [13]. For instance, in classic ferroelectric BaTiO3, Ti4C shifts along C4, C2 and
C3 axises (see fig. 2) and stabilizes in different temperature ranges with tetragonal, orthorhombic
or rhombohedral structures with different spontaneous polarizations [14]. Most of ferroelectric
perovskite oxides, with transition metal ions at B sites as BaTiO3, have empty d electron (d0).
But, keeping in mind, this is not necessary for A-site driven ferroelectrics such as Pb2C and Bi3C
based oxides. Moreover, in both B-site driven ferroelectrics and A-site driven ferroelectrics, the
force favoring ferroelectric state is the long-range coulomb interaction, shortening one or several
B-O or A-O distances [15].
Different to ferroelectricity, the magnetism is governed by quantum-mechanical exchange
interactions, including double exchange interaction and superexchange interaction. The double
exchange interaction induces ferromagnetism [16,17] which is the most promised magnetic
ordering for multiferroic materials used in multi-state memory devices. Unfortunately, the
perovskite materials with ferromagnetic ordering commonly bring itinerant electrons, which
increase the conductivity and destroy ferroelectricity as they screen the long-range coulomb
interactions even if such interactions exist. Thus, the additional attention must be paid to con-
firm the ferroelectricity in magnetic perovskites [18,19]. In general, the perovskite compounds
with double exchange interaction can hardly be multiferroic materials.
Comparison with double interaction, the superexchange interaction in perovskite-type
oxides can induce either ferromagnetism or antiferromagnetism [20–24]. Moreover, these
compounds are commonly insulators, giving ways to combine ferroelectricity and
72 H. LIU AND X. YANG

Figure 3. Strong antiferromagnetic order (a), weak antiferromagnetic order (b), weak ferromagnetic order
(c), ferromagnetic order (d), and antiferromagnetic order (e) induced by superexhange interaction. (f)
represents the legends of electronic orbits for B, B’ and O ions.

magnetism together. For magnetic perovskite oxides, B site cation has partly filled d elec-
trons (dn) and splits into two energy states in oxygen octahedral environment: two high-
energetic eg orbitals (dx2¡y2, d3z2¡r2) and three low energy t2g orbitals (dxy, dyz, dzx) [25]. The
orbitals of two neighboring magnetic cations, coupling through non-magnetic O2¡, can be
parallel or orthogonal, resulting in different magnetic orders (see fig. 3). In short, it is the
configurations of d electrons deciding the magnetic order of materials. For instance, in BFO,
Pb(Fe2/3W1/3)O3 (PFW), PbFe0.5Nb0.5O3 (PFN) and PbFe0.5Ta0.5O3 (PFT), in which B site
occupied by Fe3C(3d5, S D 5/2) with each d orbital filled by single electron, the orbitals of
neighboring Fe3C are parallel with opposite spin directions, producing G-type antiferromag-
netism through Fe3C-O2¡-Fe3C (see fig. 3(a)). Similarly, ferromagnetism could be
produced if the neighboring orbitals of cations are orthogonal with same spin directions, a
case for some double perovskite oxides A(BB’)O3, ordered B and B’ cations with empty and
half-filled eg orbitals (see fig. 3(c)).

2.2. Dzyaloshinsky-Moriya interaction

The model multiferroic BFO, relaxor ferroelectric PFW, PFN and PFT are antiferromagnetic
oxides. But antiferromagnetism is not a primary ferroic order parameter, thus it is less favor-
able for the innovation of memory devices. However, it was reported that a week ferromag-
netism could build on antiferromagnetic order through Dzyaloshinsky-Moriya interaction
[26,27], which is commonly expressed as:

HDM D DBB’ .SB £SB’ / DBB’ / .x£rBB’ / (2)

in which rBB’ is the vector connecting the site B to the site B’ and x is the displacement of the
ligand ion (in perovskite oxides, it is O 2¡) from the BB’ line. From a view of geometry, the
antiferromagnetism is based on 180 of B-O-B’ bond angle and the bending of B-O-B’ bond-
ing in distorted perosvkite would give additional magnetic interaction. By decreasing
exchange interaction and increasing Dzyaloshinsky-Moriya interaction, week ferromagnetic
could be induced [28].
 FERROELECTRICS 73

2.3. Magnetoelectric couling and mutual control

For a multiferroic system, the Landau free energy can be wrote as the function of applied
electric field E and applied magnetic field H [6,29]:

1 1
F.E; H/ D F0 ¡ Pi Ei ¡ Mi Hi ¡ e0 eij Ei Ej ¡ m0 mij Hi Hj
2 2 (3)
1 1
¡ aij Ei Hj ¡ bij Ei Hj Hk ¡ g ijk Hi Ei Ek
2 2

in which a describes the linear magnetoelectric couping, and b and g represent bilinear mag-
netoelectric couping. Pi and Mi are the spontaneous polarization and magnetization in direc-
tion i; e0 and m0 are the permittivity and permeability of free space; and eij and mij are the
relative dielectric permittivity and relative magnetic permeability. The linear magnetoelectric
coupling coefficient a can only occur in ferromagnetic or antiferromagnetic point groups.
Moreover, from Eq. 3 we can see that the electric field (or magnetic field) can induce magne-
tization (or polarization) if a exists in a multiferroic system. Brown proposed the upper
boundary of linear ME coupling as [30]:
pffiffiffiffiffiffiffiffiffiffi
eij mij
aij  (4)
c0

here c0 is the speed of light in vacuum. The formula highlights that large linear ME coupling
can be gotten by large electric permittivity and magnetic permeability even without ferroic
orders. Nevertheless, large permittivity and permeability are commonly expected for
ferroelectric and ferromagnetic materials, although they are not the prerequisites.
It should be noted at here that a can be zero for a multiferroic material because a multi-
ferroics does not necessary to be a magnetoelectric material [29]. And for the applications in
data storage, the most interesting properties are the directions of the magnetization or the
spontaneous polarization can be controlled by an electric or magnetic field respectively[31].
Commonly such effects are achieved by complex scenarios and the following formulas are
used to evaluate the coupling effects:

e.H/ ¡ e.0/
hD £100%
e.0/
P.H/ ¡ P.0/
hD £100%
P.0/
(5)
x.E/ ¡ x.0/
hD £100%
x.0/
M.E/ ¡ M.0/
hD £100%
M.0/

Probably the model material for controlling polarization by magnetic field is TMO, in
which small polarization (0.08 mC/cm2) can be rotated by 90 using a magnetic field at low
temperatures [4]. The flop of polarization was firstly explained by Mostovoy [32,33], which
was argued [34] and replaced by a trilinear magnetoelctric coupling term in the Landau free
energy expansion [35]. From a view of structure, the flop of polarization coincides with a
74 H. LIU AND X. YANG

first-order transition to magnetic commensurate phase[36]. The electric control of spin hel-
icity was also revealed in the material by neutron scattering [37].
To fabricate a four-state memory device, 180 switching of ordering parameter is most
promising property. According first principles calculations, this is possible in the pervokiste
with magnetic cation occupied A-site [38]. In such compound if antiferromagnetism is built
though A-B-A superexchange interaction, a week ferromagnetism could be induced and can
be switched between 180 symmetry equivalent states with an applied electric field [38].
However, a rather large distortion of lattice has to be induced to shorten A-B for producing
superexchange interaction, because in ideal cubic perovskite A-O distance is shorter than
A-B distance. The distortion is related to two different BO6 rotation modes, which are also
termed as antiferrodistortive and service as bridges for polar and magnetic orders.

3. Recent progress on the study of multiferroic perovskite

3.1. Beyond d0-dn scenario
As we have mentioned in the pervious section, perovskite magnets require dn electron con-
figuration with n different from zero while classic FE with d0 electron configuration, what is
so called d0-dn dilemma after Hill explaining why common ferromagnetic perovskite oxides
can hardly to be ferroelectrics [7,39]. There are at least three ways to beyond d0-dn dilemma
and achieve multiferroicity in perovskite: (1) Let polar and magnetic active ions occupying
different Wyckoff positions. For instance, in BiFeO3, ferroelectric active cation Bi3C occupies
A site while magnetic cation Fe3C stays at B site of perovskite. And conversely in EuTiO3,
magnetic cation Eu2C occupies A site while ferroelectric Ti4C stays at B-site. (2) Prepare dou-
ble perovskite in which one of sublattice is magnetic and the other is ferroelectric. (3)
Prepare magnetic perovskite in which ferroelectricity is strongly related to spiral magnetic
order.

3.2. A-site driven ferroelectric multiferroics

It was commonly believed that the off-center shift of B-site cation is the origin of ferroelec-
tricity in perovskite oxides after the finding of ferroelectric BaTiO3. The study by first princi-
ples revealed that the lone-pair electrons of A-site cation also can induce ferroelectricity, as
in another classic ferroelectric perovskite PbTiO3 [15]. These type ferroelectric materials can
be termed as A-site driven ferroelectrics and can include magnetism through B-site magnetic
cation replacement, for instance in BiFeO3 [5] and BiMnO3 (BMO) [40].
After finding of large polarization in BFO thin film [5], there are enormous studies
focusing on this A-site driven ferroelectric multiferroics. An excellent review paper has been
written by Gustau Catalan and J.F. Scott [41]. Recent research has been focused on cycloidal
spin modulation [42–44], canted FM order [45–49], antiferroelectric phase [50], and magne-
toelectric coupling [51–53].
One of great achievements in the study of multiferroic BFO is the clarification of canted
ferromagnetic order. The bulk BFO does not show magnetic properties because of the exis-
tence of cycloidal spin modulation, which is a less favorable case for applications in devices.
Surprisingly, interested ferromagnetism was found in BFO thin film [5]. The result was of
debates [45,46]. On experimental side, it was shown that the Fe3C reduction [47] and size
 FERROELECTRICS 75

effect [48] could induce ferromagnetic property in BFO. On theoretical side, the ferromag-
netic property in BFO thin film was explained by spin canting according to first principles
method [54], which is the result of oxygen octahedra tilting [49]. The canted ferromagnetism
was confirmed recently by polarized small-angle neutron scattering method [55]. And more-
over, the it was evidenced that epitaxial strain pays a critical role on magnetic properties of
BFO, i.e., pseudo-collinear antiferromagnetic ordering [56,57].Recent studies also find inter-
esting spin glass state at low temperatures in BFO [58,59]. Keep in mind that the existence
of ferromagnetism of short-range is the base of spin glass phase transition.
There are also several sophisticated studies on the mutual control of polar and magnetic
orders recently. On electric field control of magnetic properties, experimentally it was found
that magnetic easy plane could be rotated by 71 polarization switching [53]; the spin waves
could be controlled by electric field [60]. Theoretically according to first-principles-based
simulations, it was shown that magnetic chirality vector could be switched by 180 polariza-
tion reorientation [61]; and the magnetism of multiferroic BFO in Pmc21 phase could be
switched by electric field [62]. On magnetic field control of polarization, it was found that a
polarization of 0.02 mC cm¡2 in single crystal BFO because of cycloidal spin order can be
controlled by magnetic field [51].
The recent studies on BFO also find that the ferroelectric Curie temperature strongly
decreases as strain increases, and the cycloidal spin modulation is destroyed by large strain
[57]. We can see that epitaxial strain is an additional freedom to tailor both ferroelectricity
and magnetism. The findings are very important for applications since thin film materials
have to be used for the fabrications of memories or/and spintonics devices.
BMO is another A-site driven multiferroics, which was firstly theoretical predicted by Hill
and Rabe [40]. Different to BFO, BMO displays direct ferromagnetic order below 110K[63]
or 100 K [64] because of orbital anharmonicity and next-nearest neighbor vibronic interac-
tion [65]. However, the ferroelectricity of BMO is still with controversy [66]. Previously, the
polarization in BMO ceramic was measured by ferroelectric hysteresis loop with remanent
polarization Pr values around 0.04-0.06mC/cm2 [67,68], but which was argued recently [69].
Moreover, theoretical investigation suggests that BMO is impossible to be a ferroelectrics
due to symmetry consideration [70–73]. It was also reported that the thin films of BMO
have large polarizations [74–76], i.e., Pr of about 9-16 mC/cm2 was found in BMO with dou-
ble SrTiO3 (STO) buffer layers [76]. This could be related to the epitaxial strain in thin films,
but according to first principle calculations the ferroelectricity can not be induced by epitax-
ial strain [77]. From experiments of synchrotron x-ray diffraction and Raman spectroscopy,
it was suggested that ferroelectricity could only appear in BMO at pressure range between
37 GPa and 53GPa [78].

3.3. B-site driven ferroelectric multiferroics

Recently, there are also focused studies on EuTiO3 (ETO), which is a potential B-site driven
ferroelectric multiferroics. ETO is a G-type antiferromagnet below 5.3 K [79–81], crystalliz-
ing in cubic Pmm space group as STO, so called quantum paraelectric antiferromagnet with
strain induced ferroelectricity [82,83]. Although the center symmetry structure prohibits the
possibility of ferroelectricity in ETO, the STO-like antiferrodistortive phase transition exists
in it, which is believed to be strongly associated with antiferroelectricity [84]. The first prin-
ciples calculation predicted three possible antiferrodistortive phases [85]. An
76 H. LIU AND X. YANG

antiferrodistortive phase transition was found at 282K [86] by specific heat measurement
and 235K [87] by synchrotron x-ray powder-diffraction with I4/mcm space group. However,
this phase transition was not confirmed by later experiments[81].
In polycrystalline samples, it was predicted that the strong spin-lattice coupling in fact sup-
presses the polar order in ETO [88]. Fortunately, under large biaxial compressive strain it was
predicted that ETO exhibits strong ferromagnetism (spontaneous magnetization, »7 Bohr
magnetons per Eu) and strong ferroelectricity (spontaneous polarization, »10 mC/cm2) simul-
taneously [89]. Later experiment has confirmed the multiferroic state with biaxial tension [90],
and the estimated polarization could be about 29 mC¢ cm¡2 [91], waiting to be confirmed by
direct ferroelectric hysteresis loop. An additional way to induce ferroelectricity in ETO is
doping, i.e., both Eu0.8Y0.2MnO3 [92] and EuxSr1-xMnO3 [93,94] show ferroelectricity.
The strong magnetoelectric coupling in ETO has been confirmed by variations of dielec-
tric (magnetic) properties under the magnetic (electric) field [95–100]. Recently, it was evi-
denced that electric field can switch the magnetic ground state to ferromagnetic in
compression film [101], and such property even exists without strain according to the pre-
diction of Landau-Ginzburg-Devonshire theory [102].

3.4. Double and complex perovskite

Substitution of B with B’ in perovskite ABO3 leads to solid solution AB1-xBxO3, which is
called complex perovskite, or double perovskite if x D 0.5 [103]. In fact, before the declara-
tion of Hill on the d0-dn dilemma, fabrication of a complex (or double) perovskite, in which
one of the sublattices is magnetic and the other consists of ferroelectric d cation, was histor-
ically considered to achieve magnetically ordered ferroelectrics [104] and is still very active
in the recent renaissance of multiferroics [105].
The double perovskites multiferroics include Bi2NiMnO6 [106], Bi2FeCrO6 [107] Lu2Mn-
CoO6 [108], Y2NiMnO6 [109] and etc. All these compounds have rock-salt-type arrange-
ment of B-site cations in a double-perovskite unit cell. Both polar and magnetic phase
transition temperatures are very low for these materials, except Bi2FeCrO6 which is a room
temperature multiferroics in thin film form [107]
In contrast to double perovskites, Pb(Fe2/3W1/3)O3 (PFW), PbFe0.5Nb0.5O3 (PFN) and
PbFe0.5Ta0.5O3 (PFT), so called relaxor ferroelectrics with G-type antiferromagnetic order,
have relatively high polar and magnetic ordering temperatures, i.e., TC at 150K (our recent
experimental result), 370K [110,111], and 240K [112] respectively, and TN at 350K [113],
143K [114], and 180K [112] respectively. Among these, PFW, which has the highest mag-
netic ordering temperature, is very promising for achieving room temperature multiferroic-
ity by preparing solid solutions with classic ferroelectrics, i.e., PbTiO3(PTO) [115–119].
We summarized the results based on experiments of differential scanning calorimetry
(DSC), Raman spectra and dielectric measurement of both ceramics and single crystals, and
plotted the polar and magnetic phase diagrams in fig. 4. As shown in fig. 4 (a), the ferroelec-
tricity of the solid solution generally enhances with the increasing of PTO content, realizing a
relaxor to normal ferroelectic phase transition with structure transiting from pseudo cubic to a
P4mm structure. Tc approaches room temperature with 20% (mol) doping of PTO.
In contrast to polar phase diagram, the magnetic phase diagram is of controversy as
shown in fig. 4 (b). Two magnetic phase transition temperatures, paramagnetic-
antiferromagnetic phase transition temperature TN2 and ferromagnetic or spin glass
 FERROELECTRICS 77

Figure 4. Polar and magnetic phase diagrams of PFW-PTO. For polar phase diagram, except down-trian-
gles which are the results from single crystal data [117], all others are based on experimental date of
ceramics based on DSC [115], Raman spectra [118] and dielectric measurement [124]. For magnetic phase
diagram, the black squares and red circles are based on SQUID [116] and AE [119] experiments of ceramic,
and green triangles are based on SQUID of single crystal [117].

phase transition temperature TN1 have been found. With increasing of PTO, SQUID
measurement suggests that TN2 deceases sharply for ceramic [116] but keeps constant
for single crystal [117]. Acoustic emission (AE) measurement indicates it keeps con-
stant even for ceramic [119]. The SQUID measurement suggests spin glass phase at low
temperature for single crystal [117].
Recently, there are several results suggesting interesting weak ferromagnetism at room
temperature for several PFW-PZO systems, i.e., 0.8PFW-0.2PTO thin films [120], (1-x)
PFW- x PTO ceramics (x D 0.10-0.30) [121,122], and PFW itself [121,123]. These findings
could be related to occurrence of Fe2C and oxygen vacancies [121], or a weak superexhange
of Fe3C-O-B-O-Fe3C in the ordering region [113] as in PFW, or canted antiferromagnetic
interaction [54] as in pure BFO. In each of these models, the sub-nano region ordering is
critical to induce the attractive magnetic behaviors.
78 H. LIU AND X. YANG

In solid solution systems, more remarkable findings have been found in solid solutions
with classic piezoelectric material PbZr0.53Ti0.47O3 (PZT). In PFW-PZT, magnetic control of
large polarization at room-temperature has been found [124]. Although there were some
controversies [125,126], similar results were found in PFT-PZT [127–130] and PFN-PZT
[131]. These compounds with remarkable magnetic, polar and magnetoelectric properties
contain only 20% (mole) of Fe at B site randomly distributed. The ferromagnetic and magne-
toelectric properties due to spins clustering [127–133], is of short range chemical order.
Therefore, ferromagnetic and magnetoelectric properties can exit at room temperature even
though the long-range magnetic order establishes far below the room temperature [134].

3.5. Manganites
Manganites are a group of materials exhibiting very interesting magnetoelectric properties,
i.e., magnetic control polarization in TMO [4] and electric field control magnetism in
HoMnO3 (HMO) [135]. In TMO thin film, a larger temperature range for magnetoelectric
coupling has been also reported recently [136]. However, the polarization in these com-
pounds is usually very small. According to first principle calculations, it was predicted that
E-type antiferromagnets could have large polarization and magneolectric coupling, i.e.,
6mCcm¡2 in orthorhombic perovskite HMO [137]. The compound has been synthesized
by soft-chemistry conditions [138] with large magnetodielectric effects [139], but the mea-
sured polarization is still very small, among 0.009mCcm¡2 [[140] and 0.24mCcm¡2 [[141].
CaMnO3 is another manganite in which the ferroelectricity and magnetism is expected to
be driven by Mn cation [142]. Although no experimental results have been found, interest-
ingly, attractive multiferroic properties were found in quadruple manganite CaMn7O12
which has fully ordered A-site Ca2CMn3C[[143]. Moreover, because of combination of rota-
tion and tilt of BO6, strained Ca3Mn2O7 should reverse the direction of magnetization by
external electric field according to first principle calculations [144,145]. In fact, BO6 defor-
mation on multiferrocity has been predicted before [146]. More detailed review on perov-
skite manganites could be found in a recent literature [147].

4. Summary and perspectives

In this brief review, we introduced some recent progress on perovskite muliferroics combin-
ing experimental and theoretical investigations. From these fantastic findings it can be seen
that strain engineering is a powerful tool to achieve multiferrocity. Materials in thin film
form are necessary not for miniaturized microelectronic devices but for unique properties
only existing in thin films, i.e., ferroelectricity, magnetism and magnetoelectric coupling.
The findings also emphasize the important of BO6 deformation on multiferroicity. In
G-type antiferromagnetic perovskites,ferromagnetism origins from BO6 rotation. In man-
ganites, both ferroelectric and magnetic properties could be related to the combination of
BO6 rotation and tilt. In a general consideration, octahedral tilt is one of structural instabil-
ities for both polar and magnetic perovskites. The tilt of BO6 influences the symmetry of
crystal lattice which decides the possibility of ferroelectricity. Moreover, B-O-B bonding is
highly controlled by BO6 tilt. Therefore, both ferroelectric and magnetic properties can be
adjusted by the deformations of BO6.
 FERROELECTRICS 79

For perspectives, one big issue for multiferroics is leakage current. The ferroelectricity
could be screened by poor insulating property of materials. Therefore, any effects correlated
to increasing conductivity should be avoided. For most of perovskite oxides, insulating prop-
erties generally deteriorate because of the reduction of magnetic ions and/or oxygen vacan-
cies. Moreover, the bandgap of some multiferroics could be narrower than classic
ferroelectrics [148]. As a result, the conductivity generally increases. Thus, except experi-
mental methods to decrease defects, a comprehensive understanding the relation between
electronic energy-band structure and conductivity is needed for perovskite multiferroics
especially those with narrow bandgaps.
Another deserved perspective for multiferroics is developing new methods and facilities
to characterize properties. We can see that several novel multiferroic materials have rather
small polarization. For instance, in multiferroic manganites, the typical polarization is
1000 times less than classic ferroelectrics, which gives difficulty to precisely characterize.
Alternatively, the spontaneous polarization is commonly calculated by integrating pyroelec-
tric current, a less persuasive way because of possible parasitic effect by trapping carries.
Moreover, only few laboratories in the world can perform well established magnetoelectric
coupling measurement, which greatly limits the research in the area. Thus, developing sim-
ple and standard method to characterization multiferrocity is also of emergence.

Funding
This work was supported by Start-up grant from Shanghai University of Engineering Science under
Grant No. 2014-35, and fund for young Teachers from Shanghai Municipal Education Commission
under Grant No. ZZgcd14009.

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