PROGRESS REPORT
Piezoelectric Materials
Development of Bismuth Ferrite as a Piezoelectric
and Multiferroic Material by Cobalt Substitution
Hajime Hojo,* Kengo Oka, Keisuke Shimizu, Hajime Yamamoto, Ryo Kawabe,
and Masaki Azuma*
Bismuth ferrite (BiFeO3) is the most widely studied multiferroic material with
robust ferroelectricity and antiferromagnetic ordering at room temperature.
One of the possible device applications of this material is one that utilizes
the ferroelectric/piezoelectric property itself such as ferroelectric memory
components, actuators, and so on. Other applications are more challenging
and make full use of its multiferroic property to realize novel spintronics and
magnetic memory devices, which can be addressed electrically as well as
magnetically. This progress report summarizes the recent attempt to control
the piezoelectric and magnetic properties of BiFeO3 by cobalt substitution.
1. Introduction
Bismuth ferrite (BiFeO3) is the most widely studied multifer-
roic material with robust ferroelectric and magnetic orderings
at room temperature. Although this material was first discov-
ered in the 1950s,[1] it took approximately half a century until
its intrinsic ferroelectric and magnetic properties were elu-
cidated. It crystallizes in a rhombohedral perovskite structure
(space group: R3c), where the ferroelectric polarization is along
the [111] of the perovskite cell in pseudocubic notation, which
we use throughout the article. In 2003, Wang et al. reported
the fabrication of (001)-oriented BiFeO3 thin films with a
remanent polarization Pr of ≈55 µC cm−2 (≈95 µC cm−2 along
[111]),[2] which is substantially larger than those previously
reported for single-crystal samples[3] and is comparable to that
Dr. H. Hojo,[+] Dr. K. Shimizu, Dr. H. Yamamoto,[++] R. Kawabe,
Prof. M. Azuma
Laboratory for Materials and Structures
Tokyo Institute of Technology
Yokohama 226-8503, Japan
E-mail: hojo.hajime.100@m.kyushu-u.ac.jp; mazuma@msl.titech.ac.jp
Dr. K. Oka
Department of Applied Chemistry
Faculty of Science and Engineering
Chuo University
Tokyo 112-8551, Japan
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201705665.
[+]Presentaddress: Department of Energy and Material Science, Kyushu
University, Kasuga 816-8580, Japan
[++]Present address: Institute of Multidisciplinary Research for Advanced
Materials, Tohoku University, Sendai 980-8577, Japan
DOI: 10.1002/adma.201705665
Adv. Mater. 2018, 1705665 1705665  (1 of 15)
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expected from its crystal structure.[4] The
piezoelectric coefficient, d33, of the BiFeO3
thin films was reported to be ≈60 pm
V−1. The first report on large polarization
(≈100 µC cm−2) along the [111] direction
for bulk BiFeO3 was made later in 2007
for single-crystal samples.[5] This situation
is clearly related to the fact that stoichio-
metric BiFeO3 without impurity phases
is difficult to synthesize,[6] which has also
hampered our understanding of the mag-
netic properties of BiFeO3, especially in
the form of thin films. It was reported
in the 1960s that BiFeO3 is a G-type anti-
ferromagnet with a Néel temperature (TN) of ≈640 K.[7] The
presence of a cycloidal modulation with a period of 62 nm was
later discovered by Sosnowska et al.[8] based on a neutron dif-
fraction study. Recently, small-angle neutron scattering studies
revealed an average local magnetization of 0.06 µB f.u.−1 that
rotates in a way similar to the cycloidal ordering with vani­shing
magnetization.[9] The origin of the cycloidal modulation has
been ascribed to an inhomogeneous magnetoelectric coupling
that arises from the non-centrosymmetric nature of BiFeO3.[10,11]
Although the origin is different, this spin structure is essentially
the same as that of TbMnO3,[12] the material in which electric
polarization induced by magnetic ordering was first discovered.
Indeed, a steep change in electric polarization was observed in
a single crystal of BiFeO3 in a magnetic field of 18 T, which cor-
responds to the appearance of a collinear spin structure with an
estimated remanent magnetization of 0.03 µB f.u.−1.[13] Recently,
a novel electric polarization that is orthogonally coupled to the
cycloidal spin rotation plane has been discovered.[14]
The paper by Wang et al. evoked a great deal of experimental
and theoretical studies on BiFeO3 because it also reported a large
magnetization (≈1 µB f.u.−1) in a BiFeO3 thin film. Since BiFeO3
without the cycloidal modulation is expected to be a weak ferro-
magnet with canted spins,[15] one of the most plausible mecha-
nisms of the enhanced magnetization in the epitaxial thin films
is a stabilization of the collinear phase with an enhanced spin
canting because of epitaxial strain.[16] Although subsequent
studies have revealed that epitaxial strain does destroy the
cycloidal modulation,[17] it is still an open question as to whether
epitaxial strain can intrinsically enhance the magnetization of
BiFeO3 thin films. At present, the intrinsic magnetization of
BiFeO3 epitaxial thin films without the cycloidal modulation is
thought to be less than 0.1 µB f.u.−1, which comes from spin
canting. An elaborate review of the basic properties of BiFeO3
was issued by Catalan and Scott in 2009.[18]
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To date, many attempts have been made to modify the fer-

roelectric/piezoelectric and magnetic properties of BiFeO3 by Hajime Hojo received his
epitaxial strain and/or chemical substitution.[19,20] Here, we B.S. in industrial chemistry
mainly focus on the chemical modification of BiFeO3. After in 2003 and his Ph.D. in
introducing representative studies on this issue, we summa- material chemistry in 2008
rize our approach to controlling the piezoelectric and magnetic from Kyoto University.
properties of BiFeO3 by cobalt substitution. From 2008 to 2011 he was
a postdoctoral fellow in the
lab of Prof. Yuichi Ikuhara
at Tokyo University. In 2011,
2. Chemical Substitution of BiFeO3
he was appointed as an
2.1. Ferroelectric and Piezoelectric Properties Assistant Professor in the lab
of Prof. Masaki Azuma at the
As a ferroelectric/piezoelectric material, one of the drawbacks of Tokyo Institute of Technology. Currently, he is an Associate
BiFeO3 is the large leakage current often reported in both bulk Professor in the Department of Energy and Material
and thin-film forms. Since BiFeO3 is a charge-transfer insulator, Sciences at Kyushu University. His research interests
where the conduction band is mainly composed of the 3d orbital include materials chemistry and catalyst chemistry.
states of iron ions, changes in the valence state of iron ions from
3+ (possibly because of the presence of oxygen vacancies and/ Kengo Oka received his
or bismuth deficiencies generating carriers) can be the cause of B.S. in material chemistry
the leakage current. Substituting the iron ions with manganese from the Kyoto Institute of
and chromium ions, which would form midgap states trapping Technology in 2005 and his
charged carriers, is known to be a practical and efficient way to Ph.D. in science in 2010 from
reduce the leakage current.[21,22] Another drawback is its large Kyoto University. In 2010, he
coercive field (hundreds of kV cm−1) compared with that of the was a postdoctoral fellow
typical ferroelectric/piezoelectric material PbZr1−xTixO3 (some in the lab of Prof. Masashi
dozens of kV cm−1). Since the 6s2 lone pair of bismuth ions Tokunaga at Tokyo University.
(Bi3+) mainly induces the ferroelectricity, substituting the bis- From 2011 to 2014, he was
muth ions with other ions such as lanthanide ions is expected appointed as a Designated
to strongly affect both the ferroelectric polarization and coercive Assistant Professor in the lab
fields. Indeed, it has been demonstrated that 15% lanthanum of Prof. Masaki Azuma at the Tokyo Institute of Technology.
substitution reduces the coercive field to 90 kV cm−1, which was Currently, he is an Assistant Professor in the Department
accompanied by an increase in the domain wall density.[23] of Applied Chemistry at Chuo University in the lab of
Great efforts have been made to improve the piezoelectric Prof. Katsuyoshi Oh-ishi. His research interests include
response of BiFeO3 by chemical substitution since the d33 of solid-state chemistry and materials science.
BiFeO3 thin films (≈60 pm V−1)[2] is substantially smaller than
those of Pb-based piezoelectric materials. The important guide- Masaki Azuma received
line for this approach is to realize a compositionally driven phase his B.S. in science in 1990
transition, the so-called morphotropic phase boundary (MPB), and his Ph.D. in science in
because it is known that the excellent piezoelectric properties of 1995 from Kyoto University.
PbZr1−xTixO3 manifest itself at the border between the Zr-rich From 1995 to 2003 he was
rhombohedral and Ti-rich tetragonal phases.[24] Fujino and co- an instructor in the lab of
workers fabricated samarium-substituted BiFeO3 thin films by a Prof. Mikio Takano at Kyoto
combinatorial method. It was reported that the dielectric constant University. In 2004, he was
and the d33 sharply increased to ≈400 and 100 pm V−1 at ≈14% appointed as an Associate
samarium content. This phenomenon was later explained as an Professor in the lab of
electric field–induced structural transformation from a paraelectric Prof. Yuichi Shimakawa.
orthorhombic phase to the polar rhombohedral phase.[25] Nanodo- Currently, he is a Professor in
mains found in these thin films also supported this picture.[26] the Laboratory for Materials
and Structures at the Tokyo Institute of Technology. His
research interests include solid state chemistry and mate-
2.2. Magnetic Properties rials science.

Chemical substitutions have also been widely explored to induce

a net magnetization in BiFeO3. Although there have been many
reports on enhanced magnetization by chemical modifica-
tion, surprisingly, the origin of the magnetic signal is unclear
in nearly all cases.[27–30] This is because macroscopic magnetic
measurements cannot distinguish the intrinsic magnetic signal
of BiFeO3 from that of magnetic impurities such as γ-Fe2O3.[31–33]
One of the possible ways to realize net magnetization in
BiFeO3 is to suppress the cycloidal modulation to stabilize
the collinear spin structure with canted spins. Indeed, it is
well known that the cycloidal state can be destroyed or the

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period of the cycloidal modulation is elongated by substituting
rare-earth elements (lanthanum[34] and neodymium[35]) for
bismuth or manganese[36] for iron. However, we have to note
that stabilizing the collinear spin structure does not necessarily
mean that spins are canted to give spontaneous magnetization
or that the sample is free from magnetic impurities. Micro-
scopic approaches such as X-ray magnetic circular dichroism
in combination with spin structure analysis such as neutron
diffraction and/or Mössbauer spectroscopy would be crucial to
undoubtedly identify the origin of the magnetic signals.
3. BiFeO3–BiCoO3 Solid Solution
We chose to substitute cobalt at the iron site of BiFeO3. This
can be regarded as making a solid solution between BiFeO3 and
BiCoO3. BiCoO3 can be stabilized by high-pressure synthesis.[37]
Pioneering work on this system was reported in 1979,[38] but the
perovskite phase was not obtained because the samples were
prepared at ambient pressure. Perovskite BiCoO3 is isostruc-
tural with PbTiO3 but has a significantly larger polar distortion
(c/a = 1.27) than PbTiO3 (c/a = 1.06). It exhibits C-type antifer-
romagnetic ordering below a TN of 420 K at ambient pressure.
The ordered magnetic moment is 3.24 µB at 5 K, indicating that
Co3+ is in the high-spin t2g4eg2 state. BiCoO3 is known to show a
pressure-induced spin-state transition accompanied by a struc-
tural change to a centrosymmetric GdFeO3-type structure,[39,40]
which can be exploited to realize useful multifunctionality with
the aid of chemical modification.[41] Through a comprehensive
study on the crystal structure of bulk BiFe1−xCoxO3 prepared by
high-pressure synthesis, we constructed the composition–tem-
perature phase diagram as shown in Figure 1a.[42] The crystal
Figure 1.  a) Composition–temperature phase diagram of bulk BiFe1−xCoxO3. Adapted with permission.[42] Copyright 2008, The Japan Society of Applied Physics.
b) Neutron diffraction patterns for bulk BiFe0.8Co0.2O3 and BiFeO3 at 10, 135, and 195 K. Adapted with permission.[34] Copyright 2013, American Chemical
Society. c) The crystal structure of monoclinic BiFe0.70Co0.30O3. Broken and solid lines represent the monoclinic and pseudocubic unit cells, respectively.
Adv. Mater. 2018, 1705665
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structure at room temperature is the rhombohedral BiFeO3
type in the iron-rich region (x ≤ 0.2) and the tetragonal BiCoO3
type in the cobalt-rich region (x  ≥ 0.4). Therefore, there exists
the so-called MPB at approximately x  = 0.3. Several attempts
have been made to improve the ferroelectric/piezoelectric prop-
erties of BiFeO3 thin films by cobalt substitution.[43–45] It has
been suggested that we can utilize the structural discontinuity
between the rhombohedral and tetragonal phases to achieve
gigantic responses including piezoelectricity.[46] Interestingly,
we identified a monoclinic phase at this composition. Our
approach to correlate the “polarization rotation” in this mono-
clinic phase and the piezoelectric properties of bulk[47] and
thin films[48] of BiFe1−xCoxO3 is summarized in Section 3.1.
On the other hand, through a detailed spin structure analysis
using powder neutron diffraction, it was revealed that the spin
structure of rhombohedral BiFe0.8Co0.2O3 changes from a low-
temperature cycloidal one to a high-temperature collinear one
at 120 K, as shown in Figure 1b.[34] Only the collinear phase
showed a ferromagnetic-like behavior, indicating that the spins
in the collinear phase are canted to give spontaneous magneti-
zation. The important point of this discovery is that the spin
structure changes as a function of temperature between col-
linear and cycloidal phases with and without spontaneous mag-
netizations, respectively. Therefore, we can confirm that the
magnetization comes from BiFe0.8Co0.2O3, and not from mag-
netic impurities. Since BiFe1−xCoxO3 maintains the ferroelec-
tric rhombohedral R3c structure below x = 0.2, BiFe0.8Co0.2O3 is
expected to be ferroelectric and weakly ferromagnetic at room
temperature. Systematic studies on the spin structure of bulk
and thin films of BiFe1−xCoxO3 are summarized in Section 3.2.
The correlation between the two orders in BiFe1−xCoxO3 single
crystals is discussed in Section 3.3.
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3.1. Polarization Rotation in BiFe1−xCoxO3
3.1.1. Studies on Bulk Samples
PbZr1−xTixO3 is a typical piezoelectric material and is used
in a wide range of applications. It shows a maximum piezo-
electric response near the MPB, x  ≈ 0.5, the boundary sepa-
rating the tetragonal P4mm (Ti-rich) and the rhombohedral
R3m (Zr-rich) phases in the phase diagram. In 1999, Noheda
et al. reported the presence of a monoclinic phase at x  = 0.52
below 250 K through powder X-ray diffraction (XRD) studies.[49]
The monoclinic phase has a √2a  ×  √2a × a cell with a space
group of Cm. The discovery of the monoclinic phase provided
a new explanation for the enhanced piezoelectric response in
PbZr1−xTixO3. That is, because of the lack of a symmetry axis,
the ferroelectric polarization vector can rotate between that of
the tetragonal [001] and that of the rhombohedral [111], leading
to the enhanced piezoelectric response.[50–54] The similar mon-
oclinic Cm phase is found in pure PbTiO3 under pressure[55]
and in other Pb-based piezoelectric perovskites such as (1 − x)
[PbMg1/3Nb2/3O3] − xPbTiO3[56] and (1 − x)[PbZn1/3Nb2/3O3] −
xPbTiO3.[57]
Although the polarization rotation mechanism successfully
explains the enhanced piezoelectric response of PbZr1−xTixO3
at the MPB, the presence of the monoclinic phase as a dis-
tinct phase is still in dispute. The structural analysis based
on diffraction studies faces difficulty due to the insufficient
difference in the pseudocubic unit cell parameters of tetrag-
onal, rhombohedral, and monoclinic phases. The c/a ratio of
tetragonal (P4mm) PbZr0.52Ti0.48O3 at 325 K is close to unity
(1.02), and the α of rhombohedral (R3m) PbZr0.60Ti0.40O3 at
295 K is nearly orthogonal (90.45°).[58] The monoclinic phase
has an intermediate structure between the tetragonal and
the rhombohedral ones. Therefore, their diffraction peaks
greatly overlap. Even more, there is another rhombohedral
phase (R3c) at a low temperature, and an electron diffraction
(ED) study by Mishra et al. also found evidence for an addi-
tional low-temperature monoclinic phase in PbZr0.515Ti0.485O3
below 189 K.[59] A follow-up structural study by Hatch et al.
determined the actual unit cell and the space group of this
low-temperature monoclinic phase to be √2a  ×  √2a  × 2a
and Cc, respectively.[60] The tilting of the (Zr,Ti)O6 octahedra
results in the doubling of the c-axis, altering the space group
from R3m to R3c and Cm to Cc. Because of the presence
of five competing phases (P4mm, R3m, R3c, Cm, and Cc)
with similar crystal structures in the vicinity of the MPB for
PbZr1−xTixO3, the presence of a Cm monoclinic phase as a
single phase is doubtful. Obtaining a single Cm monoclinic
phase would be crucial to clarify the role of polarization rota-
tion in the piezoelectric materials.
We conducted a detailed crystal structure analysis of
BiFe1−xCoxO3 with x  ≅ 0.3, where the monoclinic phase was
identified. The crystal structure was tetragonal at x  = 0.4,
in accordance with our previous report.[42] As we decreased
the cobalt content, a 101 reflection in the XRD pattern split
into two (not shown). We indexed these peaks as −111 and
111 reflections of a monoclinic phase with a √2a  ×  √2a  × a
cell. This structural transition was of the second order: the
structure continuously changed from the tetragonal P4mm
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to the monoclinic phase. Further decreasing the cobalt sub-
stitution resulted in the appearance of the rhombohedral R3c
phase below x = 0.30. The ED patterns (not shown) confirmed
the √2a  ×  √2a  × a cell with space group Cm of the mono-
clinic phase, as shown in Figure 1c. This monoclinic struc-
ture was identical to that reported for PbZr1−xTixO3 above
189 K. Figure 2a shows the composition dependence of the
lattice parameters of the Cm phase. As the cobalt content x
increased, the lattice parameters a/√2 and b/√2 decreased lin-
early because the ionic radius of cobalt is smaller than that of
iron (Co3+: 0.61 Å, Fe3+: 0.65 Å),[61] while the lattice parameter
c was nearly constant. The monoclinic angle β also decreased
with x. To study the crystal structure in detail, we performed
Rietveld analyses of the synchrotron XRD (SXRD) patterns
of x = 0.28, 0.30, and 0.37 samples. The refined crystal struc-
ture of the monoclinic BiFe1−xCoxO3 was similar to its parent
compound, tetragonal BiCoO3, where the ordering of the dxy
orbital resulted in the CoO5 pyramidal coordination. We can
expect a large spontaneous polarization of 120 µC cm−2 based
on a point-charge model.[39] Monoclinic BiFe1−xCoxO3 retained
the large polar distortion with a giant c/a ratio, and the spon-
taneous polarizations were calculated to be 117 µC cm−2 for
x  = 0.28, 117 µC cm−2 for x  = 0.30, and 121 µC cm−2 for x  =
0.37, which are approximately twice as large as that reported
for PbZr0.52Ti0.48O3 at 20 K (54 µC cm−2).[58] The polarization
vector of the tetragonal phase pointed to the [001] direction
and that of the rhombohedral phase pointed to the [111] direc-
tion. The polarization in the monoclinic Cm phase was in the
(110) plane, between the [001] and [111] directions. The dou-
bling of the unit cell was required to tilt the polarization direc-
tion in the (110) plane. The polarization direction reported
for PbZr0.52Ti0.48O3 at 20 K is tilted from the [001] direction
by 24°.[58] In monoclinic BiFe1−xCoxO3, the tilting angles
were 17° for x  = 0.28, 12° for x  = 0.30, and 2° for x  = 0.37
(Figure 2b). Because of the large distortion along the [001]
direction, the polarization directions were close to the [001]
direction compared with that of PbZr1−xTixO3. The polariza-
tion direction approached the [001] direction as the cobalt con-
tent increased, indicating that the polarization direction con-
tinuously changed. This is the first observation of the polari-
zation rotation predicted for a monoclinic perovskite.
Then, we studied the thermal stability of the monoclinic
phase. The temperature dependence of the SXRD patterns
of BiFe0.7Co0.3O3 (not shown) revealed a second-order struc-
tural transition from monoclinic Cm to tetragonal P4mm
structures at elevated temperature. The monoclinic distortion
angle β decreased on heating and reached to 90° above 673 K,
as shown in Figure 2c, indicating that the structural transi-
tion was complete. The polarization direction was tilted from
the [001] direction by 12° at 300 K, 6° at 373 K, 2° at 423 K,
and 0° at 673 K (Figure 2d). This result clearly demonstrates
that the polarization rotation also occurred during heating. An
enhanced piezoelectric response is expected if such a polariza-
tion rotation is induced by an electric field, as suggested for
PbZr1−xTixO3. Unfortunately, high leakage current presumably
at grain boundaries prevented us from evaluating the piezoelec-
tric properties in a ceramic form. Thin-film samples are indis-
pensable to evaluate the piezoelectric properties of monoclinic
BiFe1−xCoxO3.
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Figure 2.  a) Composition dependence of the lattice parameters of monoclinic bulk BiFe1−xCoxO3 (0.27 ≤ x  ≤ 0.40). b) The polarization vectors of
BiCo1−xFexO3 (x = 0.28, 0.30, and 0.37) at 300 K and PbZr0.52Ti0.48O3 at 20 K.[58] The indices [001], [100], [110], and [111] are based on the pseudocubic
unit cell. c) Temperature dependence of the lattice parameters of bulk BiCo0.30Fe0.70O3. d) Temperature dependence of the polarization vectors, which
reveals the temperature-induced polarization rotation. Adapted with permission.[47] Copyright 2012, Wiley.

3.1.2. Studies on Epitaxial Thin Films
To stabilize the epitaxial thin films of monoclinic BiFe1−xCoxO3
with a giant c/a ratio, we used LaAlO3 (001) as the substrate. It is
known that BiFeO3 thin films crystallize in a similar monoclinic
structure with a giant c/a ratio when fabricated on substrates
with a compressive strain over 4.5%, such as LaAlO3.[62,63] The
two monoclinic phases are different in the direction of the
polarization: the polarization of monoclinic BiFeO3 tilts toward
[101], while that of BiFe1−xCoxO3 tilts toward [111]. They have
been designated MC-type and MA-type, respectively, by Vander-
bilt and Cohen.[64] By carefully optimizing the growth condi-
tions, c-axis-oriented epitaxial thin films of BiFe1−xCoxO3 (x  =
0–0.50, thickness: ≈90 nm) without a detectable impurity phase
in XRD patterns were obtained by using pulsed laser deposi-
tion (PLD).[48] Reciprocal space mapping (RSM) near the 103
and 113 reflections of LaAlO3 was performed to investigate the
crystal structure in detail. Figure 3a shows the RSMs for the
BiFe1−xCoxO3 thin films with x  = 0.10, 0.15, 0.30, and 0.50 as
representative results. When x was 0.10 or less, the 103 reflec-
tions of BiFe1−xCoxO3 split into three spots, while the 113
reflections split into two spots, indicating that the crystal struc-
ture was an MC-type monoclinic. This structure is schematically
illustrated in Figure 3b and is identical to that of the afore-
mentioned MC-type BiFeO3 thin film with a giant c/a ratio. On
the other hand, the 103 reflections split into two spots, while
the 113 reflections split into three spots when x was further
increased to 0.20 and 0.30. This result indicates that the crystal
structure changed from the MC-type monoclinic phase to an
MA-type monoclinic phase, as illustrated in Figure 3c. This MA-
type monoclinic structure was identical to that observed in bulk
monoclinic BiFe1−xCoxO3 at the MPB. Note that MA- and MC-
type monoclinic phases coexisted at x = 0.15. The crystal struc-
ture became a tetragonal BiCoO3 type at x = 0.5 (Figure 3d), as
is evident from the fact that a single spot was observed for both
the 103 and 113 reflections. Thus, successive structural transi-
tions from MC-type to MA-type monoclinic phases and finally
to a tetragonal phase were identified in the BiFe1−xCoxO3 thin
films as the Co content (x) increased.
To clarify the nature of the structural transitions, the lat-
tice parameters were calculated from the RSM data, and the
composition dependence of these is plotted in Figure 4. In the

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Figure 3.  a) Reciprocal space mapping of BiFe1−xCoxO3 thin films on LaAlO3 (001) with x = 0.10, 0.15, 0.30, and 0.50 around 103 and 113. Schematic
illustrations of b) MC-type monoclinic, c) MA-type monoclinic, and d) tetragonal structures. Note that the polarization tilts toward the [101] and [111]
in the MC-type and MA-type monoclinic structures, respectively. Reproduced with permission.[48] Copyright 2016, Wiley.

MC-type monoclinic region (x  = 0–0.10), the out-of-plane lat-
tice parameter c decreased as x increased, while the in-plane
lattice parameters apc and bpc increased, and the average of
these approached the pseudocubic lattice parameter of the
LaAlO3 substrate (≈3.79 Å). This result indicates that a larger
tensile strain was imposed on the BiFe1−xCoxO3 thin films as
x increased. However, this behavior is contrary to our expec-
tation because BiCoO3 has smaller in-plane and larger out-of-
plane lattice constants compared with those of MC-type mono­
clinic BiFeO3. It can be explained by the fact that a fraction
of the “rhombohedral-like phase” decreased. It is well known
that the MC-type monoclinic phase and rhombohedral-like
phase coexist in BiFeO3 thin films on LaAlO3 substrates thicker
than 50 nm, and the region is noticeable as a striped area in
atomic force microscopy (AFM) images.[67] The rhombohedral-
like phase is introduced to accommodate the lattice mismatch
between the MC-type monoclinic phase and the substrate. Our
AFM observations (not shown) revealed that the striped area
decreased as x increased, indicating the decrease of the rhom-
bohedral-like phase. An MA-type monoclinic phase started to
appear when x was increased to 0.15. The lattice parameter c
increased abruptly when the structure changed from MC-type to
MA-type monoclinic phases, indicating that this structural
phase transition was of the first order. On the other hand,
the lattice parameters of the MA phase gradually approached
those of the tetragonal phase as x increased in a second-order
manner. Such a behavior was observed in bulk BiFe1−xCoxO3, as
was demonstrated in Section 3.1.1. The only difference was the
absence of the rhombohedral phase in the iron-rich region for
the BiFe1−xCoxO3 thin films, which was transformed into the
MC-type monoclinic phase by epitaxial strain.
Finally, the piezoelectric properties of these thin films were
investigated. Unipolar ac electrical fields at a frequency of
1 kHz and a bias of ≈880 kV cm−1 were applied directly on bare
BiFe1−xCoxO3 thin films using a conductive cantilever to obtain
local strain versus electric field (S–E) curves (not shown). We
calculated the effective piezoelectric constant (SMAX/EMAX) from
the S–E field curves, and the result is plotted in Figure 4e. The
SMAX/EMAX decreased from 39.8 to 36.3 pm V−1 as x increased,
presumably reflecting the larger tensile strain imposed by the
substrates. These values were comparable to that reported
previously for MC-type BiFeO3 thin films (≈30 pm V−1).[68]
The SMAX/EMAX increased from 52.1 to 57.5 pm V−1 in the MA
structure. Interestingly, the maximum value was observed at

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Figure 4.  Composition dependence of a) out-of-plane lattice parameter c,
b) in-plane lattice parameters apc and bpc, c) c/a ratio, and d) monoclinic
β angle, as obtained from RSMs for BiFe1−xCoxO3 thin films on LaAlO3
(001). The unit cell is defined as apc × bpc × cpc and √2apc × √2bpc × cpc
in the MC-type and MA-type monoclinic phases, respectively.[65,66] e) The
effective piezoelectric constant (SMAX/EMAX) for BiFe1−xCoxO3 thin films.
The enhanced piezoelectric responses were achieved in a single phase
of the MA-type monoclinic structure with a large deviation in the β angle
from 90°. Adapted with permission.[48] Copyright 2016, Wiley.
x = 0.20 rather than at x = 0.15. Since x = 0.15 is the so-called
MPB composition between the MC and MA phases, this result
means that the enhanced piezoelectric responses were achieved
in a single phase of the MA phase rather than at the MPB
between MC and MA phases.[69] The SMAX/EMAX of the tetrag-
onal phase (x = 0.50) was as small as 10.8 pm V−1. From these
results, it was demonstrated that the piezoelectric response
was enhanced in the monoclinic phases because of the polari-
zation rotation and that the polarization rotation worked more
effectively in the MA phase than in the MC phase, which was
consistent with the theoretical prediction by Fu and Cohen.[70]
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Moreover, we noticed that a larger deviation in the β angle from
90° resulted in an enhanced piezoelectric response. This should
be related to the fact that BiFe1−xCoxO3 thin films with a smaller
β angle have more room for the polarization to rotate. It should
be noted that the piezoelectric responses of our BiFe1−xCoxO3
thin films were significantly smaller than those of PbZr1−xTixO3
and still smaller than those of BiFe1−xCoxO3 thin films on
SrTiO3 (001) substrates.[45] According to the Landau–Ginz-
burg–Devonshire theory, the piezoelectric coefficient comes
from the product of the dielectric constant and polarization,
and the dielectric constant decreases faster than the polariza-
tion increases.[71–74] Therefore, the small piezoelectric response
of the present BiFe1−xCoxO3 thin films should be attributed
to their large spontaneous polarization. As mentioned in
Section 3.1.1 the spontaneous polarization of BiFe1−xCoxO3
with x = 0.30 was calculated to be 117 µC cm−2,[47] while that of
PbZr1−xTixO3 at MPB composition was ≈37.6 µC cm−2.[75] From
these results, we concluded that the MA-type monoclinic phase
with smaller spontaneous polarization and larger deviation in β
angle from 90° would be desirable to achieve the replacement
of PbZr1−xTixO3.
3.2. Spin Structure Change in BiFe1−xCoxO3
3.2.1. Studies on Bulk Samples
We discovered a temperature-induced spin structure change
from a cycloidal to a collinear one in bulk BiFe0.8Co0.2O3, as
mentioned in the introduction of Section 3. To clarify the
nature of this spin structure change, the composition depend-
ence of the magnetic properties was studied in detail.[76] The
temperature dependence of the magnetic susceptibility of
BiFe1−xCoxO3 (x  = 0.05, 0.10, 0.15, and 0.20) is shown in
Figure 5a. The results for the x = 0.20 sample were consistent
with our previous report.[34] That is, the susceptibility increased
at ≈120 K upon heating, indicating that the spin structure
changed from a cycloidal one to a collinear one with canted
spins. The increase in the magnetic susceptibility was also
observed for the other compositions, with increased transi-
tion temperatures as x decreased from 0.20 to 0.05. We noticed
the presence of a temperature hysteresis of 3–4 K between the
data on heating and cooling near the transition temperature, as
shown in Figure 5b, suggesting that the transition was of the
first order. Figure 5c shows the magnetization curves at 300 K.
A clear ferromagnetic-like hysteresis with a remanent magneti-
zation of 0.02 µB f.u.−1 was observed for samples with x ≥ 0.10.
The values of remanent magnetization slightly changed with x
but were not proportional to x. Such a behavior indicated that
the observed magnetization was intrinsic to BiFe1−xCoxO3 and
not from magnetic impurities. The value of saturation magneti-
zation can be reproduced when we assume Fe3+ (S = 5/2) with
a canting angle of 0.23° and low-spin Co3+. Co3+ in BiCoO3 is
in the CoO5 pyramidal coordination, and the high-spin state
is stabilized.[39] On the other hand, we can expect the low-spin
state of Co3+ in CoO6 octahedra in rhombohedral BiFe1−xCoxO3
(x  ≤ 0.20). The fact that the lattice parameters shrunk with
cobalt substitution in BiFe1−xCoxO3 is in accordance with the
low-spin state of Co3+.[42]
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Figure 5.  a) Temperature dependence of magnetic susceptibility of bulk BiFe1−xCoxO3 (x = 0, 0.05, 0.10, 0.15, and 0.20) measured at a magnetic field of
μ0H = 1 T under heating (closed circles) and cooling (open circles) conditions. b) Magnified view of panel (a) where temperature hysteresis is evident.
c) Magnetization curves measured at 300 K. d) 57Fe Mössbauer spectra for 57Fe-enriched bulk BiFe0.9Co0.1O3 measured at 78, 200, 245, 260, 275, and
300 K. Blue dotted and green dashed lines are fitting results of contributions from the Bhf // Vzz and Bhf ⊥ Vzz components. e) Temperature depend-
ence of the fraction of the collinear phase estimated from the Mössbauer spectra and that of the magnetic susceptibility. Adapted with permission.[76]
Copyright 2016, The Physical Society of Japan.

Mössbauer spectroscopy is a powerful tool to study the
spin structure of magnetic materials and has been applied to
bulk,[77–79] nanoparticle,[80–82] and thin-film[83–86] samples of
BiFeO3. Here, we applied 57Fe Mössbauer spectroscopy to bulk
BiFe0.9Co0.1O3 to confirm the temperature-dependent change
in the spin structures. Figure 5d shows the spectra at 78, 200,
245, 260, 275, and 300 K. The spectrum at 300 K had a Zeeman
sextet with a symmetric height with an isomer shift (IS) of
0.34(1) mm s−1, quadruple shift (QS) of −0.20(1) mm s−1, and
hyperfine field (Bhf) of 47.6(1) T. The symmetric spectrum sug-
gested that the spin structure was collinear. The value of IS
was characteristic of Fe3+ ions in octahedral coordination. The
negative QS value indicated that the spins were aligned perpen-
dicularly to the electric field gradient (Vzz), which was along the
[111] direction of a perovskite cell (here, Vzz  > 0[79,82,87]). This
result agrees with the neutron diffraction study.[34] On the other
hand, the spectrum at 77 K was asymmetric in height, as that
of pure BiFeO3.[79] This result indicates that there was a dis-
tribution in either the magnitudes of QS or the directions of
Bhf. Since the directions of spins continuously changed from
parallel to perpendicular to Vzz with the propagation along the
[1−10] direction in the cycloidal spin phase,[8] the latter inter-
pretation is plausible. Here, we used an approximate fitting
model with two representative components with spins parallel
(positive QS) and perpendicular to the electric field gradient Vzz
(negative QS) to analyze the spectra. The ratios of QS values of
Bhf // Vzz and Bhf ⊥ Vzz were fixed to 2: −1. The spectrum at 77 K,
where the spin structure was expected to be cycloidal from the
magnetic susceptibility data, could be fitted using an ≈1:1 area
ratio of the two components, suggesting that this model was
appropriate under the resolution of the present Mössbauer
spectra. We analyzed the spectra at the intermediate tempera-
ture likewise. Since both the cycloidal and the collinear phases
contributed to the component with Bhf ⊥Vzz (negative QS), the
fraction of the collinear phase can be regarded as the difference
between the fractions of components with Bhf ⊥ Vzz and Bhf //
Vzz. Figure 5e shows the temperature dependence of estimated
fraction of the collinear phase together with the magnetic

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susceptibility. The good agreement of these two values supports

our picture that spins were in the (111) plane in the collinear
phase, and the spin structure change occurred as a function of
temperature between the collinear and the cycloidal phases in
BiFe1−xCoxO3.
We studied the nature of the spin structure change in bulk
BiFe1−xCoxO3 and confirmed that BiFe1−xCoxO3 is intrinsically
a weak ferromagnet at room temperature for x  ≥ 0.10. Since
BiFe1−xCoxO3 maintained the polar R3c structure below x = 0.2,
it was expected to also be ferroelectric. Unfortunately, a high
leakage current, presumably at grain boundaries, prevented us
from evaluating the ferroelectric properties in a ceramic form.
Thin-film samples are indispensable to evaluate the ferroelec-
tric properties of BiFe1−xCoxO3. Thin-film samples are also
favorable for device applications.

3.2.2. Studies on Epitaxial Thin Films

The observation of the temperature-dependent spin structure

change is crucial to undoubtedly confirm that BiFe1−xCoxO3
thin films are a weak ferromagnet. For this purpose, the choice
of substrate is important because the spin structure of BiFeO3
is known to be sensitive to structural distortion because of epi-
taxial strain. Recently, Sando et al. have systematically studied
the spin structure of 70 nm thick BiFeO3 thin films grown on
various perovskite (001) substrates using conversion electron
Mössbauer spectroscopy (CEMS). They found that virtually
unstrained thin films grown on GdScO3 display asymmetric
spectra typical of the cycloidal spin structure, while strongly
strained thin films have symmetric spectra indicative of the col-
linear spin structure.[83] In this study, SrTiO3 (111) was used as
the substrate to stabilize the rhombohedral BiFe1−xCoxO3 thin
films.[88–90] Epitaxial BiFe1−xCoxO3 thin films were fabricated
using PLD.[91] The thickness was set to 200 nm to obtain fully
relaxed thin films.[89,90] An epitaxial SrRuO3 layer with a thick-
ness of 10 nm was grown as the bottom electrode. The θ–2θ
XRD patterns (not shown) confirmed that the BiFe1−xCoxO3
thin films grew along the [111] direction without detectable
impurity phases. We confirmed that the symmetry of the
BiFe1−xCoxO3 thin films was rhombohedral by the RSMs near
the 312 reflection of SrTiO3 and the φ-scans (not shown). We
then calculated the lattice parameter a and rhombohedral dis-
tortion angle α of the films in the pseudocubic notation from
the RSM results. The values of a for the films and bulk sam-
ples were close to each other for all compositions, while the
values of α were slightly larger than those of the bulk samples
for x = 0.10 and 0.15. This result indicates that these thin films
suffered from a large lattice strain. The effect of this strain is
Figure 6.  a) Polarization and current as a function of the electric field
discussed later in the magnetic measurement part.
for BiFeO3 and BiFe0.9Co0.1O3 thin films on SrTiO3 (111). b) Tempera-
We studied the ferroelectric properties of BiFe1−xCoxO3 ture dependence of the in-plane Mr for BiFe1−xCoxO3 thin films. The spin
thin films at room temperature. Figure 6a shows the polari- structure change can be clearly seen near 220 and 130 K for BiFe0.9Co0.1O3
zation (P) and current (I) versus electric field (E) for x  = 0 and BiFe0.85Co0.15O3 thin films, respectively. The inset is the temperature
(BiFeO3) and x  = 0.10 thin films. The BiFeO3 shows a well- dependence of the in-plane magnetization for the BiFe0.9Co0.1O3 thin film.
saturated ferroelectric P–E loop. The P–E loop of the x = 0.10 c) In-plane magnetization curves at 300 K for BiFe1−xCoxO3 thin films.
Adapted with permission.[91] Copyright 2017, Wiley.
thin film became rounded as the leakage current increased,[45]
which is noticeable in the I–E curve. We could not observe leakage current. From these results, we confirmed that the
a ferroelectric switching behavior in the P–E measurements BiFe1−xCoxO3 thin films (x  ≤ 0.1) were ferroelectric at room
for the x = 0.15 thin film because of a further increase in the temperature.

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Next, the magnetic properties of the BiFe1−xCoxO3 thin films
were studied. Figure 6b plots the in-plane remanent magnetiza-
tion (Mr) as a function of temperature for BiFe1−xCoxO3 with
x  = 0, 0.05, 0.10, and 0.15. When we applied the magnetic
field during the measurements, the intrinsic magnetic signal
from the BiFe1−xCoxO3 thin films was masked by diamagnetic
and ferromagnetic contributions from the SrTiO3 substrate
and SrRuO3 bottom electrode (Tc  ≈ 150 K), as shown in the
inset of Figure 6b. Therefore, we switched off the magnetic
field after magnetizing the sample at 400 K with a magnetic
field of 1 T and measured Mr during cooling. The Mr values
of the BiFeO3 thin film were nearly zero in this temperature
range. In contrast, a change in Mr similar to that observed in
bulk BiFe1−xCoxO3 was clearly seen for the x  = 0.10 and 0.15
thin films at ≈220 and 130 K, respectively.[34] This result indi-
cates that the spin structure change from the cycloidal one to
the collinear one also occurred in the thin-film samples. Note
that, unlike bulk samples, a non-negligible Mr was observed
for x  = 0.10 and 0.15 thin films below the transition tempera-
tures, where the spin structure is expected to be cycloidal with
no spontaneous magnetization. Since we found that x  = 0.10
and 0.15 BiFe1−xCoxO3 thin films suffered from large lattice
distortions compared with those of x  = 0 and 0.05 thin films
mentioned in the first paragraph of this section, this non-neg-
ligible Mr should be attributed to a partial stabilization of the
collinear phase from epitaxial strain. In-plane magnetization
curves at 300 K are shown in Figure 6c. The diamagnetic con-
tribution from the SrTiO3 substrate was subtracted, assuming
that the magnetization of BiFe1−xCoxO3 thin films saturated at
high (>2 T) magnetic fields. Ferromagnetic-like hysteresis loops
were clearly seen for the x  = 0.10 and 0.15 BiFe1−xCoxO3 thin
films. The value of Mr, 0.038 µB f.u.−1 at room temperature,
was comparable with that of bulk BiFe1−xCoxO3[34] and with that
estimated from the high-field experiments for BiFeO3 single
crystals.[13,14] From these results, it is most likely that the x  =
0.10 and 0.15 thin films were weakly ferromagnetic at room
temperature because of spin canting. It should be noted that
the Mr values of the out-of-plane magnetization curves (not
shown) were found to be, respectively, ≈1/4 and ≈1/2 of those
of the in-plane configuration for the x  = 0.10 and 0.15 thin
films, indicating that the spontaneous magnetization was in the
(111) plane. This is in accordance with our neutron diffraction
study[34] and CEMS study,[91] as shown later. Since the electric
polarization was along the [111] direction with the rotation of
the oxygen octahedra around the [111] direction, the sponta-
neous magnetic moment generated by the Dzyaloshinskii–
Moriya (DM) interaction should also be in the (111) plane.[15]
Shape anisotropy can contribute to the anisotropy field, but its
contribution is at best equal to the magnetization of the thin
film, µ0Hd = magnetization ≈ 2.5 mT, and should be negligible.
To verify that the spin structure change also occurred in thin-
film samples, CEMS measurements were performed on an
≈100% 57Fe-enriched x = 0.10 thin film. The spectra at 300, 235,
215, 200, and 150 K are shown in Figure 7a. The spectrum at
300 K was well fitted by one component with a Zeeman sextet
with a symmetric height and an IS of 0.385 mm s−1, QS of
−0.216 mm s−1, and Bhf of 47.6 T. The symmetric spectrum is
indicative of the collinear spin structure.[83] The values of IS,
QS, and Bhf were comparable with those of the bulk sample,
as mentioned in Section 3.2.1.[76] The area intensity ratio

Figure 7.  a) CEMS spectra measured at 300, 235, 215, 200, and 150 K for the 57Fe-enriched BiFe0.9Co0.1O3 thin film on SrTiO3 (111). At 300 K, the spin
structure is collinear with spins in the (111) planes. b) Temperature dependence of the estimated ratio of the collinear phase from the CEMS spectra
and that of the Mr of the BiFe0.9Co0.1O3 thin film. Portions of the BiFeO3 lattice of the cycloidal and the collinear phases with only Fe ions shown at
the bottom of panel (b), respectively. The blue arrows indicate the Fe3+ moment direction. The spiral period in the cycloidal phase is reduced, and the
angle of spins in the collinear phase is exaggerated for illustrative purposes. Adapted with permission.[91] Copyright 2017, Wiley.

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of the six lines was close to 3:4:1:1:4:3. It is well known that
the area intensity ratio reflects the angle between the spins and
the incident direction of the γ-rays; it is 3:4:1:1:4:3 when they
are orthogonal, while 3:0:1:1:0:3 when they are parallel. There-
fore, we know that the spins were aligned in the (111) plane
for the x  = 0.10 thin film in the experimental setup, and the
incident γ-rays were normal to the thin-film surface. Note that
when the sample is polycrystalline and the orientation of the
spins is random with respect to the γ-rays, the intensity ratio
becomes 3:2:1:1:2:3, as was observed for bulk BiFe1−xCoOxO3
(Figure 5d). The negative value of QS also indicated that the
spins were aligned perpendicularly to the electric field gradient
(Vzz), which was along the [111] direction of BiFe1−xCoxO3. As
the temperature decreased, the relative intensities of lines 2
and 5 gradually decreased, indicating that some of the spins
were tilted toward the incident direction of the γ-rays. For bulk
samples, the spins in the cycloidal phase rotated in a plane
defined by the [1−10] and [111] directions.[8] The present result
also suggests the appearance of the cycloidal phase in the
thin-film sample at lower temperatures, as was indicated by
the temperature dependence of magnetization. To analyze the
spin structure of the low-temperature phase, we used a similar
approximate model with two representative components (posi-
tive and negative QSs with a 2:1 ratio in absolute value) as was
applied for the analysis of the bulk BiFe0.9Co0.1O3.[76] The only
difference was that we added the constraint that the intensity
ratio of the first component with negative QS was 3:4:1:1:4:3,
which represents the in-plane spin component of the cycloidal
phase and the collinear phase. The intensity ratio of the second
component, which represents the out-of-plane spin component,
was set at 3:0:1:1:0:3. The QS ratio of the two components was
fixed at −1:2. Importantly, the area of the second component
increased with decreasing temperature, indicating that the ratio
of the cycloidal phase increased. Figure 7b shows the fraction
of the collinear phase estimated from the area ratio of each
component, together with the Mr–T curve. The change in the
ratio of the collinear phase nearly agreed with the change in Mr.
This result clearly demonstrates the coexistence of the collinear
phase and cycloidal phase below 300 K. The reason the spectra
evidently looked symmetric even at 150 K was probably because
the volume fraction of the cycloidal phase in the x = 0.10 thin
film was expected to be only ≈0.5, and the degree of asym-
metry in the cycloidal phase was basically small as seen for
bulk BiFe0.9Co0.1O3.[76] It should also be noted that anharmo-
nicity in the cycloidal modulation, which is taken into account
to describe the Mössbauer spectra of BiFeO3 thin films[83] and
nanoparticles,[82] was not considered explicitly in this analysis.
This was due to difficulty in distinguishing the anharmonicity
in the cycloidal phase and the coexistence of the collinear and
the cycloidal phases, both of which would affect the relative
ratio of the in-plane and out-of-plane spin components.
3.3. Correlation between Ferroelectric and Weak Ferromagnetic
Orders in BiFe1−xCoxO3
A coupling between ferroelectric and weakly ferromag-
netic orderings is a prerequisite for controlling magnetiza-
tions of multiferroic materials by an electric field. We can
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expect a correlation between the two orders in rhombohedral
BiFe1−xCoxO3 since the weak magnetization is confined in the
plane orthogonal to the electric polarization.[76,91] To experi-
mentally demonstrate this issue, we studied the macroscopic
remanent mgnetization (Mr) of a multidomain single crystal
of BiFe0.892Mn0.008Co0.1O3 grown at a high pressure of 3 GPa
before and after polarization switching.[92] We substituted 0.8%
of iron with manganese to reduce the leakage current.[22] This
enabled us to obtain a saturated P–E hysteresis loop at 150 K.
The magnetic property of the BiFe0.892Mn0.008Co0.1O3 single
crystal was essentially the same as that of bulk BiFe0.9Co0.1O3.
It showed a steep increase in magnetic susceptibility toward
higher temperatures at ≈230 K and a weak ferromagnetism at
room temperature. The single crystals typically had a plate-like
shape with a (100) face in pseudocubic notation [(100)c], and the
size was typically several hundreds of micrometers. Because
BiFe1−xCoxO3 is paraelectric under pressure,[93] the single
crystal is expected to have eight ferroelectric domains with elec-
tric polarization in the eight equivalent [111]c directions.
First, we explain the Mr anisotropy expected for the single
crystal with magnetic easy planes perpendicular to each elec-
tric polarization. When the single crystal is magnetized along
[010]c, the spontaneous magnetization m because of canted
spins is confined within the magnetic easy plane perpendicular
to the electric polarization with the projection along the [010]c
being m cos35.5°, as schematically illustrated in Figure 8a.
Because the same holds true for all ferroelectric domains, the
values of Mr along the [100]c, [010]c, and [001]c are expected to
be constant regardless of the fraction of ferroelectric domains,
as illustrated in Figure 8b. On the other hand, values of Mr
along the [110]c, [−110]c, [011]c, [0−11]c, [101]c, and [10−1]c direc-
tions are expected to be dependent on the fraction of each ferro-
electric domain. The expected contribution of each ferroelectric
domain after magnetic poling along the [−110]c is illustrated in
Figure 8c. Here, the remanent magnetization of each domain
is defined as mr. The spontaneous magnetization is expected
to be in the (220) planes as drawn by the blue lines, for the
domains with electric polarization along the [111]c, [11−1]c,
[−1−11]c, and [−1−1−1]c directions. The values of mr for these
domains are equal to m. For the domains with electric polari-
zation along the [1−11]c, [−111]c, [1−1−1]c, and [−11−1]c direc-
tions, mr of each domain is in the (110) plane (red lines) with a
value of m cos54.5°. Therefore, Mr along [110]c, [−110]c, [011]c,
[0−11]c, [101]c, and [10−1]c is expected to be dependent on the
fractions of the eight ferroelectric domains. This is illustrated
in Figure 8d, where Mr along [−110]c is larger than that along
[110]c. The same tendency is expected for the directional pairs
of [011]c and [0−11]c, [101]c, and [10−1]c. We have measured the
Mr anisotropy for single-crystal BiFe0.892Mn0.008Co0.1O3 with a
cuboidal shape of 320 µm × 200 µm × 210 µm and confirmed
that the results are fully consistent with the above discussion.[92]
Finally, the reorientation of the magnetic easy plane by an
electric field was investigated. As schematically illustrated
in Figure 9a,b, it is expected that the values of Mr along the
[100]c, [010]c, and [001]c (Figure 9a) and those along the [110]c
and [−110]c (Figure 9b) are not sensitive to electric poling along
[001]c because the values of mr for polarization-up and polari-
zation-down domains are the same. On the other hand, the Mr
along the [011]c, [0−11]c, [101]c, and [10−1]c is expected to change
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Figure 8.  a) Schematic illustration of the eight ferroelectric domains and Mr in the (101) plane after magnetizing the crystal along the [010]c direction.
The blue, red, apricot, and orange arrows, respectively, represent P, m, the projection of m along the [010]c in each ferroelectric domain (mr,010), and the
Mr. b) Illustration of the ferroelectric domains and Mr viewed along the [001]c. The same Mr is expected along the [100]c, [010]c, and [001]c. c) Schematic
illustration of the eight ferroelectric domains and Mr in the (110) and (220) planes after magnetizing the crystal along the [−110]c. d) Illustration of the
ferroelectric domains and Mr along the [−110]c and [110]c. Adapted with permission.[92] Copyright 2017, American Chemical Society.

by electric poling along the [001]c. This is evident in Figure 9c,
where the ferroelectric domains and Mr viewed along the [100]c
are illustrated. In this figure, Mr along the [0−11]c was larger
than that along the [011]c. Electric poling along the [001]c would
cause 71° ferroelectric switching and the magnetic easy plane
in the domains on the left side of the figure, as highlighted
by green, would be simultaneously reoriented. Consequently,
the values of Mr along the [011]c and [0−11]c would become
the same because the fractions of red and blue domains were
equivalent. The same discussion would be true for the [101]c
and [10−1]c directions.
Figure 9d shows the Mr anisotropy of single-crystal
BiFe0.892Mn0.008Co0.1O3 at 300 K before and after electric poling
along the [001]c at 150 K. We used a plate-like crystal with a
size of 180 µm × 160 µm × 70 µm for the ease of ferroelec-
tric polarization switching. Because of the shape anisotropy,
Mr was smaller along the [001]c than those values along the
[100]c and [010]c. The effect of electric poling was consistent
with the above discussion. That is, the values of Mr along the
[100]c, [010]c, [001]c, [110]c, and [−110]c were not sensitive to
electric poling, whereas the difference in Mr values along the
[0−11]c ([10−1]c) and [011]c ([101]c) directions were suppressed,
demonstrating the reorientation of the magnetic easy plane by
an electric field. It should be noted that the difference between
them was not suppressed completely because of imperfect
electric poling; the coverage of the electrode was not perfect.
From these results, we successfully demonstrated the coupling
between ferroelectric and weakly ferromagnetic orderings in
rhombohedral BiFe1−xCoxO3.
4. Conclusion
In summary, we reported the progress in controlling the
piezoelectric and magnetic properties of BiFeO3 by cobalt sub-
stitution. We identified the monoclinic Cm phase (MA-type)
with a giant c/a ratio as a distinct phase in bulk BiFe1−xCoxO3
(x  ≈ 0.3), where the polarization rotates as functions of com-
position and temperature. BiFe1−xCoxO3 thin films with the
MA-type and MC-type monoclinic phases and the tetragonal
phase with a giant c/a ratio were fabricated to evaluate the
piezoelectric properties. Indeed, the piezoelectric responses
were enhanced in the MA-type monoclinic phase with a large
monoclinic distortion, which can be attributed to increased
room for the polarization to rotate. Unfortunately, the d33 of
the BiFe1−xCoxO3 thin film was still small (≈60 pm V−1) because
of the large spontaneous polarization. The MA-type mono-
clinic phase with a small spontaneous polarization would be
desirable to replace PbZr1−xTixO3. On the other hand, we dis-
covered that the spin structure changed from the low-temper-
ature cycloidal one to the high-temperature collinear one in
rhombohedral bulk BiFe1−xCoxO3 (x  < 0.2). The temperature-
dependent spin structure change was also observed in the
rhombohedral BiFe1−xCoxO3 thin films. It was confirmed that
x  = 0.10 BiFe1−xCoxO3 thin films were weakly ferromagnetic
because of spin canting and were also ferroelectric at room
temperature. The coupling between ferroelectric and weakly
ferromagnetic orderings was demonstrated for single crystals
of BiFe0.892Mn0.08Co0.1O3 as the reorientation of the magnetic
easy plane by applying an electric field.

Adv. Mater. 2018, 1705665 1705665  (12 of 15) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 9.  a) Illustration of the ferroelectric domains and Mr along the [010]c ([001]c) viewed along the [001]c ([100]c) directions. The domains reversed
by the electric field are highlighted by green. b) Illustration of the ferroelectric domains and Mr along the [110]c and [−110]c viewed along the [001]c
direction. c) Illustration of the ferroelectric domain and Mr along the [011]c and [0−11]c viewed along the [100]c direction. d) The Mr along 18 crystal-
lographic directions for the plate-like BiFe0.892Mn0.008Co0.1O3 single crystal (shown in the photograph) before and after electric poling along the [001]c.
Reproduced with permission.[92] Copyright 2017, American Chemical Society.

Magnetization reversal by an electric field is yet to be
proven in this system. To clarify the magnetic domains for
the present BiFe1−xCoxO3 thin films, X-ray magnetic circular
dichroism photoemission electron microscopy[94,95] would
be useful since the magnetization is in plane in the present
thin films. Another option is to use a probe microscope such
as magnetic force microscopy (MFM) to detect the magnetic
domains. For this purpose, however, achieving an out-of-plane
component of magnetization by fabricating thin films on
substrates with different orientations would be crucial since
MFM is generally not sensitive to the in-plane component of
magnetization. In either case, controlling the oxygen octahe-
dral rotation, which determines the DM vector and hence the
weak magnetization, is expected to be important to achieve
the magnetization reversal by an electric field, as suggested
theoretically by Ederer and Spaldin[15] and experimentally by
Heron et al. for BiFeO3 thin films.[95] Another open question
is whether we can intrinsically enhance the magnetization of
BiFeO3 by chemical substitution and/or epitaxial strain. Theo-
retical approaches would be effective to tackle this issue. Our
preliminary first-principles calculations indicated that the
cobalt substitution can enhance the canting angle of weak
magnetization;[91] however, more systematic and compre-
hensive studies would be necessary for quantitative discus-
sions. The cycloidal spin structure itself is a fascinating target
of research. Strong coupling between the ferroelectric and
cycloidal spin orders is well known.[96] Recently, Gross et al.
have shown that a single-spin magnetometer can be used to
detect the cycloidal order in BiFeO3.[97]
We hope this progress report serves as a milestone toward
further developing the piezoelectric and multiferroic prop-
erties of BiFeO3 and promotes practical studies aiming
for device applications based on BiFeO3 and BiFeO3-based
materials.

Adv. Mater. 2018, 1705665 1705665  (13 of 15) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Acknowledgements
This study was supported by JSPS KAKENHI (Grant Nos: 16H00883,
16H02393, 16K05731, 17H04952, 17H05489), by the Kanagawa Institute
of Industrial Science and Technology (KISTEC), and by Asahi Glass
Foundation.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
multiferroic materials, piezoelectric materials, polarization rotation,
weak ferromagnetism
Received: September 29, 2017
Revised: March 6, 2018
Published online:
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