Physica B 510 (2017) 104–108

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Physica B
journal homepage: www.elsevier.com/locate/physb

Impact of low level praseodymium substitution on the magnetic properties MARK

of YCrO3 orthochromites
⁎
Surendra Kumara, Indrani Coondoob, Ashok Raoc, Bo-Han Lud, Yung-Kang Kuod, , Andrei
⁎
L. Kholkinb,e, Neeraj Panwara,
a
Department of Physics, Central University of Rajasthan, Bandarsindri 305817, Rajasthan, India
b
Department of Physics & CICECO-Aveiro Institute of Materials, University of Aveiro, 39810-193 Aveiro, Portugal
c
Department of Physics, Manipal Institute of Technology, Manipal University, Manipal 576104, Karnataka, India
d
Department of Physics, National Dong-Hwa University, Hualien 974, Taiwan
e
School of Natural Sciences and Mathematics, Ural Federal University, 620000 Ekaterinburg, Russia

A R T I C L E I N F O A BS T RAC T

Keywords: Praseodymium (Pr) modified yttrium orthochromites (YCrO3 with Pr =0% and 5% at Y-sites) have been
1. Chromites investigated with the aim of exploring the impact of low level Pr substitution on the magnetic properties
2. Magnetization reversal including magnetization reversal, spin reorientation, and exchange bias of YCrO3 compound. The samples
3. Spin reorientation exhibit a distorted orthorhombic structure with Pnma space group. A negative magnetization (or magnetization
4. Exchange bias
reversal) was observed under zero-field cooled (ZFC) mode for the pristine YCrO3 sample, whereas such a
feature disappeared with a 5% Pr substitution. In addition, the Pr-doped samples exhibited a spin reorientation
behaviour which was absent in the pristine sample. Most interestingly, the ZFC magnetic hysteresis loops
revealed a left and upward shift, resembling a negative exchange bias effect. These results indicate the
effectiveness of low level doping in tailoring the magnetic properties of orthochromites.

1. Introduction [13]. This results in a new unidirectional magnetic anisotropy at the

Rare earth orthochromites with general formula RCrO3 (R=tri-
valent rare earth or Yttrium ion), have been extensively investigated
due to their interesting physical and chemical properties. For example,
they exhibit magnetization reversal (i.e. change of polarity in magne-
tization), spin reorientation (SR) and canted antiferromagnetism
(CAFM) below the Neel temperature (TN) that ranges from
110−280 K [1–7]. Their high chemical stability at elevated tempera-
tures makes them suitable candidates for catalysts, electrolytes, fuel
cells, and refractory ceramics [8]. The interplay of magnetic field and
temperature with Cr-R interaction is considered to be responsible for
these fascinating magnetic properties of these compounds [9]. The
temperature induced flipping of magnetization, i.e. negative magneti-
zation or magnetization reversal, is very unusual and such a concept
can be utilized in making thermomagnetic switches. Some of the RCrO3
compounds also display an exchange bias (EB) effect [8,10–12]. The
EB occurs in the systems with ferromagnetic (FM) and antiferromag-
netic (AFM) interface. Such effect weakens with increasing temperature
and completely disappears at the Neel temperature. Exchange bias
refers to a shift of the ferromagnetic hysteresis loop along the field axis
magnetic interface [14] that is useful for magnetic field sensors and
current generation in magnetic read heads [15]. Positive as well as
negative exchange bias-like effects have been reported in doped
orthochromites [10]. In some studies, exchange bias and its sign were
related to the presence of magnetization reversal [6,16,17]. As far as
the parent compound YCrO3 is concerned, it exhibits biferroic nature
with canted antiferromagnetism below Neel temperature TN ~140 K
and relaxor ferroelectric behaviour below 450 K [18,19]. The smaller
ionic size of yttrium makes the geometric tolerance factor t < 1,
resulting in Cr-O-Cr bond angle less than 180°. The anti-symmetric
Dzyaloshinski-Moriya exchange interaction causes spin canting in G-
type antiferromagnet with weak ferromagnetism along the crystal-
lographic c-axis or Г4 mode in Bertaut's notation [20–22]. In this
article, we report the effect of Pr substitution at Y sites on the structural
and magnetic properties of YCrO3 compound. Although Y0.9Pr0.1CrO3
system has already been studied and reported [10], in our present
investigation we carried out a low level of 5% Pr substitution and
performed the magnetic measurements under a relatively high mag-
netic field of 2000 Oe. It was found that the 5% Pr substitution induced
a spin reorientation and a left and upward shift in the ZFC magnetic

⁎
Corresponding authors.
E-mail addresses: ykkuo@mail.ndhu.edu.tw (Y.-K. Kuo), neeraj.panwar@curaj.ac.in (N. Panwar).

http://dx.doi.org/10.1016/j.physb.2017.01.003
Received 5 December 2016; Received in revised form 2 January 2017; Accepted 3 January 2017
Available online 04 January 2017
0921-4526/ © 2017 Published by Elsevier B.V.
S. Kumar et al. Physica B 510 (2017) 104–108

hysteresis loops. These findings revealed that the magnetic properties YCrO 3
of YCrO3 can be significantly altered by a small amount of Pr
substitution.

2. Experimental details (a)

Intensity(a.u.)
Yobs
Polycrystalline samples of YCrO3 and Y0.95Pr0.05CrO3 were pre- Ycal
pared following the solid state reaction method by taking high purity Yobs-Ycal
Pr6O11, Y2O3 and Cr2O3 as starting materials. The mixtures were Bragg position
pulverised properly and calcined at 600 °C and 900 °C for 12 h each
(with intermediate grinding). The obtained powders were crushed and *
pelletized in the form of uniform and compact pellets, which were
sintered up to 1350 °C for 24 h in air. Temperature and field variations
of magnetization measurements were carried out by using SQUID
magnetometer (Quantum Design). Magnetization versus temperature 20 30 40 50 60 70 80
(M-T) data were recorded in the temperature range 4−300 K in both 2 (degree)
zero field cooled (ZFC) and field cooled (FC) modes under external field
of 2000 Oe. Here, zero field cooled protocol refers to sample cooling
from 300 to 4 K and then collecting the magnetization data in warming Y0.95Pr0.05CrO3
under 2000 Oe applied field whereas field cooled mode refers to sample
cooling from room temperature to 4 K in an applied field and then
taking the measurement while heating the sample in the same applied (b)
field.

Intensity (a.u.)
3. Results and discussion

3.1. Structural and morphological analysis

Fig. 1 depicts the x-ray diffraction patterns of pristine YCrO3 and *

5% Pr-doped Y0.95Pr0.05CrO3 orthochromite powder samples. The
structure was refined using Rietveld Fullprof software assigning
Pnma space group. Both the samples exhibited a distorted orthorhom-
bic structure with lattice parameters as follows: a = 5.5147 Å,
b = 7.5358 Å, c = 5.2465 Å, along with the goodness of fitting
χ2 = 5.11, Rwp = 11.5% for YCrO3 and a = 5.5157 Å, b = 7.548 Å,
c = 5.258 Å and χ2 = 2.97, Rwp = 9.86% for Y0.95Pr0.05CrO3. The lattice
parameters of pure YCrO3 sample are consistent with previous report
[23]. Moreover, the comparison of the lattice parameters for the
present samples reveals that cell volume increases with Pr-substitution
which can be understood in terms of the bigger ionic size of Pr3+(1.179
Å) than that of Y3+(1.075 Å) [24]. The theoretical density also increases
from 5.636 g/cm3 to 5.791 g/cm3 with Pr-doping. We also noticed a
small intensity peak (marked by an asterisk) corresponding to un-
reacted and non-magnetic Y2O3 in the diffraction patterns of the
studied samples. Such a peak has been also reported previously in
YCrO3 and YCoO3 samples prepared by combustion and sol-gel
methods, respectively and in YCrO3 nanoparticles synthesized using
the droplet confinement of miniemulsions [19,25,26]. Probably, a high
oxygen pressure or sintering for a longer duration is required to
complete the reaction.
The surface morphologies of the samples are shown in the insets of
Fig. 1. Irregular shaped grains and heterogeneous morphology can be
observed in the case of YCrO3 sample along with the porous structure.
However, for Y0.95Pr0.05CrO3 sample the grain to grain contact
increases, the grain shape improves, and the porosity diminishes.
These findings indicate that the sample quality of YCrO3 can be
improved by low level of Pr doping, which is consistent with the
XRD result.
3.2. Magnetic studies
The temperature variation of magnetization under an applied
magnetic field of H=2000 Oe in ZFC and FC protocols for both the
samples is shown in Fig. 2(a-b). There is a clear bifurcation between the
ZFC and FC curves below paramagnetic-antiferromagnetic transition
temperature TN, for both systems. The ZFC magnetization curve shows
20 30 40 50 60 70 80
2 (degree)
Fig. 1. : XRD patterns of (a) YCrO3 and (b) Y0.95Pr0.05CrO3 samples. Insets show the
surface morphology of these samples.
a sharp peak below TN and then drops to negative value for the YCrO3
sample. This indicates a coexistence of weak ferromagnetic and
antiferromagnetic (WFM-AFM) components, arising from the canted
antiferromagnetic state. Similar behaviour has also been reported for
HoCrO3 chromite [27]. The possibility of negative magnetization in
YCrO3 due to trapped field during the measurement is ruled out since
such a phenomenon was not observed in our Pr-doped sample. In the
FC mode, almost all the spins tend to align in the direction of applied
magnetic field (H = 2000 Oe) and hence a Brillouin-like behaviour can
be noticed. Similar trend has been observed by Tsushima et al. in
EuCrO3 [28]. With only 5% doping of Pr in YCrO3, negative magnetiza-
tion disappears and the magnetization becomes positive in the entire
temperature range of measurement In perovskite orthochromites with
space group Pnma, it was shown that the canted antiferromagnetic
order of Cr3+ ions produces an internal field at the rare-earth site,
whose direction is opposite to the net Cr3+ moments [29]. The fact that
Pr3+ and Cr3+ ions couple antiferromagnetically has also been verified
by the neutron diffraction experiments [30]. Further, MPr3+ is expected
to be greater than MCr3+ and this will be confirmed in the later section
by showing that the FM component decreases with Pr doping. As a
consequence, the net magnetization would be positive for
Y0.95Pr0.05CrO3 that has been experimentally observed in the present
study.
It is clearly seen that the FC magnetic nature of Y0.95Pr0.05CrO3
sample is quite different from that of YCrO3 sample (Fig. 2a-b). For the
Y0.95Pr0.05CrO3 sample, MFC-T curve displays a broad hump below TN,
reaches a maximum magnetization of about 117 emu/mol near 100 K,

105
S. Kumar et al. Physica B 510 (2017) 104–108

250 15
T = 21 K
200 YCrO 10 SR
3
Y0.95 Pr0.05 CrO
5 3
150
H= 2000 Oe
0
100
M (emu/mol)

FC
YCrO 3
-5

dM/dT
50 ZFC
-10
0
-15 T
N
-50
-20 FC
-100 (c)
(a)
-25

0 50 100 150 200 250 300 0 50 100 150 200 250 300
T (K) T (K)

120 300 YCrO 3

Y Pr CrO 3
0.95 0.05 Pr 0.05 Y 0.95 CrO 3
100 250

1/ Oe-mol/emu)
80 H= 200 0 Oe 200
M (emu/mol)

FC
60 ZFC 150

100
)

40

20 (b) 50
(d)

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
T (K) T (K)
Fig. 2. : (a-b) M-T curves under different protocols; (c) dM/dT versus T; (d) temperature variation of inverse of susceptibility for YCrO3 and Y0.95Pr0.05CrO3 samples (solid lines are
guide to the eye).

and thereafter with lowering temperature the magnetization decreases.
Below 21 K the decreasing rate of magnetization becomes slower,
indicating a possible second magnetic transition in Y0.95Pr0.05CrO3. We
plotted the derivative of MFC as a function of temperature for both
samples and the results are shown in Fig. 2c. There is a slight increase
in TN with Pr doping due to the higher Neel temperature (~237 K) of
PrCO3 [1]. It can be further seen that the pure YCrO3 sample has only
one anomaly (corresponding to TN) whereas the Y0.95Pr0.05CrO3 sample
exhibits two distinct peaks. The low-T peak at TSR is presumably
attributed to spin reorientation (ordering) of Pr3+-Pr3+ moments. It is
also argued that there is a spin structure change from the high
temperature canted Γ4 to collinear Γ2 at TSR for the Y0.95Pr0.05CrO3
sample. For the YCrO3 sample, Y3+ ion is non-magnetic and hence Γ4
remains present up to the lowest temperatures.
Above the Neel temperature, the magnetic susceptibility data was
fitted to the Curie-Weiss law Fig. 3:
(T − θCW ) 3kB
χ −1 = = 2
(T −θCW )
C NA μeff
where C is the Curie constant, NA is the Avogadro number, µeff is the
effective magnetic moment, θCW is the Curie-Weiss temperature, and kB
is the Boltzmann constant. The fitting of Eq. (1) is shown as solid lines
in Fig. 2d. For the YCrO3 compound, theoretical values of µeff for three
localized 3d electrons are 3.87 µB/f.u. and 1.73 µB/f.u. corresponding
to high- (S=3/2) and low-spin state (S=1/2), respectively. The experi-
mentally observed values using Eq. (1) are 5.80 µB/f.u. for YCrO3 and
4.29 µB/f.u. for Y0.95Pr0.05CrO3, suggesting that Cr is in the high spin
state in the presently studied samples. Further, the deduced Curie-
Weiss temperature values are −309 K for YCrO3 and −380 K for
Y0.95Pr0.05CrO3 orthochromites. The large negative θCW validates the
existence of a strong AFM interaction in these systems. It is noticed
that 1/χ in the paramagnetic region decreases rather linearly with
temperature for Y0.95Pr0.05CrO3, suggesting the presence of only one
type of magnetic phase in this sample. However, Deng et al. noticed
two slopes in Y0.9Pr0.1CrO3 sample and suggested the coexistence of
two magnetic phases [10]. Remarkably, the two-slope behaviour is
clearly seen in our pristine YCrO3 sample (Fig. 2d). A similar magnetic
behaviour in the paramagnetic region has also been reported recently
by Oliveira et al. in undoped YCrO3 sample [31].
To further understand the magnetic nature of the samples, we have
carried out M-H loop measurements in ZFC protocol at 300 K and 4 K.
Fig. 3a demonstrates the M-H plots at 300 K taken in a field sweep
from −70 to +70 kOe. There is no hysteresis for both samples and this
kind of behaviour is expected for paramagnetic materials. On the other
hand, M-H curve measured at 4 K for YCrO3 sample shows a
pronounced hysteresis without any sign of saturation while a similar
M-H behaviour but a much weaker hysteresis is observed for
Y0.95Pr0.05CrO3 (Fig. 3b). The M-H curve confirms the existence of
(1) canted antiferromagnetic contribution in the studied samples where
the anti-parallel spins have a nonzero magnetization. Therefore, the
high-field part of the M(H) loop can be described as M(H)=χAFH+Ms,
where χAFH is the antiferromagnetic contribution and Ms is the
saturation magnetization of the weak ferromagnetic component [18].
The calculated values of Ms are 0.038 µB/f.u. and 0.007 µB/f.u. for
YCrO3 and Y0.95Pr0.05CrO3, respectively. The small deduced values of
saturation magnetization further attest a small non-compensated
canting of the spins in both compounds. Canting angle α was estimated
using a simple relation between saturation magnetization Ms and that
represents the orbital quenched Cr3+ moment [32]:

106
S. Kumar et al. Physica B 510 (2017) 104–108

T = 300 K as compared to YCrO3 is due to the presence of a magnetic ion (Pr)

300
between two antiferromagnetically ordered Cr-magnetic planes along
200 YCrO (010) which effectively reduces the magnetocrystalline anisotropy since
3
coercivity is related to magnetic anisotropy [33]. Therefore, YCrO3 is
M (emu/mol)

Y0.95Pr0.05CrO3
100 expected to exhibit a larger magnetic anisotropy than that for
Y0.95Pr0.05CrO3. This is corroborated with our observations in M-T
0 curves, i.e. a large irreversibility between ZFC and FC curves below TN
for YCrO3 as compared to Pr-doped sample [Fig. 2(a-b)]. Thus, it is
-100 evident that small amount of Pr substitution is very effective in
modifying the magnetic properties of YCrO3 compound. Further, the
-200 minus sign of HEB reveals a negative EB effect in these samples
(a)
(Table 1). In a recent study on SmCrO3, Gupta et al. claimed that the
-300
phenomenon of EB was closely related to negative magnetization [6].
-80 -60 -40 -20 0 20 40 60 80 However, our present study revealed that it is not a necessary condition
H (kOe) as we have observed EB in Y0.95Pr0.05CrO3 sample but without any
negative magnetization behaviour (Fig. 3b). It appears that the
1000 coupling between weak FM and AFM components of Cr3+ ions is
T=4K responsible for the observed negative exchange bias in the studied
800
samples, whereas the additional coupling between weak FM compo-
600 YCrO3 nent of Cr3+ and ordered Pr3+ ions (magnetization opposite to that of
Cr3+) leads to the enhancement of HEB value (Table 1) for Pr-doped
M (emu/mol)

400 Y0.95Pr0.05CrO3
YCrO3 sample. In order to further understand the complex magnetic
200 nature of these samples, thermal measurements including thermal
0 conductivity and specific heat are in progress and will be reported
elsewhere.
-200
-400 4. Conclusions
-600
(b) Pr substituted yttrium orthochromite samples have been studied to
-800 shed light on their magnetic properties, particularly the features of
-80 -60 -40 -20 0 20 40 60 80 negative magnetization, spin reorientation and exchange bias. In
addition to the increase in lattice volume, the surface morphology
H(kOe) and sample quality were found to be improved with Pr-doping. The
Fig. 3. : M-H curves for pristine and 5%Pr doped YCrO3 samples at 300 K (a) and 4 K parent YCrO3 sample exhibited large magnetic irreversibility along with
(b). negative magnetization. With only 5% Pr substitution, irreversibility
diminished and the negative magnetization behaviour disappeared.
Table 1: Furthermore, the Y0.95Pr0.05CrO3 sample showed the spin reorientation
Exchange bias and effective coercive field values for the studied samples. transition at low temperatures. The magnetization versus magnetic
field curve demonstrated a hysteretic behaviour with no sign of
Compound HEB (kOe) Hceff (kOe)
saturation up to 7 T at 4 K for both compounds. Most interestingly,
YCrO3 −1.6430 10.2496 the presently studied samples exhibited negative exchange bias and the
Y0.95Pr0.05CrO3 −1.9728 −1.2494 coercive field decreased with Pr doping. These results have clearly
revealed that the magnetic properties of YCrO3 are significantly
influenced by a small amount of Pr substitution at Y sites, and the
MS
tanα = observed phenomena can be explained on the basis of the coupling
gμBS (2) between weak ferromagnetic and antiferromagnetic components of
Cr3+ and ordered Pr3+ ions.
where g is the Lande’ g factor and S=3/2. Estimated values of α are 2.0°
and 0.4° for pure and 5% Pr-doped samples, respectively. These values
Acknowledgements
indicate that canted antiferromagnetism is more prominent in the pure
YCrO3 sample resulting in a higher value of saturation magnetization, a
The authors (S.K. and N.P.) would like to thank University Grant
larger hysteresis loop, and also a negative magnetization. Such finding
Commission, New Delhi for providing Rajiv Gandhi National
can be understood in terms of the bigger ionic size of Pr3+ than Y3+ ion
Fellowship (RGNF) and UGC Start-up-grant, whereas I.C. acknowl-
that provides a lesser space for the bond to tilt, in accordance with an
edges the financial support from FCT, Portugal through SFRH/BPD/
increase in geometric tolerance factor ‘t′ with Pr doping.
81032/2011. Support from the Ministry of Science and Technology of
Most interestingly, it is apparent from the M-H loops (Fig. 3b) that
Taiwan under Grants No. MOST-103–2112-M-259-008-MY3 to Y.K.K.
they are shifted to left and upward, resembling a negative exchange
is also acknowledged. A.L.K. acknowledges CICECO-Aveiro Institute of
bias (EB) behaviour. The exchange bias field (HEB) and the effective
Materials (Ref. FCT UID/CTM/50011/2013) financed by National
coercive field (Hceff) values can be determined using the relations
Funds Through the FCT/MEC and, when applicable, co-financed by
HEB = (H1+H2)/2 and Hceff = (H1-H2)/2. Here, H1 and H2 are the
FEDER under the PT2020 Partnership Agreement.
coercive fields values on the left and right sides, respectively, which
correspond to the loop crossing the M=0 axis of M-H curve. The
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