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Structural, dielectric, electrical and magnetic characteristics of lead-free

multiferroic: Bi(Cd 0.5 Ti 0.5 )O 3 BiFeO 3 solid solution

Article  in  Journal of Alloys and Compounds · March 2018

DOI: 10.1016/j.jallcom.2018.03.114

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Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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journal homepage: www.elsevier.com

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Structural, dielectric, electrical and magnetic characteristics of lead-free multiferroic:
Bi(Cd0.5Ti0.5)O3 BiFeO3 solid solution
Nitin Kumara, ∗, Alok Shuklaa, R.N.P. Choudharyb
a

PR
Department of Physics, National Institute of Technology Mizoram, Aizawl-796012 India
b
Department of Physics, Siksha O Anusandhan (Deemed to be University) Bhubaneswar-751030, India

ARTICLE INFO ABSTRACT

Article history: This communication provides the detailed description of the synthesis and characterization of a lead-free mul-
Received 29 January 2018 tiferroic solid solution of Bi(CdTi)O3 and BiFeO3 of a general chemical composition Bi(Cd0.45Ti0.45Fe0.10)O3
Received in revised form 8 March 2018

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(abbreviated as BCTFO). The material has been synthesized via a solvent-free solid-state reaction approach by
Accepted 9 March 2018
utilizing high-purity oxides and carbonate in appropriate stoichiometric amount. The structural, morphologi-
Available online xxx
cal, molecular structure, electrical and magnetic characteristics of as-synthesized electronic system were ex-
amined by the powder X-ray diffraction, field emission scanning electron microscopy, vibrating sample mag-
Keywords: netometer and impedance spectroscopy techniques respectively in different experimental conditions. Analysis
Solid solution of X-ray diffraction data of BCTFO shows a single-phase formation of the material in orthorhombic crystal
Micro-structural properties symmetry with very fine powder (average linear crystallite dimension = 30 nm). Detailed studies of dielec-
Electrical characteristics tric parameters (dielectric constant, tangent loss and polarization) in a selected frequencies (1 kHz–1.5 MHz)
CT
Ferroelectric properties and temperatures (300 K–773 K) clearly exhibit one of the important components of multiferroics (i.e., ferro-
Magnetic properties
electricity). Studies of some components of electrical parameters (dielectric, impedance, electric modulus and
Multiferroics
conductivity) of complex spectroscopy confirmed the existence of non-Debye type and other type of dielec-
tric relaxation process in the material. The correlation between the real and idealized circuit response at sev-
eral temperatures has been investigated by using ZSIMP WIN software and impedance data. Study of another
component of multiferroics (i.e., field dependent magnetization) of BCTFO shows the significantly higher
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value of remnant and spontaneous magnetization. Thus, the existence of dielectric polarization and magneti-
zation is single phase (orthorhombic) in a distorted perovskite confirms the multiferroicity of bismuth ferrite
modified bismuth cadmium titanate (BCTFO) at room temperature, and hence the material can be used for
some multifunctional applications.
© 2018.

1. Introduction the such type of materials, some materials, namely YMnO3, TbMnO3,
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BiMnO3 and BiFeO3 have widely been studied and found to have
Materials having simultaneously one or more ferroic order parame- interesting features in them. Except BiFeO3, all other materials dis-
ters (charge, spin or/strain phenomenon), namely ferromagnetism, fer- play both magnetic as well as ferroelectric ordering at a very low
CO

roelectricity and ferroelasticity, in the same phase, are known as mul-
tiferroic materials [1]. Also, some recent reports on TlCdI3, PbFe12O19
nanostructures [2,3], CoTiO3/CoFe2O4 nanocomposites [4],
PbFe12O19 (lead haxaferrite) and CuFe12O19 nanoparticles [5,6] have
shown that these materials can be synthesized by the mechanical mix-
ture of reactants method, sol-gel auto-combustion techniques and us-
ing of amino acids as non-toxic reagents respectively. These materi-
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temperature, and hence, they are not useful for room temperature ap-
plications. Recent discovery of multiferroicity (ferroelectric and fer-
romagnetic) in BiFeO3 (BFO) up to much above the room temper-
ature (Neel temperature = 653 K and ferroelectric transition tempera-
ture = 1103 K) has made the material very useful for multifunctional
applications [9]. BFO has antiferromagnetic G-type of spin config-
uration character along [1 1 1]cubic or [001]hexagonal direction with

als have also many interesting properties including magnetism, which
can be utilized for multifunctional applications Multiferroics are re-
flected as attracting and promising materials for their extensive sci-
entific and industrial uses in the field of data storage devices, mul-
tiple memories, sensors, spintronic, actuators etc. [7,8]. Such type of
materials can not be easily obtained from the nature or fabricated,
therefore, they are considered as rare. Considering the importance of
∗
Corresponding author.
Email address: nitinphysicskushawaha@gmail.com (N. Kumar)
pseudocubic or rhombohedral symmetry at room temperature [10]. In
this material, the ferroelectric and ferromagnetic nature are mainly
arises due to the existence of lone pair electrons in Bi+3 and incom-
pletely filled d-orbital in Fe+3 respectively [11]. Further, BFO shows
higher value of leakage current density due to the existence of impu-
rities, defects, and nonstoichiometric nature, which limit its potential
applications. For the proper use of the material for devices, it is re-
quired to reduce or remove high leakage current and defects. Several
approaches have already been tried, including substitution of iso va-
lence/non-isovalence ions, lanthanides, alkaline earth metals and oth-
ers at the Bi-site and Mn, Co, Ti, etc at Fe-site [12–14], fabrication of

https://doi.org/10.1016/j.jallcom.2018.03.114
0925-8388/ © 2018.
2 Journal of Alloys and Compounds xxx (2018) xxx-xxx

solid solution or composites with other polar or non-polar dielectrics.
Currently, the scientific community are focusing more on lead-free
multiferroic materials due to its environmental friendly nature and
possible promising applications. That's why, an attempt has to be
made to fabricate a lead-free BiFeO3 modified Bi(Cd0.5Ti0.5)O3 [i.e.,
Bi(Cd0.45Ti0.45Fe0.10)O3] multiferroic via a cost effective solvent-free
Analyzer (Premier II P-E loop). The features of current density (J) ver-
sus electric field (E) plots of the material were studied in a temperature
range of 300–773 K along with constant temperature interval (25 K) by
utilizing programmable electrometer (Keithley-6517 B). The vibrating
sample magnetometer (LakeShore-7410) was employ to study mag-
netic behaviour of BCTFO at 300 K.

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solid state reaction approach. Based on the said approach and liter-
ature survey it is found that not much work has been reported on 3. Results and discussion

above material. Our recent work shows the improvement on its phys-
ical/multiferroic properties by the partial substitution at the B-sites
[15–20]. In view of the above, we have synthesized and character-
ized the above solid solution containing Cd and Ti electronic system,
Bi(Cd0.45Ti0.45Fe0.10)O3. In this paper, structural, microstructural, di-
electric, electrical and multiferroics properties of the said electronic
system as a function of experimental conditions are reported.
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3.1. Structural characteristics
3.1.1. Crystal system and data
Fig. 1 depicts the X-ray diffraction pattern of BCTFO calcined
powder. A standard ‘‘POWDMULT″ computer program has been
used for indexing of the major reflection peaks of the pattern in dif-
ferent structural system and unit cell configuration [21]. As the inten-

2. Experimental procedure
2.1. Material and methods
An electronic system containing a small amount (10%) of BiFeO3
in (Cd0.5Ti0.5)O3 (i.e., Bi(Cd0.45Ti0.45Fe0.10)O3 (referred as BCTFO)
has been synthesized from commercially available high-purity
PR
sity of the observed peaks is well defined and sharp, the crystalline
nature of the material is suggested. A good agreement between the ob-
served and calculated lattice spacing (d-values) and diffraction angle
for each refection confirms the orthorhombic symmetry of the mate-
rial. The selected lattice parameters in the orthorhombic system are:
a = 4.9832 (25) Å, b = 7.1734 (25) Å, c = 21.7982 (25) Å and volume
V = 1716.13 Å3 (with the lowest estimated standard deviation in lattice

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(≥99.9%, Loba Chemie and Central Drug House Ltd) oxides and car-
bonate, such as Bi2O3, CdCO3, TiO2 and Fe2O3 in an appropriate sto-
ichiometry. The cost-effective solvent-free solid-state reaction syn-
thesis approach has been performed using three-steps; (i) mechanical
(dry and wet) mixing, (ii) calcinations at 1023 K for 4 h (air atmos-
phere) and (iii) sintering at 1073 K for 6 h (air atmosphere). For syn-
CT
thesis process, high-quality (≥99.7%, alumina lab wares) crucible, disc
and boat were used. The calcined powder was mixed thoroughly with
two percent of polyvinyl alcohol solution (used as a binder), and then
pressed into a circular disk-shape pellets (referred as green pellets) at
an iso-static pressure of 4.5 106 N/m2. As-prepared green pellets have
been sintered at an optimized temperature of 1073 K in a high temper-
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dimension in parenthesis). The crystallite size of said sample, calcu-
lated using the peak width of (0 2 3) plane and other parameters of a
widely used Scherrer equation [22]; K1 λ/(β½ Cosθ) where K1 is con-
stant (0.89), β½ is peak-width at half maxima, and λ is wavelength
used (=1.5418 Å) and θ is Bragg angle, found to be 36 nm. The crys-
tallite size of BCTFO, calculated for a number of widely scattered (on
2θ scale) reflections, was found to be in the range of 20–40 nm. The
detailed information about the d-values, plane position, relative inten-
sities and its crystallite size are summarized in Table 1. The calculated
tolerance factor of perovskite type BCTFO compound is found to be
0.80, which suggests distorted perovskite nature of the material.
3.1.2. (ii) Microstructure

ature electric furnace for 6 h. Fig. 2 (a, b) shows room temperature energy dispersive X-ray mi-
cro-analysis (EDXMA) and corresponding surface micrograph of the
2.2. Characterization BCTFO compound respectively. The EDXMA analysis clearly de-
picts the presence of all elements and their atomic ratio nearly to its
The phase formation and basic structural data of BCTFO were de-
termined using X-ray diffraction data obtained by the X-ray powder
diffractometer (D8-Advance, Bruker). The pattern/data were recorded
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with a slow scan speed (2°/minute), in a wide range of Bragg an-

gles θ (20° ≤ 2θ ≤ 70°) associated with CuKα1 radiation (λ = 1.5405 Å).
Archimedes' method was employed to measure the porosity and rela-
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tive density of the as-prepared pellets. The surface morphology (grains

distribution, grain size, microstructure and voids) and correspond-
ing elemental analysis of the gold-coated pellets have been stud-
ied by field-emission scanning-electron microscope (EVOHD, Carl
Zeiss) and energy dispersive X-ray microanalysis (EDXMA) tech-
nique respectively. The FT-IR spectra of as-synthesized BCTFO pow-
der with KBr medium were examined by FT-IR spectrometer (M/
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S Alpha model, Bruker) in the frequency range from 1400 cm−1 to

400 cm−1. For dielectric and electrical measurements, both the parallel
surfaces of pellet were layered with silver paint (Alfa Aesar) and dried
for 2.5 h at 423 K to eliminate the moisture. In contrast, the tangent
loss, dielectric permittivity, capacitance (Cp in parallel combination),
phase angle (θ) and impedance factor (Z) were recorded in a wide
range of frequency (1 kHz–1.5 MHz) and temperature (300 K–773 K)
by using a computer-interfaced phase sensitive multimeter (Newton4th
Ltd, UK). The ferroelectric polarization or hysteresis loops of the Fig. 1. Powder XRD pattern of Bi(Cd0.45Ti0.45Fe0.10)O3 compound at room temper-
material have been recorded by using a Radiant Precision ature.
 Journal of Alloys and Compounds xxx (2018) xxx-xxx 3

Table 1 3.1.3. (iii) Molecular structure

Comparison of observed and calculated d-values of major reflection plane with ob- Fig. 3 illustrates room temperature FT-IR molecular spectra of
served relative intensity (I/I0) and crystallite size at room temperature. Compound de-
tail: - Bi(Cd0.45Ti0.45Fe0.10)O3 [BCTFO]. Symmetry: Orthorhombic Phase. Bi(Cd0.45Ti0.45Fe0.10)O3 in the wave number range of 1000 cm−1 to
400 cm−1. As shown, the observed IR characteristic bands at
d-spacing (obs.) d-spacing (cal.) Crystallite size 418.44 cm−1 and 443.62 cm−1 are assigned to Fe O Fe bending
Peak (Å) (Å) I/Io h k l (nm) vibration. The absorption bands at 530.42 cm−1 and 594.07 cm−1 are

F
1 4.0956 4.0926 10 1 1 0 35.79 assigned to the stretching vibrations of Fe O bond. It has clearly
2 3.8339 3.8314 16 1 1 2 31.41 been observed from the IR spectra that a broad absorption bands at

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3 3.5898 3.5867 27 0 2 0 39.63 around 443.62 cm−1 and minor band at 561.28 cm−1 appears due to
4 3.2109 3.2162 100 0 2 3 36.07 overlapping of Bi2O3 and Fe2O3 vibration bands [24]. Also, there are
5 2.9359 2.9357 86 1 0 6 31.63
6 2.7136 2.7170 75 1 1 6 33.25 two vibrational modes at around 667.37 cm−1 and 740.66 cm−1 defined
7 2.3913 2.3911 10 0 3 0 29.72 as H2O vapour stretching bands. The widely located Infra-red peaks
8 2.2618 2.2391 21 2 1 3 23.57 (three vibration) at 833.24 cm−1, 910.4 cm−1 and 950.90 cm−1 are as-
9 2.1611 2.1607 16 2 1 4 33.03 signed to the CO2 [25].
10 1.9893 1.9893 14 1 2 8 32.66
11 1.9186 1.9157 11 2 2 4 26.50
3.2. Dielectric characteristics

PR
12 1.7378 1.7367 36 2 0 9 24.46
13 1.6450 1.6448 19 2 3 4 23.08
14 1.6034 1.6042 17 2 3 5 21.79 In order to investigate the internal properties of a material, the
15 1.4929 1.4931 14 3 2 2 25.89 study of dielectric characteristics plays an important role. The inter-
nal behaviour of compound are affected by variation of elemental
composition, operating frequency and temperature, particle size, ap-
plied pressure, electric field, etc. As we know, the constitutive pa-
rameters of dielectrics belong to a complex parameter that generally

ED
counts on operating frequency and temperature. Therefore, it is crucial
to characterize the material characteristics for their best understand-
ing and applications. In view of the importance of dielectrics, various
electrical components, such as capacitance, dissipation factor, dielec-
tric constant, impedance and others were measured with the help of
computer-controlled multimeter as a function of temperature and fre-
quency of the applied field.
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3.2.1. Temperature dependent dielectric parameters
Fig. 4(a) depicts some plots of temperature dependence of dielec-
tric permittivity of BCTFO measured at selected frequencies. Ini-
tially, the nature of dielectric permittivity spectrum shows partially
independent nature at all selected frequencies with operating temper-
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atures. The plots also show that the value of dielectric permittivity
increases slowly on rising temperature. One dielectric anomaly ap-
peared at 580 K (frequency = 1 kHz) vanishes slowly with increasing
frequency. In addition, two more dielectric anomalies observed in the
R
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Fig. 2. (a, b): EDXMA analysis and corresponding FE-SEM micrograph of as-sintered
Bi(Cd0.45Ti0.45Fe0.10)O3 compound respectively at 300 K.
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compositional ratio of bismuth, cadmium, titanium, iron and oxygen.

FE-SEM micrograph clearly depicts less area of voids, compact nature
and nonuniform distribution of grains throughout the surface of sam-
ple. Most of the grains are defused and agglomerated at some sites.
The grain and grain boundaries influence are visible in the FE-SEM
image. The measured grain size (using a software ImageJ software)
was found to be in the range of 60–130 nm, which are smaller than
those of BFO [23]. Thus, as a result, the grain size of solid solution of
bismuth ferrite containing Cd and Ti is found smaller as compared to Fig. 3. The transmittance spectra of Bi(Cd0.45Ti0.45Fe0.10)O3 at 300 K.
that of bismuth ferrite.
4 Journal of Alloys and Compounds xxx (2018) xxx-xxx

tangent loss at different temperatures and frequency has been made in

Table 2.

3.2.2. (ii) Frequency dependence of dielectric parameters

Fig. 5 (a, b) depicts features of frequency dependence of dielec-
tric permittivity and tangent loss at some selected temperatures of

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the range of 300–773 K. The figure indications that the dielectric per-
mittivity has higher value at lower frequencies (1–10 kHz), which is

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slowly falls with increase in frequency. Consequently, the dielectric

Table 2
Comparison of dielectric permittivity and dielectric loss factor for
Bi(Cd0.45Ti0.45Fe0.10)O3 compound at different temperature with frequency range.

S.

PR
No Frequency Temperature 300 K Temperature 773 K

Dielectric Dielectric Dielectric Dielectric

Permittivity Loss Permittivity Loss

1 1 kHz 208 0.01 381 2.78

2 10 kHz 205 0.02 259 0.60
3 25 kHz 203 0.04 229 0.37
4 50 kHz 194 0.07 217 0.21
5 100 kHz 185 0.09 208 0.17

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6 200 kHz 179 0.07 202 0.12
7 300 kHz 174 0.05 197 0.10
8 500 kHz 173 0.04 193 0.09
9 750 kHz 171 0.03 190 0.08
10 1 MHz 170 0.02 188 0.07
11 1.5 MHz 170 0.02 185 0.06
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Fig. 4. Temperature dependence of (a) dielectric permittivity and (b) tangent losses at
selected frequencies for Bi(Cd0.45Ti0.45Fe0.10)O3.

temperature range of 425–510 K (frequency = 200–700 kHz) vanishes

slowly with simultaneously increasing of frequency. The lower tem-
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perature anomaly is associated with the created defects (during sinter-

ing process), whereas higher temperature anomaly occurs due to the
presence of anti-ferromagnetic transition [26]. As both the associated
compounds (BiFeO3 and CdTiO3) of synthesized material (BCTFO)
have high ferroelectric-paraelectric phase transition (as mentions
above), we could not observed the same in our experimental tempera-
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ture range.
We could not detect the expected transition temperature of BCTFO
due to the experimental limitation to achieve required temperature.
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Overall, at higher temperatures (615 K ≤ dielectric permittiv-

ity ≤ 773 K), the dielectric permittivity spectrum rises slowly with
growing temperature and reaches to maximum or peak value for all
operating frequencies.
Further, the frequency dependence of dielectric or tangent loss at
selected frequencies is depicted in Fig. 4 (b). Analysis of the data
has shown an important influence of similar pursues and trend on
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the nature of dielectric permittivity. It is observed from spectrum

that initially, in the low-temperature region (300–340 K), the tangent
loss decreases on increases temperature (achieving the lowest value),
and then again increases slowly with increasing temperature. The
trend of change of tangent loss is small, but at higher temperatures
(>610 K), it increases sharply with increasing temperature. The sharp
rise of tangent loss at higher temperatures at all the frequencies may
be due to the presence of various defects and charge carriers in the
studied material. As a result, both dielectric permittivity and tangent
loss increase simultaneously with increase in temperature. Thus, for
BCTFO solid solution, the comparison of dielectric permittivity and Fig. 5. (a) Frequencies dependence of (a) dielectric permittivity and (b) tangent loss
nature at selected temperature (inset shows lower temperature behaviour) for
Bi(Cd0.45Ti0.45Fe0.10)O3.
 Journal of Alloys and Compounds xxx (2018) xxx-xxx 5

permittivity shows the dispersion in nature at low frequencies. In addi-
tion, the dielectric permittivity falls linearly with increasing frequen-
cies. It is due to the evidence of insufficient dipoles, which follow
the frequency of applied electric field. For exploring the polariza-
tion mechanisms behaviour, shift of short-range may ensue to lead
the entire polarization phenomenon [27]. The well-known Koop's the-
rent density. These facts usually prevent the claim of high electric
fields on the specimen sample, and make the hysteresis loop mea-
surement quite difficult. The theoretical studies, based on the den-
sity functional theory, suggest much larger ferroelectric polarization,
which is consistent with the atomic displacements of Bi3+ and Fe3+
ions [30]. Additionally, the Cd and Ti containing BFO [i.e.,

F
ory provides the suitable description about the dielectric character- Bi(Cd0.45Ti0.45Fe0.10)O3] solid solution shows lower value of the rem-
istics of non-uniform binary structure ferrites [28,29]. Above figure nant polarization (Pr = 0.11 μC/cm2) at room temperature. The satu-

directly displays the dielectric or tangent loss, which increases sud-
denly in the low-frequency region with almost similar nature in high
frequencies. Additionally, the dielectric loss spectrum shows much
higher value in the low-frequency section. This is happening due to the
existence of iron constituents, and at high temperatures, it decreases
quickly through increase in frequency. Although, in the low-tempera-
ture (300–498 K) phase, two peaks are observed in an intermediate fre-
quency range of 10 kHz-1.5 MHz and simultaneously suppressed the
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rated hysteresis loop at room temperature (300 K) confirms the ferro-
electric nature of the material with remnant polarization (Pr) as well as
coercive field (Ec) of Bi(Cd0.45Ti0.45Fe0.10)O3. The calculated value of
Pr and Ec has been found to be ∼0.11 μC/cm2 and 14.8 kV/cm, respec-
tively. Very small value of remnant polarization (Pr) for the material
is due to nature of domain walls and statesTable 3.
As we know, maximum remnant polarization (Pr) for the polycrys-
talline ferroelectric materials depends upon the domain states. The

value at high temperatures for BCTFO. The calculated value of dielec-
tric permittivity at 1 kHz (300 K), 1.5 MHz (300 K), 1 kHz (773 K) and
1.5 MHz (773 K) is found to be 208, 170, 381 and 185 respectively.
Additionally, the value of tangent loss at the above frequencies and
temperatures is 0.019, 0.018, 3.741 and 0.0596 respectively. However,
Fig. 5(a and b) depicts decreasing trend of both dielectric permittiv-
ity as well as tangent loss on increasing frequency. At higher frequen-
PR
remnant polarization, coercive field (Ec) and shape of the loops are af-
fected by many factors, such as charged defects, mechanical stresses,
preparation conditions, thermal treatment, etc., [31,32]. The low value
of remnant polarization, high coercive field and unsaturated loop can
possibly be attributed to a nonuniform distribution of grain size, de-
fects and imperfections in the crystallites. In the present study, due
to the small grain size and number of grain boundaries, more elec-

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cies, both the dielectric parameters (dielectric permittivity and loss)
remain almost constant at high temperatures (523–773 K). Thus, it is
evident, that the dielectric parameters decreases with increasing fre-
quency showing the existence of polar nature of material studied.
3.2.3. (iii) Ferroelectric polarization
The essential electric field required to transport remnant polariza-
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tion to zero is termed as coercive field, and could be calculated from
the saturated polarization (P) versus electric field (E) hysteresis loops.
Fig. 6 shows the ferroelectric hysteretic loops of as-prepared BCTFO
material measured at 300 K on sintered pellet sample. From an ex-
perimental outlook, revealing of the ferroelectric nature of BFO at
room temperature has not proven to be an easy task. The electrical
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tric field is required to get the saturated hysteresis loop. The loss of
bismuth can create vacancies and defects in the material, which are
quite common for bismuth, based ceramic compounds. The defects
and imperfection pinned the domain wall and restrict the movement
of domain walls, resulting the low remnant polarization and high co-
ercive field. We tried to get the saturated hysteresis loop by applying
more and more electric field. However, the leakage current increases
at higher field as seen in Figure and the loop shape changes from lin-
ear to lossy loop. Again, increase in electric field results in the electri-
cal breakdown of the ceramic samples [31–34].
3.3. Electrical characteristics

measurements are more sensitive to investigate the presence of grain
boundaries and impurity phases in specimen sample. As the said de-
fects are considered more conducting, they induce high leakage cur
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3.3.1. Complex electrical impedance
The impedance nature of a poly-crystalline material could be easily
understood by utilizing the complex impedance spectroscopic (CIS)
technique. A poly-crystalline specimen involves a large number of
lesser crystallites, so-called grains combined in random orientation.
The inter-grain region (namely grain-boundary) is having

Table 3
Comparison of capacitive and resistive parameters (fitted) of
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Bi(Cd0.45Ti0.45Fe0.10)O3 compound, which operated at several higher temperature

Model Circuit: [(CR) (CQR)].

Temperature
Rb (F/ Cgb ZCPE (F/ Rgb dependent
Tempt Cb (K) cm2) (Ω.cm2) cm2) (Ω.cm2) term (n)

523 1.343E-10 1.459E7 5.503E-10 8.903E-10 7.456E7 0.1448

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573 1.376E-10 8.625E6 4.943E-10 5.568E-10 5.630E7 0.6954

623 1.098E-09 3.300E4 1.215E-10 4.578E-10 9.337E6 0.4254
673 2.337E-10 5.762E5 1.985E-10 3.912E-08 2.228E7 0.5256
698 2.161E-09 637.5 1.139E-10 2.195E-09 5.942E5 0.6417
723 6.409E-10 1.456E5 1.125E-10 1.064E-09 1.994E5 0.7748
748 1.155E-09 1.036E5 1.039E-10 8.006E-10 2.179E5 0.7819
773 2.156E-09 6.078E4 1.011E-10 6.996E-10 1.790E5 0.7898

Fig. 6. Polarization versus electric field hysteresis loop diagram of

Bi(Cd0.45Ti0.45Fe0.10)O3 material recorded at 300 K.
6 Journal of Alloys and Compounds xxx (2018) xxx-xxx

straining like bonds due to the mismatch in grains orientation. Thus,
the characteristics of grains boundary are different from their grains
features. Thus, this fact provides several remarkable and useful prop-
erties that have exploited in the commercial devices [35]. The said CIS
technique has been utilized to estimate the contribution of grains as
well as grain boundaries effects in their microstructure and electrical
better method to investigate the structural dependence of relaxation
time as well as the relaxation mechanism of ceramic materials [39].
Fig. 8 (a) shows the frequency dependence of real component of
electrical modulus (M′) of BCTFO at several sets of temperature, and
inset of figure shows intermediate temperature. The benefits of adopt-
ing modulus spectra are discrimination of (i) electrode polarization

F
processes of as-studied material, which is summarised in Nyquist for- and (ii) grain boundary effects in the conduction process. It is also no-
mulation section. ticed that the real component of electric modulus is low in the low-fre-

Fig. 7 depicts temperature-frequency dependence of Nyquist plot
(Z′ versus Z″) at selected temperatures (523 K-773 K) of
Bi(Cd0.45Ti0.45Fe0.10)O3. The experimental impedance data of Nyquist
plots have demonstrated with an equivalent [(CR) (CQR)] circuit (by
means of ZSIMP WIN software) to offer us precise portrait of electri-
cal features. Herein, Q is known as constant phase element (Q = ZCPE).
The impedance of constant phase element (ZCPE) is represented as
Z* = [A0 (jω)n]−1, where A0 gives the magnitude of dispersion and
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quency region, which increases with the rise of frequency. These val-
ues display the saturation tendency at a maximum asymptotic point.
It suggests that the conduction process reveals short-range mobility of
charge carriers. Furthermore, it also suggests the possibility of lack of
restoring forces, which is responsible for mobility of charge carriers
under an applied electric field, and thus shows the negligibly small
contribution of electrode polarization of BCTFO.
Fig. 8 (b) shows an imaginary component of electrical modulus

n is a temperature dependent parameter (for an ideal capacitor n is
equal to one and ideal resistor n is equal to zero). The better fitting of
their spectrum lines has attained parallel relationship of grain bound-
ary capacitance (Cgb) to grain-boundary resistance (Rgb) along with
the parallel combination of bulk capacitance (Cb), constant phase el-
ement of impedance (ZCPE), as well as the bulk resistance (Rb). The
symbols (solid ball shaped) and lines (solid red limes) demonstrated
PR
(M″) response at several sets of temperature. It is noticeable from dia-
gram that the variation of M″ spectra with frequency shows an asym-
metric trend of peak broadening for BCTFO. The value of M″ has a
peak at all temperatures which shift toward the low-frequency region
on increasing temperatures. Additionally, the deviation in both M′ and
M″ peak position of said compound is associated with the cation dis-
tribution and operating temperature. Moreover, the asymmetric broad-

ED
their measured and fitted parameters respectively. The Nyquist plots ening of M″ peaks proposes the conduction mechanism, which is as-
consist of a single semi-circular arc, which generally originates from sociated to non- Debye type [40].
the grains [36]. With the change of temperature as well as composi-
tion, the shape, feature of semi-circular arc, capacitive and resistive
behaviour vary significantly. The figure denotes the set of Nyquist
plots, which are separately drawn for different temperatures range. For
the temperature range of 673 K–773 K, the trend of semicircles arcs is
CT
clearly visualised for BCTFO. Moreover, it is also detected that the
rising temperature, intercept at x-axis moves towards lower Zʹ, indi-
cating decreasing trend in resistance, and also the radius of semicircle
arc decreases asymmetric, which confirms the non-ideal Debye-relax-
ation process in the compound [37,38].
RE

3.3.2. (ii) Electrical Modulus

When an electric displacement remains constant, the physical im-
pact of characteristics of electrical modulus resembles to relaxation
of electric field in the compound. The frequency dependence of char-
acteristics of electrical modulus (real and imaginary components) are
R
CO
UN

Fig. 8. Variation of frequency dependence of (a) real electric modulus (M′) and (b)
Fig. 7. Nyquist plots (Z′ versus Z″) at different temperatures. Inset shows lower temper- imaginary electric modulus (M″) at different temperatures. Inset shows lower tempera-
ature response for Bi(Cd0.45Ti0.45Fe0.10)O3 material. ture response for Bi(Cd0.45Ti0.45Fe0.10)O3.
 Journal of Alloys and Compounds xxx (2018) xxx-xxx 7

3.3.3. (iii) Electrical conductivity

The electrical conductivity is an essential qua ntity for revealing
the reliable information about the conduction mechanism (between
ions with mixed valence) and types of carriers, which are responsible
for the conduction process. The electrical features of material have a
significance role in the field of electronic/semiconductor industry. The

F
ac-conductivity of as-synthesized BCTFO has been calculated by the
dielectric data [41,42]. Fig. 9 (a) represents the variation of ac-con-

OO
ductivity in a selected range of frequency (1 kHz-1.5 MHz) at several
operating temperatures (ranging from 300 K to 773 K) for said com-
pound. The nature of figure indicates that the conductivity increases
with the rise of frequencies and temperatures. A suitable approach
namely ‘Jonscher's power law relation’ has been utilized to investigate
the frequency dependence of characteristics of the material [43];

PR
Where, σAC is the total conductivity of the material, σX is fre-
quency independent part, the parameters P and γ suggests the in-
teraction range among the mobile ions with the crystallographic lat-
tice sites and the polarizibility strength respectively.
σωσσωσωσTω = σ0+σ1ω = σ0+aωn.On the other hand, the conduc-
tivity plot shows frequency independent (partially) plateau region at

ED
lower frequency. The conductivity plots subsequently rises and
merges at high frequencies. Therefore, the conductivity growth in-
crease with operating temperature and frequency, the nature of the
plots exhibits semiconducting behaviour (i.e., negative temperature
coefficient of resistance).
Fig. 9 (b) displays the deviation of ac-conductivity with absolute
CT
inverse temperature at various set of frequencies (ranging from 1 kHz
to 1.5 MHz). To investigate the activation energy correlation/variation
with inverse of absolute temperature and frequency, we have divided Fig. 9. (a) Variation of frequency dependence ac-conductivity at different temperatures
different independent regions of the conductivity vs. inverse temper- and (b) Arrhenius plot of ac conductivity vs. (1000/T) for Bi(Cd0.45Ti0.45Fe0.10)O3.
ature diagram. The variation of ac-conductivity is very slow in the
low-temperature zone (Region I) and further increases in the inter-
RE

mediate temperature region (Region II) as well as much larger in the

high-temperature region (Region III) at all frequencies. In existence of
several operated temperatures, the linear variation with varying slopes
is detected. The activation energy (Ea) at different temperature (lower,
intermediate and higher) regions have been calculated from the con-
ductivity vs. inverse temperature plot by using the Arrhenius general
relation; σac = σo*exp (−Ea/KB*T). Thus, the calculated activation en-
R

ergy for 1 kHz at measured lower temperature of (Region-I), inter-

mediate temperature (Region-II) and higher temperature from (Re-
gion-III) are 0.08 eV, 0.53 eV, 0.89 eV, as well as for1.5 MHz are
CO

0.15 eV, 0.27 eV, 0.49 eV, respectively for BCTFO material.

3.3.4. (iv) Leakage current

For better recognition of conduction mechanism, studying of leak-
age current analysis is very necessary. Fig. 10 depicts the electric
field (E) versus current density (J) characteristic at some selected
Fig. 10. Current density (J) vrs. electric field (E) characteristics at different tempera-
UN

temperatures (300 K–773 K) for Bi(Cd0.45Ti0.45Fe0.10) compound. The tures of Bi(Cd0.45Ti0.45Fe0.10)O3.

spectrum plots clearly shows that the leakage densities values are
smaller at low electric field region and further rises rapidly with the
increase in electric field for all temperatures. Thus, the increment
trend of leakage current densities at all operated electric field ap-
proves additional feature of conduction mechanism, which is dom-
inant in conduction process [20,44]. In general, as observed higher
leakage current density (for both higher electric field and measured
temperatures) are mainly responsible for the existence of several ef-
fects as, the appearance of iron valence, oxygen vacancies and sto-
ichiometric disorder features in as-synthesized BCTFO compound
[45]. Additionally, the relationship between current density and elec-
tric field spectrum plots does not follows linear trend of nature, which
is the evidence of non-Ohmic phenomenon of said studied-compound.
Besides, at higher electric field (at above 666 V/cm) along with above
temperature of 773 K, to reveals the said measurements
8 Journal of Alloys and Compounds xxx (2018) xxx-xxx
are much challenging, because the leakage current values were higher
and showing almost constant. However, these phenomenon are orig-
inates due to the occurrence of ferrites constituents in the materials
[46].
3.4. Magnetic characteristics
Fig. 11 displays the magnetic hysteretic loop diagram of as-pre-
pared Bi(Cd0.45Ti0.45Fe0.10)O3 material measured at 300 K with an
applied magnetic field of ±12 KOe. In general, undoped BFO and
multi-element doped sample of Bi(Cd0.45Ti0.45Fe0.10)O3 material,
shows weak ferromagnetic characteristics. Although, the minor addi-
tion of iron ratio/concentration into said compound i.e., Bi(Cd1/4Ti1/
4Fe1/2)O3 material suggest much enhanced ferromagnetic ordering pa-
rameters [19]. It has well known that the bulk BFO having typically
anti-ferromagnetic nature along G-type spin ordering feature below of
the Néel temperature. Several studies have already been focused to
explain their ferromagnetic origin in antiferromagnetic materials fam-
ily and this phenomenon are mainly ascribed as; the creation of un-
compensated magnetic moments arises because of the violation takes
place in large number of bonds exchange of atoms surface [47,48].
Additionally, the formation of oxygen vacancies, leads the occurrence
of Fe3+ ions [49–52]. The presence of Fe2+ ion may perhaps causes
dual exchange interaction nature between Fe2+ and Fe3+ ions through
ED
with the oxygen atom, consequence it might enhances ferromagnet-
ism [53]. The observed quantitative remanent magnetization (Mr), sat-
uration magnetisation (Ms) and coercive field (Hc) values [calculated
from Fig. 11] of the BCTFO material were 0.003 emu/g, 0.007 emu/g
and 585.21Oe respectively.
CT
4. Conclusions
In summary, as-synthesized Bi(Cd0.45Ti0.45Fe0.10)O3 solid solution
were well characterized with the powder X-ray diffraction, energy dis-
persive X-ray microanalysis and electrical impedance spectroscopy
techniques. The XRD pattern analysis shows that the compound crys-
RE
tallizes in the orthorhombic symmetry with average crystallite size of
30 nm. The electrical parameters of said studied compound have been
calculated in extensive range of frequency from 1 kHz to 1.5 MHz
with several range of temperature from 300 to 773 K. It is detected
that the dielectric parameters (dielectric permittivity, dielectric loss)
values decrease with increasing frequency.
R
CO
UN
Fig. 11. Magnetic hysteresis loop diagram of Bi(Cd0.45Ti0.45Fe0.10)O3 material
recorded at 300 K.
These behaviours in dielectric parameters are especially at lower fre-
quencies because of the existence of electronic and interfacial po-
larization features. The complex impedance spectrum (Nyquist dia-
gram) has described by the appearance of semi-circle arc, which well
fitted in terms of equivalent electrical [(CR) (CQR)] circuit that of-
fers precise portrait of electrical features. The electrical modulus (M′
F
and M″) plots reach to their maximum constant value because of to
the relaxation process occurs at higher frequencies, nevertheless the
OO
M′ and M″ values approaches to nearly zero at the lower frequen-
cies. The frequency dependent ac-conductivity spectrum plots are de-
scribes accordingly the Jonscher's power law formulism and the con-
ductivity increases with the rise of frequencies. It is being happens
due to the electrical energy is associated with the higher frequencies.
For BCTFO compound, the calculated activation energies (1 kHz) at
lower temperature (Region-I), intermediate temperature (Region-II)
and higher temperature (Region-III) are 0.08 eV, 0.53 eV, and 0.89 eV
PR
respectively. The temperature dependent resistance and J-E character-
istics demonstrates the non–Ohmic behaviour for BCTFO compound.
It is important to mention here that the significant enhancement in
the value of remnant polarization and saturation magnetization of the
BCTFO compound observed as compared to that of the parent com-
pound (BFO). Hence, as-synthesized BCTFO compound can be used
for the potential application of new generation electronic devices.
Conflict of interest
The authors declare that they have no conflict of interest.
Acknowledgements
Mr. Nitin Kumar is very much thankful to Magnetic Material Lab-
oratory, Department of Physics, Indian Institute of Technology Guwa-
hati for providing some characterization facilities. We are also grateful
to some people around us for their kind help and guidance.
References
[1] D.H. Wang, W.C. Goh, M. Ning, C.K. Ong, Effect of Ba doping on magnetic,
ferroelectric, and magnetoelectric properties in multiferroic BiFeO3 at room tem-
perature, Appl. Phys. Lett. 88 (21) (2006), 212907.
[2] M. Ghanbari, F. Ansari, M.S. Niasari, Simple synthesis-controlled fabrication of
thallium cadmium iodide nanostructures via a novel route and photocatalytic in-
vestigation in degradation of toxic dyes, Inorg. Chim. Acta. 455 (2017) 88–97.
[3] M. Mahdiani, A. Sobhani, F. Ansari, M.S. Niasari, Lead hexaferrite nanostruc-
tures: green amino acid sol–gel autocombustion synthesis, characterization and
considering magnetic property, J. Mater. Sci. Mater. Electron. 28 (2017)
17627–17634.
[4] F. Ansari, A. Sobhani, M.S. Niasari, Simple sol-gel synthesis and characteriza-
tion of new CoTiO3/CoFe2O4 nanocomposite by using liquid glucose, maltose
and starch as fuel, capping and reducing agents, J. Colloid Interface Sci.
514 (2018) 723–732.
[5] F. Ansari, M.S. Niasari, Simple sol-gel auto-combustion synthesis and character-
ization of lead hexaferrite by utilizing cherry juice as a novel fuel and green cap-
ping agent, Adv. Powder Technol. 27 (2016) 2025–2031.
[6] M. Mahdiani, F. Soofivand, F. Ansari, M.S. Niasari, Grafting of CuFe12O19
nanoparticles on CNT and graphene: eco-friendly synthesis, characterization and
photocatalytic activity, J. Clean. Prod. 176 (2018) 1185–1197.
[7] Y. Wang, Q. Jiang, H. He, C.W. Nan, Multiferroic BiFeO3 thin films prepared
via a simple sol-gel method, Appl. Phys. Lett. 88 (2006), 142503-1–;142503–3.
[8] S.K. Pradhan, B.K. Roul, Electrical behaviour of high resistivity Ce-doped
BiFeO3 multiferroic, Physica B 407 (2012) 2527–2532.
[9] A. Kumar, N.M. Murari, R.S. Katiyar, Probing the ferroelectric phase transition
in sol–gel-derived polycrystalline bismuth ferrite thin films, J. Raman Spectrosc.
39 (2008) 1262–1267.
[10] J.M. Moreau, C. Michel, R. Gerson, W.J. James, Ferroelectric BiFeO3 X-ray and
neutron diffraction study, J. Phys. Chem. Solid. 32 (1971) 1315.
[11] S. Pattanayak, R.N.P. Choudhary, P.R. Das, S.R. Shannigrahi, Dy-substitution
on structural, electrical and magnetic properties of multiferroic BiFeO3 ceramics,
Ceram. Int. 40 (2014) 7983–7991.
 Journal of Alloys and Compounds xxx (2018) xxx-xxx
[12] V.S. Puli, A. Kumar, N. Panwar, I.C. Panwar, R.S. Katiyar, Transition metal
modified BiFeO3 with improved magnetization and linear magneto-electric cou-
pling, J. Alloy. Comp. 509 (2011) 8223–8227.
[13] W. Mao, X. Li, Y. LI, X. Wang, Y. Wang, Y. Ma, X. Feng, T. Yang, J. Yang,
Structural phase transition and multiferroic properties of single-phase
Bi1-xErxFe0.95Co0.05O3, Mater. Lett. 97 (2013) 56–58.
[14] H. Deng, M. Zhang, Z. Hu, Q. Xie, Q. Zhong, J. Wei, H. Yan, Enhanced dielec-
tric and ferroelectric properties of Ba and Ti co-doped BiFeO3 multiferroic ce-
ramics, J. Alloy. Comp. 582 (2014) 273–276.
[15] Nitin Kumar, Alok Shukla, R.N.P. Choudhary, C. Behera, Structural and dielec-
tric studies of Bi(Ni0.45Ti0.45Fe0.10)O3 ceramics, AIP Conf. Proc. 1731 (2016),
030008-1–;030008–3.
[16] Alok Shukla, Nitin Kumar, C. Behera, R.N.P. Choudhary, Structural, dielectric
and magnetic characteristics of Bi(Ni0.25Ti0.25Fe0.50)O3 ceramics, J. Mater. Sci.
Mater. Electron. 27 (2016) 1209–1216.
[17] Nitin Kumar, Alok Shukla, C. Behera, R.N.P. Choudhary, Structural, electrical
and magnetic properties of Bi(Ni0.45Ti0.45Fe0.1)O3, J. Alloy. Comp.
688 (2016) 858–869.
[18] Nitin Kumar, Alok Shukla, C. Behera, R.N.P. Choudhary, Structural and electri-
cal characteristics of (Co, Ti) modified BiFeO3, J. Mater. Sci. Mater. Electron.
27 (2016) 7115–7123.
[19] Nitin Kumar, Alok Shukla, C. Behera, R.N.P. Choudhary, Structural, electrical
and magnetic properties of (Cd, Ti) modified BiFeO3, Phys. Lett. 381 (2017)
2721–2730.
[20] Nitin Kumar, Alok Shukla, C. Behera, R.N.P. Choudhary, Structural, electrical
and magnetic characteristics of Ni/Ti modified BiFeO3 lead free multiferroic
material, J. Mater. Sci. Mater. Electron. 28 (2017) 6673–6684.
[21] B. Park, An Interactive Powder Diffraction Data Interpretations and Indexing
ED
Program Version 2.1, E. WU School of Physical Sciences, Flinders University of
South Australia, SA, 19895042.
[22] Nitin Kumar, Alok Shukla, R.N.P Choudhary, Development of Lead Free Multi-
functional Materials Bi(Co0.45Ti0.45Fe0.10)O3, Prog. Nat. Sci.: Materials Interna-
tional. (https://doi.org/10.1016/j.pnsc.2018.01.012).
[23] Pragya Pandit, S. Satapathy, P.K. Gupta, Effect of La substitution on conductiv-
ity and dielectric properties of Bi1-xLaxFeO3 ceramics: an impedance spec-
troscopy analysis, Physica B 406 (2011) 2669–2677.
[24] Subhash Sharma, J.M. Siqueiros, Gunjan Srinet, Shiv Kumar, Brijmohan Prajap-
CT
ati, R.K. Dwivedi, Structural, electrical, optical and dielectric properties of
sol-gel derived (1-x) BiFeO3 -(x)Pb(Zr0.52Ti0.48)O3 novel multiferroics materials,
J. Alloy. Comp. 732 (2018) 666–673.
[25] V.M. Gaikwad, S.A. Acharya, Investigation of spin phonon coupling in BiFeO3
based system by Fourier transform infrared spectroscopy, J. Appl. Phys.
114 (2013), 193901.
[26] Y. Ma, X.M. Chen, Enhanced multiferroic characteristics in NaNbO3-modified
RE
BiFeO3 ceramics, J. Appl. Phys. 105 (2009) 054107–054111.
[27] L.L. Hench, J.K. West, Principles of Electronic Ceramics, John Wiley & Sons,
New York, 1990.
[28] D. Maurya, H. Thota, A. Garg, B. Pandey, H.C. Verma, Magnetic studies of
multiferroic Bi1-xSmxFeO3 ceramics synthesized by mechanical activation as-
sisted processes, J. Phys. Condens. Matter 21 (2009), 026007.
[29] S. Zhang, L. Wang, Y. Chen, D. Wang, Y. Yao, Y. Ma, Observation of room
temperature saturated ferroelectric polarization in Dy substituted BiFeO3 ceram-
R
ics, J. Appl. Phys. 111 (2012), 074105.
[30] J.B. Neaton, C. Ederer, U.V. Waghmare, N.A. Spaldin, K.M. Rabe, First-princi-
ples study of spontaneous polarization in multiferroic BiFeO3, Phys. Rev. B
71 (2005), 014113.
CO
[31] G.H. Haertling, Ferroelectric ceramics: history and Technology, J. Am. Ceram.
Soc. 82 (1999) 797–818.
[32] D. Damjanovic, Ferroelectric, dielectric and piezoelectric properties of ferroelec-
tric thin films and ceramics, Rep. Prog. Phys. 61 (1998) 1267–1324.
UN
View publication stats
9
[33] A. Kumar, V.V.B. Prasad, K.C.J. Raju, A.R. James, Poling electric field depen-
dent domain switching and piezoelectric properties of mechanically activated
(Pb0.92La0.08)(Zr0.60Ti0.40)O3 ceramics, J. Mater. Sci. Mater. Electron. 26 (2015)
3757–3765.
[34] A. Kumar, V.V.B. Prasad, K.C.J. Raju, A.R. James, Ultra high strain properties
of lanthanum substituted PZT electro-ceramics prepared via mechanical activa-
tion, J. Alloy. Comp. 599 (2014) 53–59.
F
[35] A.J. Moulson, J.M. Herbert, Electro-ceramics, Chapman and Hall, New York,
1990.
[36] S. Pattanayak, R.N.P. Choudhary, D. Pattanayak, A comparative study of struc-
OO
tural, electrical and magnetic properties rare-earth (Dy and Nd)-modified
BiFeO3, J. Mater. Sci. Mater. Electron. 25 (2014) 3854–3861.
[37] S. Rani, S. Sanghi, N. Ahlawat, A. Agarwal, Influence of Bi2O3 on physical,
electrical and thermal properties of Li2O·ZnO·Bi2O3·SiO2 glasses, J. Alloy.
Comp. 619 (2015) 659–666.
[38] R. Kumari, N. Ahlawat, A. Agarwal, S. Sanghi, M. Sindhu, Structural transfor-
mation and investigation of dielectric properties of Ca substituted
(Na0.5Bi0.5)0.95-Ba0.05CaxTiO3 ceramics, J. Alloy. Comp. 695 (2017) 3282–3289.
[39] M. Kaiser, Magnetic and electric modulus properties of in substituted
PR
Mg–Mn–Cu ferrites, Mater. Res. Bull. 73 (2016) 452–458.
[40] A. Sinha, A. Dutta, Microstructure evolution, dielectric relaxation and scaling
behaviour of Dy for-Fe substituted Ni-nanoferrites, RSC Adv. 5 (2015)
100330–100338.
[41] B. Pati, R.N.P. Choudhary, P.R. Das, Phase transition and electrical properties of
strontium orthovanadate, J. Alloy. Comp. 579 (2013) 218–226.
[42] S. Dash, R.N.P. Choudhary, A. Kumar, Impedance spectroscopy and conduction
mechanism of multiferroic (Bi0.6K0.4)(Fe0.6Nb0.4)O3, J. Phys. Chem. Solid.
75 (2014) 1376–1382.
[43] A.K. Jonscher, Universal Relaxation Law, Chelsea Dielectrics Press, London,
1996.
[44] C. Karthik, K.B.R. Varma, Dielectric and AC conductivity behavior of
BaBi2Nb2O9 ceramics, J. Phys. Chem. Solid. 67 (12) (2006) 2437–2441.
[45] X. Qi, J. Dho, R. Tomov, M.G. Blamire, J.L. MacManus-Driscoll, Greatly re-
duced leakage current and conduction mechanism in aliovalent-ion doped
BiFeO3, Appl. Phys. Lett. 86 (2005), 062903.
[46] R.N.P. Choudhary, D.K. Pradhan, C.M. Tirado, G.E. Bonilla, R.S. Katiyar, Re-
laxor characteristics of Pb(Fe2∕3W1∕3)O3–BiFeO3Pb(Fe2∕3W1∕3)O3–BiFeO3 solid
solution prepared by mechanosynthesis route, J. Appl. Phys. 100 (2006),
084105.
[47] P.M. Ponnusamy, S. Agilan, N. Muthukumarasamy, T.S. Senthil, G. Rajesh,
M.R. Venkatraman, Dhayalan Velauthapillai, Mater. Char. 114 (2016) 166–171.
[48] S. Manna, S.K. De, Magnetic properties of Li and Fe co-doped NiO, Solid State
Commun. 149 (2009) 297–300.
[49] S.M.H. Shah, A. Akbar, S. Riaz, S. Atiq, S. Naseem, Magnetic, structural, and
dielectric properties of Bi1-xKxFeO3 thin films using sol-gel, IEEE Trans. Magn.
50 (2014), 2201004.
[50] A. Manzoor, A.M. Afzal, M. Umair, A. Ali, M. Rizwan, M.Z. Yaqoob, Synthe-
sis and characterization of Bismuth ferrite (BiFeO3) nanoparticles by solution
evaporation method, J. Magn. Magn Mater. 393 (2015) 269–272.
[51] S. Riaz, F. Majid, S.M.H. Shah, S. Naseem, Enhanced magnetic and structural
properties of Ca doped BiFeO3 thin films, Indian J. Phys. 88 (10) (2014)
1037–1044.
[52] F. Majid, S. Riaz, S. Naseem, Microwave-assisted sol–gel synthesis of BiFeO3
nanoparticles, J. Sol-Gel Sci. Technol. 74 (2) (2015) 310–319.
[53] F. Huang, X. Lu, W. Lin, X. Wu, Y. Kan, J. Zhu, Effect of Nd dopant on mag-
netic and electric properties of BiFeO3 thin films prepared by metal organic de-
position method, Appl. Phys. Lett. 89 (2006), 242914.