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Dielectric studies of multiferroic orthochromites Ho0.9(RE)0.1CrO3

(where RE ¼Gd and Yb)
Shubhra Mathur n, Anjali Krishnamurthy
Department of Physics, University of Rajasthan, Jaipur 302004, India

art ic l e i nf o a b s t r a c t

Article history: Dielectric studies have been made on two orthochromite systems, Ho0.9Gd0.1CrO3 and Ho0.9Yb0.1CrO3. In
Received 9 March 2016 the known multiferroic system of HoCrO3, Ho is substituted by one lower and one higher atomic number
Received in revised form rare earth element (Gd and Yb respectively). Solid state diffusion method has been used to synthesize
22 March 2016
these polycrystalline samples. X-ray diffraction patterns for both the samples show a distorted orthor-
Accepted 24 March 2016
hombic perovskite phase. Temperature and frequency dependent dielectric measurements on the Gd and
Yb substituted samples show ferroelectric nature with ferroelectric to paraelectric (FE–PE) transitions
Keywords: occurring at Curie temperature (Tc)∼530(5) K and ∼490(5) K (at excitation frequency of 1 kHz) respec-
Multiferroic tively. The two studied systems are non-Debye relaxor ferroelectrics and the FE–PE transitions exhibit
Orthochromite
high diffusiveness.
Relaxor ferroelectrics
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Dielectric relaxation
Non-Debye

1. Introduction canted antiferromagnetic order in the two samples to be slightly

Over the past few years, multiferroic materials exhibiting or-
dered magnetism and also ferroelectricity have drawn consider-
able attention. Simultaneous presence of magnetic and ferro-
electric orders makes such materials highly promising for next
generation of memory devices [1–3]. There is a big demand to
search for materials that exhibit both magnetic and ferroelectric
orders at reasonable temperatures showing good magneto-electric
coupling. Materials like BiFeO3 [4,5], BiMnO3 [6] and BiCrO3 [7],
rare earth (RE) manganites LnMnO3 [8,9] and RE chromites LnCrO3
[10–14] and a few others have been studied in some details. The RE
chromites LnCrO3 show canted antiferromagnetism with ordering
temperatures in the range ∼120 K for LuCrO3 to ∼280 K for LaCrO3.
In addition, they show ferroelectric nature with Curie tempera-
tures in the range ∼440–485 K [10]. In this paper we report di-
electric studies of Ho0.9Gd0.1CrO3 and Ho0.9Yb0.1CrO3 which are
HoCrO3 based systems. In the known multiferroic system of
HoCrO3, 10 at% of Ho is substituted by one lower and one higher
atomic number rare earth element.
The two systems have been prepared by the solid state diffu-
sion technique. Powder X-ray diffraction has been used for the
structural characterization of the prepared samples. Magnetization
measurements have shown [15] the Néel temperature of the
n
Correspondence to: Department of Physics, University of Rajasthan, Jaipur
302004, India.
E-mail address: shubh.mathur9@gmail.com (S. Mathur).
lower than of HoCrO3. Dielectric measurements as a function of
temperature and excitation frequencies have been made for both
the samples and results have been compared with reported ones
on RE chromites.
2. Materials and methods
Polycrystalline samples of Ho0.9Gd0.1CrO3 and Ho0.9Yb0.1CrO3
(hereafter referred to as HGCO and HYCO respectively) have been
prepared by the solid state diffusion technique. High-purity oxides
of Ho2O3 (99.9%), Cr2O3 (99.97%), Gd2O3 (99.9%) and Yb2O3
(99.99%) were taken as the starting materials. The stoichiometric
mixture of the oxides for the respective samples was grinded in
agate mortar. The mixture was then pre-sintered at 900 °C for 24 h
followed by heating at 1300 °C for 24 h with intermittent grinding.
Final heat treatment was carried out at 1400 °C for 24 h.
Powder X-ray diffraction (XRD) patterns were recorded at dif-
ferent stages of heating using PANalytical make X’Pert PRO MPD
diffractometer (Cu Kα radiation of 1.5418 Å) to ensure the phase
formation.
For dielectric measurements, the sintered circular pellets of the
powder samples were coated with silver paste on both the sides to
use them as disk shaped capacitors. Measurements have been
carried out using a Wayne Kerr 6500B precision impedance ana-
lyzer. Capacitance and loss tangent have been measured as a
function of temperature and frequency. The sample temperature
was varied from room temperature upto 650 K at five different

http://dx.doi.org/10.1016/j.ceramint.2016.03.195
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: S. Mathur, A. Krishnamurthy, Dielectric studies of multiferroic orthochromites Ho0.9(RE)0.1CrO3 (where
RE ¼Gd and Yb), Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.195i
2 S. Mathur, A. Krishnamurthy / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

frequencies and frequency was varied in the range 100 Hz to

1 MHz of the applied voltage at room temperature. Imaginary part
of permittivity has also been recorded with variable frequency at
different temperatures. Four probe method was used to measure
capacitance. Relative permittivity (or dielectric constant) was ob-
tained using the relation
Ct
ϵr=
ϵ0 A
where C is the measured capacitance and t and A are thickness and
cross section area of the pellet and ϵ0 is free space permittivity.

3. Results and discussion

3.1. Structural characterization

XRD patterns of the samples obtained after final heating at

1400 °C confirmed formation of distorted orthorhombic perovskite
phase without any impurities. Fig. 1(a) and (b) shows the patterns
of HGCO and HYCO respectively. Estimated lattice constants a, b
and c are respectively 5.252(2) Å, 5.521(2) Å and 7.543(3) Å for
HGCO and 5.250(3) Å, 5.520(2) Å and 7.545(4) Å for HYCO. These
values are in close agreement with the reported lattice constants
of 5.2517(2) Å, 5.5206(2) Å and 7.5467(2) Å for HoCrO3 [14].

Fig. 2. Variation of relative permittivity with temperature at different frequencies

for (a) HGCO (inset shows loss tangent versus temperature) and (b) HYCO samples.

3.2. Temperature dependence of relative permittivity and loss

tangent

Fig. 2(a) and (b) respectively show variation of relative per-

Fig. 1. X-ray diffraction patterns of (a) HGCO and (b) HYCO samples.
mittivity εr (dielectric constant) with temperature at different
excitation frequencies of 100 Hz, 1 kHz, 10 kHz, 100 kHz and
1 MHz for HGCO and HYCO samples. With rise in temperature, εr
passes through a maximum which is indicative of ferroelectric to
paraelectric transition. Inset to Fig. 2(a) shows the variation of loss
tangent (tan δ) with temperature at different frequencies for
HGCO sample. The shape of tan δ versus temperature curves for
both the samples is similar to that of εr versus temperature curves.
Temperature corresponding to maximum εr, which we take as
Curie temperature (Tc), is ∼530(5) K for HGCO and ∼490(5) K for
HYCO for an excitation frequency of 1 kHz. The values are some-
what higher than, but are of the same order as reported for other
RE chromites. For example the peak maximum temperature re-
ported for ErCrO3 is 453 K [10]. In contrast to the reported litera-
ture [10] that Tc increases with decreasing ionic size, it has been
observed that Tc for the smaller Yb substituted sample is lower
than for the Gd substituted one. The maximum value of relative
permittivity (i.e. εmax) at Tc for HGCO is ∼7900 and for HYCO is
∼8000 at a frequency of 1 kHz. These are of the order of the value
of 9000 reported [10] for ErCrO3 at peak maximum temperature
for frequency 1 kHz.
Fig. 2(a) and (b) shows that both εr and tan δ decrease with
increasing frequency. We will discuss this aspect in next sub-sec-
tion while referring to Fig. 4. As we go to higher excitation

Please cite this article as: S. Mathur, A. Krishnamurthy, Dielectric studies of multiferroic orthochromites Ho0.9(RE)0.1CrO3 (where
RE ¼Gd and Yb), Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.195i
 S. Mathur, A. Krishnamurthy / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 3

Fig. 4. Variation of relative permittivity with frequency for HGCO (─■─) and HYCO
( ) samples.

3.3. Frequency dependence of relative permittivity and loss tangent

Fig. 4 displays variation of εr as a function of logarithm of fre-

quency (log f) for the two samples at room temperature. For both
the samples, εr decreases with increasing frequency upto a certain
frequency which is about 104 Hz in the case of HYCO and 105 Hz in
the case of HGCO and thereafter it attains a constant value. For low

Fig. 3. Variation of log(1/εr  1/εmax) with log(T  Tc) at 1 MHz for (a) HGCO and
(b) HYCO samples.

frequencies, the peak maximum in εr versus temperature curves

(and also in tan δ versus temperature curves) shifts to higher
temperatures. Dispersion in the values of εr is larger below Tc and
tends to quickly become frequency independent above Tc. Overall
nature of the curves for the two samples is similar to those for
other orthochromites and is indicative of their relaxor type of
ferroelectric behavior [10].
Broad peaks occurring in εr versus temperature curves are
suggestive of diffuse nature of phase transitions [16]. In order to
determine the degree of diffuseness of the phase transition, a
modified Curie–Weiss law [16,17]
⎡1 1 ⎤
log ⎢ − ⎥ = γ log ⎡⎣ T − Tc ⎤⎦ + constant
⎣ ϵr ϵmax ⎦ (1)

is used where εr is the relative permittivity at a temperature T and

εmax corresponds to its value at peak maximum temperature Tc. In
Fig. 3 we have plotted log (1/εr–1/εmax) versus log (T–Tc) at a fre-
quency of 1 MHz for both the samples. Linear fit gives γ∼1.44 for
HGCO and 1.86 for HYCO. It is to be noted that parameter γ has
values between 1 and 2. A value of 1 is indicative of a normal
ferroelectric obeying Curie–Weiss law and a value of 2 is indicative
of completely disordered system [16–18]. The obtained γ values for
the two samples under study are suggestive of high diffuseness Fig. 5. Variation of imaginary part of relative permittivity (ɛ′′) with frequency at
and is higher for HYCO sample. different temperatures for (a) HGCO and (b) HYCO samples.

Please cite this article as: S. Mathur, A. Krishnamurthy, Dielectric studies of multiferroic orthochromites Ho0.9(RE)0.1CrO3 (where
RE ¼Gd and Yb), Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.195i
4 S. Mathur, A. Krishnamurthy / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎
Fig. 6. (a) Variation of loss tangent (tan δ) with log f and (b) normalized plots of tan
δ/(tan δ)max with log (f/fmax) for HGCO (─■─) and HYCO ( ) samples.
measuring frequencies, dipoles are able to follow the field and the
value of relative permittivity corresponds to its quasistatic value.
With increasing frequency, as the dipoles start lagging behind the
field, εr drops and beyond certain frequency, the dipoles no longer
follow the field making εr attain the high frequency value [19,20].
Frequency dependence of the imaginary part of relative per-
mittivity (ε′′) is shown in Fig. 5(a) and (b) for the two samples at
different temperatures. With rise in temperature, the values of
permittivity in low frequency region (below 10 kHz) show sig-
nificant increase. At higher frequencies they become constant ir-
respective of the temperature. Now, the dielectric constant of a
material has contributions from different types of polarizations
[21] (i.e. interfacial, space charge, orientation, dipolar, ionic and
electronic). In the low frequency regime, interfacial and space
charge polarizations are the main contributors which are strongly
temperature dependent. At higher frequencies the observed rela-
tively insignificant variation of dielectric constant is attributed to
electronic polarization which is both temperature and frequency
independent [21].
Fig. 6(a) shows tan δ as a function of frequency for the two
samples at room temperature. The observed frequency depen-
dence is suggestive of dielectric relaxation. The normalized plots of
tan δ/(tan δ)max with log (f/fmax) are shown in Fig. 6(b), where fmax
is the frequency corresponding to (tan δ)max. Curves for the two
samples nearly coincide into a single master curve. Asymmetric
nature of the curves implies more than one relaxation time for the
ions meaning non-Debye relaxation [22]. Exponent β in the
Kohlrausch–Williams–Watts law for distribution of relaxation
Please cite this article as: S. Mathur, A. Krishnamurthy, Dielectric studies of multiferroic orthochromites Ho0.9(RE)0.1CrO3 (where
RE ¼Gd and Yb), Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.195i
times is given [23] as
1. 14
β=
FWHM
where FWHM is full width at half of the peak maximum. The
curves in Fig. 6(b) give the value of β which is 0.75 for HGCO and
0.77 for HYCO. β having values less than 1 implies non-Debye
relaxation for the two samples [24]. For the case of typical Debye
relaxation, β must have a value of 1.
4. Conclusions
We have investigated dielectric behavior of two HoCrO3 based
systems – Ho0.9Gd0.1CrO3 and Ho0.9Yb0.1CrO3. The samples have
been prepared using the solid state diffusion technique. Powder
X-ray diffraction confirmed a distorted orthorhombic perovskite
phase for the two systems. Temperature dependent dielectric
measurements of Gd and Yb substituted samples show them to
exhibit FE–PE transitions at Tc∼530(5) K and ∼490(5) K respec-
tively (at excitation frequency of 1 kHz). Also the relative permit-
tivity (dielectric constant) values are of the order of those reported
for other RE chromites. The two systems are relaxor ferroelectrics,
the FE–PE transitions exhibit high diffusiveness and show strong
non-Debye relaxation.
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Please cite this article as: S. Mathur, A. Krishnamurthy, Dielectric studies of multiferroic orthochromites Ho0.9(RE)0.1CrO3 (where
RE ¼Gd and Yb), Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.195i