Article

Complex Dielectric and Impedance Spectroscopic

Studies in a Multiferroic Composite of
Bi2Fe4O9-BiFeO3
Panda Alaka and Ramanujan Govindaraj *
Materials Science Group, HBNI, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu,
India; lkpanda@igcar.gov.in
* Correspondence: govind@igcar.gov.in




Received: 4 November 2018; Accepted: 28 November 2018; Published: 2 December 2018


Abstract: Complex dielectric and impedance spectroscopic studies have been carried out in a
detailed manner on the system comprising of Bi2 Fe4 O9 -BiFeO3 composite particles dispersed in a
α-Fe2 O3 matrix as prepared using ball milling and controlled annealing treatments. This multiferroic
composite is observed to exhibit a giant dielectric constant associated with a low tangent loss.
A non-Debye type of relaxation has been deduced based on complex modulus analysis. Based on
these studies, the important role played by bismuth ferrite nanoshell in the core-shell composite
of Bi2 Fe4 O9 -BiFeO3 is elucidated for the observed complex impedance spectroscopic properties of
the system. Electron hopping across Fe2+ /Fe3+ and oxygen vacancies are deduced to be playing
an important role in conduction mechanisms based on activation energy analysis of the complex
impedance spectroscopy results.

Keywords: Bi2 Fe4 O9 ; dielectric; multiferroic; composite

1. Introduction
Coexistence of ferroelectric (paraelectric), ferromagnetic (antiferromagnetic), and ferroelastic
properties in certain materials result in wide applications, such as sensors, actuators, and multistate
memory and spintronic devices [1,2]. Yet, very few single-phase materials, such as BiFeO3 , show this
property at or near room temperature [3]. A thin film of BiFeO3 has been demonstrated to show very
large polarization [1], but it is deduced that the grain boundaries in a polycrystalline film and defect
structures could result in degradation of ferroelectric polarization effects and leakage characteristics.
Thus, the need for studies of multiphase or composite oxides based on bismuth iron oxides exhibiting
multiferroic properties is very important [4–7]. To be considered as important, the composite
material concerned should exhibit strong coupling effects, for example, between ferroelectric and
antiferromagnetic properties [8,9]. Systems consisting of oxides, such as BiMnO3 , BiFeO3 and
Bi2 Fe4 O9 [10] are reported to exhibit strong coupling of ferroelectric and antiferromagnetic properties.
To look for efficient ways to improve significantly the dielectric response of materials, such as BiFeO3 ,
by composite oxides based on the former, which exhibit multiferroic properties at room temperature,
is very important with respect to developing multifunctional devices.
This paper reports the results of detailed complex impedance spectroscopic studies on
Bi2 Fe4 O9 -BiFeO3 composite and explores its suitability for making charge storage devices based
on high frequency applications. BiFeO3 exhibits antiferromagnetic ordering (TN = 643 K) and is also
ferroelectric (TC ~ 1103 K) at room temperature. On the other hand, another bismuth iron oxide based
Bi2 Fe4 O9 is also multiferroic (TC ~ 260 K, TN ~ 250 K). With respect to dielectric studies, single phased
Bi2 Fe4 O9 is observed to possess a low value of dielectric constant (~30–40) whereas BiFeO3 single

Condens. Matter 2018, 3, 44; doi:10.3390/condmat3040044 www.mdpi.com/journal/condensedmatter

Condens. Matter 2018, 3, 44 2 of 15

Condens. Matter 2018, 3, 44 2 of 15

single phased Bi2Fe4O9 is observed to possess a low value of dielectric constant (∼30–40) whereas
BiFeO3 single phase exhibits a high value of dielectric constant of the order of ∼40–50 [11] Posed by
the limitations
phase exhibits aof thevalue
high usageofofdielectric
BiFeO3 based systems
constant of the for electrical
order of ~40–50applications
[11] Posedmainly due to leaky
by the limitations of
behavior,
the usage this work3 aims
of BiFeO basedtosystems
study theforcomplex
electricalimpedance
applicationsbehavior
mainly ofdueBiFeO 3-Bi2Fe
to leaky 4O9 composite.
behavior, this work
aims This paper
to study reports the
the complex bulk structural
impedance behavior ofcharacterization
BiFeO3 -Bi2 Fe4 Oof BiFeO3-Bi2Fe4O9 composite as
9 composite.
prepared by ball milling and local structural and magnetic
This paper reports the bulk structural characterization of BiFeO properties using Mossbauer
3 -Bi2 Fe4 O9 composite as
spectroscopy.
prepared Electrical
by ball milling properties of the BiFeO
and local structural and3-Bi 2Fe4O9 composite
magnetic properties system have beenspectroscopy.
using Mossbauer studied in a
detailed
Electrical properties of the BiFeO3 -Bi2 Fe4 O9 composite system have been studied in a different
manner using complex impedance spectroscopic techniques to understand detailed
relaxations,
manner using andcomplex
are discussed.
impedance spectroscopic techniques to understand different relaxations,
and are discussed.
2. Results and Discussion
2. Results and Discussion
2.1. Structural Analysis
2.1. Structural Analysis
X-ray diffraction pattern obtained in the ball milled and annealed sample shows mainly the
X-rayofdiffraction
presence α-Fe2O3 and pattern
α -Biobtained in the 1).
2O3 (Cf. Figure ballThis
milled
can and annealedbased
be deduced sample on shows
the stickmainly the
patterns
presence of α-Fe
provided corresponding O
2 3 and α-Bi O (Cf. Figure 1). This can be deduced based on the
to α-2 Fe32O3 and α- Bi2O3. XRD pattern corresponding to the case of ball stick patterns
provided
milled and corresponding
annealed (BMA) to α-Fesample
2 O3 andconfirms
α-Bi2 O3 . XRD pattern corresponding
the formation of Bi2Fe4O9 to andtheBiFeO
case of3 ball milled
phases as
and annealed (BMA) sample confirms the formation
expected along with Fe2O3. This implies a significant interaction of Bi Fe
2 4 9 O and BiFeO phases as
of Bi2O3 3along with α-Fe2O3,expected
along with
resulting inFe 2 Oformation
the 3 . This implies a significant
of Bi2Fe 4O9 as wellinteraction of Bi2 O3Aalong
as BiFeO3 phases. with α-Fe
significant 2 O3 , resulting
presence of Bi2Fe4Oin9 has
the
formation
been of Bi2in
observed Fe4the
O9 ball
as well as BiFeO
milled phases. A
and 3annealed significant
sample, hencepresence
Bi2Fe4Oof9 has
Bi2 Fe 4 O9 prepared
been has been observed
through
in thestate
solid ball milled
reaction and annealed
and sample,
the resulting XRDhence Bi2 Fe(Figure
pattern 4 O9 has1c)
been prepared
shows through
that the sample solid state reaction
contains a single
and theofresulting
phase Bi2Fe4O9.XRD pattern (Figure 1c) shows that the sample contains a single phase of Bi2 Fe4 O9 .

Figure
Figure 1. 1. XRD
XRDpatterns
patternscorresponding
corresponding toto
(a)(a)
ball milled,
ball (b)(b)
milled, ballball
milled andand
milled annealed ball ball
annealed milled and
milled
annealed
and annealed (BMA) sample
(BMA) withwith
sample broadened
broadenedpeaks indicative
peaks of composite
indicative of compositestructure as compared
structure as comparedto (c)
to
Bi2Fe
(c) Bi24O
Fe94prepared through
O9 prepared solid
through state
solid reaction.
state Also
reaction. shown
Also shown are
arethe
thestick
stickpatterns
patternscorresponding
corresponding to
α-Bi22OO33and
andα-Fe
α-Fe22OO3.3 .

2.2. TEM
2.2. TEM Studies
Studies
Transmission electron
Transmission electron microscopy studies reveal
microscopy studies reveal that
that there
there are
are core-shell
core-shell structured
structured particles
particles
occurring in the ball milled and subsequently annealed sample (Cf. Figure 2). Based on the analysis
occurring in the ball milled and subsequently annealed sample (Cf. Figure 2). Based on the analysis
of the
of the selected
selected area
area electron
electron diffraction
diffraction (SAED)
(SAED) pattern corresponding to
pattern corresponding to the
the core,
core, it
it is
is deduced
deduced that
that
the core is basically composed of Bi2 Fe4 O9 . Based on the FFT analysis, it is deduced that the shells
Condens. Matter 2018, 3, 44 3 of 15

Condens. Matter 2018, 3, 44 3 of 15

Condens.
the coreMatter 2018, 3, 44
is basically composed of Bi2Fe4O9. Based on the FFT analysis, it is deduced that the shells 3 of 15
are
amorphous in nature,
the core is basically thus these
composed particles
of Bi are deduced as having Bi2Fe4O9 as the core and a shell of
2Fe4O9. Based on the FFT analysis, it is deduced that the shells are
amorphous
amorphous
are amorphous bismuth
in nature, ferrite
thus
in nature, and
these
thus alpha-Fe
particles
these 2O3. The presence of BiFeO3 and alpha-Fe2O3 have been
areare
particles deduced as as
deduced having
having Bi2Bi
Fe24Fe
O94 O
as9 the core
as the andand
core a shell of
a shell
deduced
amorphous
of based
amorphous on
bismuth the
bismuth results
ferrite of
ferriteand XRD and
andalpha-Fe
alpha-Fe Mössbauer
2OO3. The
studies. of
. Thepresence
presence of BiFeO
BiFeO3 andand alpha-Fe2O O3 have
have been
2 3 3 2 3
deduced based on the results of XRD
XRD and
and Mössbauer
Mössbauer studies.
studies.

Figure 2. Transmission electron micrograph showing the presence of core-shell particles.

Figure
Figure 2. Transmission
Transmission electron micrograph showing the presence
presence of
of core-shell
core-shell particles.
particles.
2.3. Mössbauer Studies
2.3. Mössbauer Studies
2.3. Mössbauer Studies
Mössbauer studies have been carried out in transmission geometry in order to mainly
Mössbauer
understand
Mössbauer the studies
local
studies have
structure
have been carried
and
been out inout
magnetic
carried transmission
properties ofgeometry
in transmission the phases in order
geometry to
inmainly
existing in the
order understand
tosamples.
mainly
the local
Resultant structure
Mossbauer and magnetic
spectra properties
(Cf. Figure of
3) the
and phases
analyzedexisting in
hyperfine
understand the local structure and magnetic properties of the phases existing in the samples.the samples.
parameters Resultant
(Cf. Mossbauer
Table 1) are
spectra
shown. (Cf. and
Resultant Mossbauer spectra (Cf. Figure 3) and analyzed hyperfine parameters (Cf. Table 1)only
In Figure
the ball 3)
milled analyzed
sample, ithyperfine
is observed parameters
that almost (Cf. Table
all Fe 1)
atomsare shown.
are In
associated the ball
with milled
are
α-Fe 2O3, it
sample, implying
is observedthat most
that α-Fe
almost 2O
all3 particles
Fe atoms exist
are as a single
associated phase.
with Only
only
shown. In the ball milled sample, it is observed that almost all Fe atoms are associated with only α-Fe about
2 O 3 , 4% of
implying Fe atoms
that are
most
observed
α-Fe
α-Fe22O to be associated
O33, implying
particles exist as with
that most a singleBiFeO
α-Fe 3. While
phase. Onlyin about
the Bi24%
Fe4Oof9 sample
Fe atoms prepared through
are observed
2O3 particles exist as a single phase. Only about 4% of Fe atoms are
to the solid state
be associated
route,
with it
BiFeO is . observed
While in
observed to3 be associated with that
the Bi Mössbauer
Fe O
2 BiFeO sample spectrum
prepared could
through be de
the convoluted
solid state route,
4 9 3. While in the Bi2Fe4O9 sample prepared through the solid into
it is two
observed doublets
that
state
characteristic
Mössbauer
route, it isspectrumof Bi2Fe4could
observed Othat
9, withbe Fe convoluted
de atoms occupying
Mössbauer into two
spectrum octahedral
doublets
could be de and tetrahedralofsites.
characteristic
convoluted Bi2 Fe
into It4 O
two is 9observed
,doublets
with Fe
that
atoms in addition
occupying to the doublet
octahedral corresponding
and tetrahedral to Bi 2Fe4It
sites. O ,
9is there occurs
observed broad
that
characteristic of Bi2Fe4O9, with Fe atoms occupying octahedral and tetrahedral sites. It is observed in modified
addition sextets
to the related
doublet
to BiFeO
that 3 evolved in
corresponding
in addition to Bi
to the Fethe
4 studied
O
2 doublet
9 , there BMA sample,
occurs
corresponding broadto Biand the corresponding hyperfine3 parameters
modified sextets related to
2Fe4O9, there occurs broad modified
BiFeO evolved are
in the
sextets related
presented
studied BMAin Table
sample,1. and the corresponding hyperfine parameters
to BiFeO3 evolved in the studied BMA sample, and the corresponding hyperfine parameters are are presented in Table 1.
presented in Table 1.

Figure 3. Mössbauer spectra corresponding to (a) ball ball milled

milled mixture
mixture of
of Bi
Bi22O
O33 and Fe22O33,, (b)
(b) BMA,
BMA,
and (c) Bi22Fe O
Figure 3. Mössbauer9 sample.
Fe4 O9 sample.
4
spectra corresponding to (a) ball milled mixture of Bi2O3 and Fe2O3, (b) BMA,
and (c) Bi2Fe4O9 sample.
Condens. Matter 2018, 3, 44 4 of 15

Table 1. Hyperfine parameters obtained through Mössbauer spectroscopy of samples subjected to

different annealing treatments.

Γi δi ∆i Bhf
Sample Details i fi
mm/sec mm/sec mm/sec Tesla
1a 0.48 0.38 -0.21 51.8 0.75
1b 0.45 0.36 -0.15 50.3 0.18
BM-α-Fe2 O3 -Bi2 O3
1c 0.18 0.33 -0.14 53.4 0.04
2a 0.22 0.30 0.38 40.4 0.03
1a 0.22 0.34 -0.18 51 0.34
1b 0.26 0.33 -0.15 52 0.12
2d 0.28 0.48 0.24 47.3 0.06
BMA 2b 0.26 0.44 1.09 46 0.05
2c 0.24 0.50 0.23 35.5 0.07
3a 0.25 0.24 0.82 0 0.14
3b 0.3 0.38 0.53 0 0.22
3a 0.32 0.29 0.86 0 0.51
Bi2 Fe4 O9 (SSR)
3b 0.32 0.39 0.33 0 0.49

Mössbauer results presented in Table 1 show the presence of phases, such as α-Fe2 O3 , BiFeO3-x ,
and Bi2 Fe4 O9 , indicated as 1, 2, and 3, respectively. Here, 1a ,1b ,1c corresponds to α-Fe2 O3 , while 2 and
3 are due to Fe atoms associated with phases, such as BiFeO3 and Bi2 Fe4 O9 , respectively.
Hyperfine parameters deduced in the ball milled sample show mostly alpha-Fe2 O3 commensurate
with XRD results. Mössbauer studies carried out in Bi2 Fe4 O9 prepared through the solid state route
(Cf. Figure 3 and Table 1) show Fe atoms occupying tetrahedral and octahedral sites. In the case
of BMA, it could be deduced that about 46% of Fe atoms are associated with alpha-Fe2 O3 , and the
remaining fractions associated with magnetic interactions are due to BiFeO3 .
Importantly, it is seen from the hyperfine components corresponding to BiFeO3 that the presence
of oxygen vacancies in this phase could be deduced as indicated by higher values of isomer shift
compared to 0.3 mm/s corresponding to Fe3+ . Hence, based on the XRD and Mössbauer results, it can
be deduced that the system of the present study BMA is characterized to be a composite of Bi2 Fe4 O9 ,
BiFeO3 and α-Fe2 O3 .
In the following section, we will mainly discuss the results of complex impedance spectroscopic
studies in this composite.

2.4. Complex Modulous Spectroscopic Studies

Complex modulous spectroscopy is an important tool for determination, analysis,
and interpretation of dynamical aspects of electrical transport properties in materials, such as
carrier/ion hopping rate and conductivity relaxation. Modulous spectroscopy results are mainly useful
for distinguishing spectral components of materials having similar values of resistances, but different
capacitances. These results are mainly used for suppressing electrode effects and to get the intrinsic
effects corresponding to the sample.

2.4.1. Dielectric and Impedance Studies

Dielectric response of a system represents the variation of resistive and capacitive
behavior with frequency and temperature as well distinguishing any anomaly around the
transition temperature giving information about the possible magnetodielctric, magnetocapacitive,
or magnetoelectric coupling.
Dielectric properties of the BMA sample are measured and compared in terms of frequency
dependence of real part of the dielectric constant (ε1 ) at different temperatures of the samples
(Cf. Figure 4). As shown in Figure 4a, a sharp decrease in the dielectric constant with an increase in
frequency is indicative of a Maxwell-Wagner type relaxation due to space charge release, creating a
Condens. Matter 2018, 3, 44 5 of 15

high impedance barrier at the sample electrode interface and thus a high value of the dielectric constant.
With an increase in the frequency of the applied electric field, the dipoles are unable to follow the
applied field and thus the dielectric constant (ε) decreases and becomes independent of temperature in
a high frequency region. A significantly large value of the dielectric constant has been observed in
the sample. The step like dielectric relaxation is observed at low frequencies for low measurement
temperatures. While the trend according to Koop theory is followed in both the cases, there is a plateau
region in the low frequency region as seen in the ε1 vs. f plot, and correspondingly there occurs a
peak in the tangent loss shown as the inset in the case of the ball milled and annealed sample (BMA).
This plateau region is further observed to shift to a high frequency region with increasing temperature.
This can be attributed to a new relaxation phenomena appearing in the case of the BMA sample due to
the presence of off stoichiometric BiFeO3 as deduced from the Mössbauer results.
The frequency value at which the step like behavior occurs is observed to increase with
an increasing temperature of the sample. The step like dielectric relaxation as observed at low
temperatures in the case of BMA is understood to be due to polaron relaxation, which results from the
carrier hopping process between Fe2+ and Fe3+ . Such a polaron hopping includes a dielectric relaxation
process roughly explained by Debye theory. At low temperatures, electric dipoles freeze due to the
relaxation process. The relaxation process is mainly dictated by the rate at which the polarization
occurs and the frequency of the applied electric field.
The dielectric relaxation is, in general, represented as:

ε (ω) = ε∞ + (εo − εω )/(1 − iωτ) = ε1 (ω) + i·ε2 (ω)

where ω is the angular frequency, and εo and ε∞ are the static dielectric constant (ω → 0) and permanent
dielectric constant (ω → ∞). Where τ is the relaxation time and ε1 (ω) and ε2 (ω) are the real and
imaginary parts of the dielectric response, respectively. The loss factor is given as tanδ = ε2 (ω)/ε1 (ω),
while δ is the phase difference between the applied electric field and induced current. While ε2 (ω) can
be obtained from the above equation as ε2 (ω) = ω ·τ/1 + (ω ·τ)2 and the maximum of ε2 (ω) lies around
ω ·τ ≈ 1.
A close observation of the plots (cf inset 4(a) show that a dielectric peak corresponding to a
dielectric loss peak (cf Figure 4a(i),(ii)) is observed, which shifts to a high frequency with an increase in
temperature. The presence of such a peak is indicative of conductive losses due to relaxing dipoles
in the sample [12]. This occurs in a transition temperature range of Bi2 Fe4 O9 (~300 K) and shifts
towards the magnetic transition temperature of BiFeO3 (~500 K). Being a sum property, εeff ’ is expected
to include ε values from the phases in the composite that is from Bi2 Fe4 O9 , BiFeO3 , and Fe2 O3 as
well. An observation of a similar anomaly in the dielectric constant has been previously observed
and discussed for BiFeO3 [13]. The shifting of the loss peak implies that it is a thermally activated
process [13].
The dielectric relaxation time, τ, is given as τ−1 = τ 0 −1 exp(−Ea /kB T), with Ea as the activation
energy required for relaxation and kB T as the thermal energy. As the maximum of ε2 (ω) lies around
ω ·τ ≈ 1, from the tangent loss curve corresponding to different temperatures, the values of the
dielectric relaxation time have been obtained. Plotted in Figure 4c is the variation of the natural
logarithm of dielectric relaxation time with inverse temperature. From the slope of the linear graph,
the value of the activation energy for relaxation could be obtained as around 0.6 eV, matching well with
the thermally activated mechanism of charge carrier transport across the interface of the grain/grain
boundary. The loss peak could be fitted with the Arrhenius equation and fitted with a straight
line [14]. The activation energy obtained is 0.6 eV (cf Figure 4c), which is close to that of the energy
corresponding to Fe2+ /Fe3+ electron hopping due to the oxygen vacancies present in the constituting
phases [15]. The insets in Figure 4a show the discontinuity around the transition temperature region of
both the phases.
Condens. Matter 2018, 3, 44 6 of 15
Condens. Matter 2018, 3, 44 6 of 15

(a)

(b) (c)
FigureFigure
4. Temperature dependence
4. Temperature of (a) dielectric
dependence permittivity.
of (a) dielectric Corresponding
permittivity. variations
Corresponding marked
variations marked
inside rectangular panels are magnified and shown in insets as (i) and (ii), respectively. (b)
inside rectangular panels are magnified and shown in insets as (i) and (ii), respectively. (b) showsshows the the
core-shell structured
core-shell particle
structured having
particle havingdielectric constants, εεCC and
dielectricconstants, and ε ε, sfor
s
, for
thethe
corecore
and and shell,
shell, respectively.
respectively. While
While (c) (c) shows
shows the variation
the variation of ln(τ ·of
tanln(δ)τ∙tan
withδ)1000/T.
with 1000/T.

The high
Thedielectric response
high dielectric is mainly
response contributed
is mainly by theby
contributed shell
theandshellinterfacial polarization
and interfacial i.e., i.e.,
polarization
Maxwell–Wagner polarization. In a core-shell structure, which is present in a medium
Maxwell–Wagner polarization. In a core-shell structure, which is present in a medium with a dielectric with a
dielectric constant,
constant, ε, with
ε, with the the
corecore having
having a dielectric
a dielectric constant, εC ,εCand
constant, , and thickness,L,L,while
thickness, whileif ifthese
thesevalues
valuescorresponding
correspondingtotothetheshell areεSεSand
shellare andd,d,the
theeffective
effectivedielectric
dielectricconstant
constantat atlow
lowfrequencies
frequenciesisisgiven,
ω, as:
given,ω, as:
*
ε* ≈ (ε εC≈/ ε(ε)C+/ε)
( ε+ (ε /(ε δ [1 + iωτ])) ≈ Lε /d
S / (εS δ [1 + iωτ ])) ≈ LεS /d S
Condens. Matter 2018, 3, 44 7 of 15

where in the above equation δ is given as d/L. In the present case, taking the value of the dielectric
constant (of εS ) of BiFeO3−x as around 50 and d as typically of the order of a few nm (≈1 nm) and L as a
few micron, we could get the value of ε* typically of the order of 0.5 × 105 , typically matching with the
results around low frequencies obtained in this study, and thus elucidating the giant dielectric response
of Bi2 Fe4 O9 and bismuth iron oxide in a core-shell structure. Further, the presence of insulating
α-Fe2 O3 in the outer shell significantly enhances the effect of polarization of charges at the bismuth
ferrite interface. In the present case, it is important to note that both the basic value of the intrinsic
dielectric constant (εS ) and the interface effect in terms of the thickness of the shell and interface effects
contribute for the enhanced value of the giant dielectric relaxation.
Thus, the strong polarization effects are understood to be due to between electron trapped oxygen
vacancies of BiFeO3 and that in any other cation (Bi3+ ), thus inducing space charges between the
insulating core (Bi2 Fe4 O9 ) and inner surface of the shell of α-Fe2 O3 . High values of permittivity
associated with a strong maximum in the dielectric losses have been reported in bismuth iron oxide
based thin films and core-shell structures.
Variation of the real part of impedance with frequency at different temperatures are shown
Variation of the real part of impedance with frequency at different temperatures are shown in
in Figure 5. The Z’ value decreases with increase in T and merges at a higher frequency and
Figure 5. The Z’ value decreases with increase in T and merges at a higher frequency and becomes
becomes constant.
constant. This implies
This implies space
space charge charge
release release
in the in the
material [16].material
The zoomed[16].in The
regionzoomed
in Figurein5aregion
in Figure 5a shown as arrow depicting the constancy of the modulus value
shown as arrow depicting the constancy of the modulus value at the low frequency region, which at the low frequency
region, whichwith
decreases decreases with
frequency andfrequency
becomes zero.andAbecomes zero. peak
corresponding A corresponding
is observed in thepeak is fobserved
Z” vs plot in
the Z”(Cfvs. f plot
Figure (Cfwhich
5b), Figure 5b),broad
shows whichand shows broad and
asymmetric peaksasymmetric peaksa shifting
shifting towards towards
high frequency anda high
indicative
frequency andofindicative
the non-Debye
of thetype due to thetype
non-Debye distribution
due to of
therelaxation as theofwidth
distribution of the peak
relaxation as thevaries
width of
for different temperatures [17]. The Arrhenius fitting of the peak frequency versus
the peak varies for different temperatures [17]. The Arrhenius fitting of the peak frequency versus the inverse of the
temperature (Figure 5c) could be fitted with a straight line with a high value of activation
inverse of temperature (Figure 5c) could be fitted with a straight line with a high value of activation energy
possibly due to the inhomogeneous grain boundary effects due to the occurrence of multiple
energy possibly due to the inhomogeneous grain boundary effects due to the occurrence of multiple
multiferroic phases.
multiferroic phases.

6 10
(a) 623 K
Z'(*10 ohms)

8
5 593 K
(i)
Z'(*108 ohms)

6 573 K
5

4 543 K
4
3 2
2 0
0 1 2 3 4 5 6 7 8
1 10 10 10 10 10 10 10 10 10
f (Hz)
0
2.5 423 K 443 K 473 K
(b) 493 K 523 K 543 K
573 K 593 K 623 K
2.0 6
5 (ii)
Z" (*108 ohms)

Z" (*10 ohms)

1.5 4
3
6

2
1.0
1
0
0.5 0 1 2 3 4 5 6 7 8
10 10 10 10 10 10 10 10 10
f (Hz)
0.0

0 1 2 3 4 5 6 7 8
10 10 10 10 10 10 10 10 10
f (Hz)

(a) and (b)

Figure 5. Cont.
 0.0

0 1 2 3 4 5 6 7 8
10 10 10 10 10 10 10 10 10
f (Hz)

Condens. Matter
Condens. Matter 2018,
2018, 3,
3, 44
44 88 of 15
of 15
(a) and (b)

(c)
(c)
Figure 5.
Figure 5. (a)
(a) and
and (b)
(b) show
show the
the frequency
frequency dependence
dependence of of the
the real
real (top)
(top) and
and imaginary
imaginary (bottom)
(bottom) part
part of
of
1
the impedance, respectively. Shown in the insets are magnification of rectangular panels
the impedance, respectively. Shown in the insets are magnification of rectangular panels showing the showing the
variation of
variation of Z’
Z’ and
and Z”
Z" with
with frequency.
frequency. While
While (c)
(c) shows
shows Arrhenius
Arrhenius fitting
fitting of
of the
the peak
peak frequency
frequency of
of the
the
variation of
variation of Z”.
Z’’.

The imaginary
The imaginaryand andrealreal part
part of impedance
of impedance valuesvalues
plottedplotted (Cf Figure
(Cf Figure 6) showing
6) showing semicircles
semicircles known
known
as as a Cole-
a Cole-Cole plot isCole plot in
effective is separating
effective inoutseparating
the spectraloutcomponent
the spectral component
contribution of contribution
resistance from of
resistance
the from boundary,
grain, grain the grain, and grain boundary,
electrodes. and
The electrodes.
shifting of theThe shifting
intercept on of the intercept
abscissa correspondson abscissa
to the
corresponds
total resistancetocontribution
the total resistance contribution
and is observed and an
to shift with is observed
increase into shift withindicative
temperature an increase in
of the
temperature
resistive indicative
property that isofthethebulk
resistive property
resistance, that This
Rb [18]. is theimplies
bulk resistance,
that, withRincreasing
b [18]. This implies that,
temperatures,
withconductivity
the increasing temperatures,
of the samplethe conductivity
increases as more ofelectrons
the sample areincreases as more electrons
free to contribute to conductionare freedueto
contribute to conduction due to available thermal energy. The observation
to available thermal energy. The observation of a semicircle may indicate that the constituent phases of a semicircle may
indicate
must that the constituent
be existing in a compact phases
manner,must bethe
like existing in a compact
core-shell manner, like
type of particles, due the core-shell
to which type of
the overall
particles, dueistocoming
contribution which as theaoverall contribution
single semicircle evenis coming
thoughas a single
three phasessemicircle even As
are present. though three
the grain
phases
and areboundary
grain present. Asare the grain anddifferent
distinctively grain boundary are distinctively
in their order of magnitude, different in their
it is difficult to order
get two of
magnitude,corresponding
semicircles it is difficult to to get
the two
grainsemicircles corresponding
and grain boundary on one to scale
the grain and grain
[19]. Thus, boundary
modulus analysison
one
is an scale [19].plot
effective Thus, modulus
to observe analysis
this is an effective
effect prominently as,plot to observe
instead this effect
of resistance, prominently by
it is characterized as,
instead of effects
capacitive resistance,
in theit sample,
is characterized by capacitive
which comes close for effects
the grainin the
andsample, which comes
grain boundary. This close for the
is discussed
grain
in and
detail grain boundary. This is discussed in detail subsequently.
subsequently.

Figure 6.
Figure 6. Cole-Cole plot of the
the composite
composite (inset
(inset zoomed
zoomed in
in region
region shown
shown in
in box).
box).

2.4.2.
2.4.2. Modulus
Modulus Analysis
Analysis
Modulus
Modulus analysis
analysis is
is an
an impressive
impressive technique
technique to
to rule
rule out
out completely
completely or
or suppress
suppress the
the electrode
electrode
effect and deal with the electrical conduction mechanisms (hopping) occurring in the sample
effect and deal with the electrical conduction mechanisms (hopping) occurring in the sample in terms
in
Condens. Matter 2018, 3, 44 9 of 15

of the grain and grain boundary only. This helps in separating the region with similar resistances and
different capacitances, and thus suppress the electrode effect to understand the relaxation properties
of ionic conductors and polycrystalline materials [20]. The Argand plot of modulus can get rid of the
ambiguity that comes from the grain and grain boundary effect and is shown in Figure 6.
The modulus represents the relaxation of the electric field in the material when electric
displacement remains constant so that the electric modulus represents the real dielectric relaxation
process [21]. For all the temperature ranges, to start with the M’ value is small, which implies the
negligible/zero electrode effect [22]. M’ measures the ability of the material to store energy and M”
is effective to understand the ionic conduction mechanism [23]. The plot of M’ and M” (Cf. Figure 7)
shows continuous dispersion with frequency, implying short range mobility of the charge carriers.
The observation of a plateau in the mid frequency region shifts, which implies the existence of frequency
relaxation in the material [24]. The increase in M’ with frequency shows that the relaxation distribution
is spreading over the range of frequency and is accompanied by a peak in M” plots. The broad and
asymmetric peak in M” is again indicative of the non-Debye type relaxation with a distribution of
relaxation time. The ions that interact in its surrounding will introduce a perturbed potential and affect
the motion of neighboring ions. Thus, this cooperative motion will give rise to a distribution of the
relaxation time [25]. In general, the region to the left of the M”peak implies a range in which charge
carriers are mobile over long distances, and that to the right is the range in which the carriers are
confined to potential wells over a short range [13,26]. Shown in Figure 8 is also the Arrhenius fitting of
M” peaks in terms of the variation of ln (M(τ)) with 1000/T. The variation shows the occurrence of
two distinct slopes. Similar observation on ZrTiO4 is discussed by Victor et al. [19], wherein they got
two peaks with an activation energy 0.52 eV for the high frequency and 1.32 eV for the low frequency.
The low frequency peak with higher activation energy is attributed to the grain boundary barrier
formation against electron conduction where the ionic motion is more easily compared to the tightly
packed grains. The low frequency grain with lower activation energy is understood as if the electron is
trapped in shallow potential wells or oxygen vacancies. In this case, the observation of two peaks in M”
can be understood as governed by the inhomogenities due to the presence of different phases of the
composite system. Shifting of the M” peak toward the high frequency with an increase in temperature
is similar to that of ionic conductors and semiconductor [19]. The activation energy and relaxation
time corresponding to the two peaks of the M” plot are given in Table 2. The presence of two activation
energies is indicative of the two conductive mechanisms viz., conduction through the grain and grain
boundary that is occurring in the sample, which could be deduced from modulus plots more clearly.
The Argand plot M” vs. M’ (Cf. Figure 8) shows two semicircles corresponding to the
grain boundary and grain, respectively, with no sign of a third semicircle (due to electrode effect).
The intercept of the first semicircle is the inverse of the grain boundary capacitance and that of the
second is the inverse of the total capacitance in series [19].

Table 2. Arrhenius fitting of tangent loss and impedance for the ball milled and annealed (BMA)
sample with two peaks corresponding to two peaks in M” (upper inset) for Bi2 Fe4 O9 prepared through
solid state route (SSR) corresponding to one peak.

Plot Sample Ea (eV) τ 0 (s) Possible Mechanism Involved

Tan δ vs. f BM 3 step 0.6 2.853 × 10−13 Fe2+ /Fe3+ electron hopping
Z” vs. f BM 3 step 1.5 1.28 × 10−16 Grain boundary barrier
M” vs. f BM 3 step low f peak 1.13 2.97 × 10−15 Grain boundary barrier
M” vs. f BM 3 step high f peak 1.01 8.77 × 10−15 Oxygen vacancies
M” vs. f Bi2 Fe4 O9 SSR 0.6 7.02 × 10−14 Fe2+ /Fe3+ electron hopping
 Condens. Matter 2018, 3, 44 10 of 15
Condens. Matter 2018, 3, 44 10 of 15
Condens. Matter 2018, 3, 44 10 of 15

Figure 7. Variation of real and imaginary part of the electric modulus (top left and right) with
frequency
Figure
Figure at different
Variation
7. Variation ofofreal temperatures.
real
andand imaginary
imaginary partpart
of theofelectric
the electric modulus
modulus (top left(top
and left and
right) right)
with with
frequency
frequency
at differentattemperatures.
different temperatures.

(a) (b)
Figure 8. (a)8.shows
Figure (a)
the variation
(a) shows the variation of ln(τ(M’’))
of ln(τ(M”)) withwith
1000/T argand
1000/T plotplot
argand (b)
of M” vs. M’M'
of M"vs is is
shown inin
shown (b).
(b).
Figure 8. (a) shows the variation of ln(τ(M’’)) with 1000/T argand plot of M"vs M' is shown in (b).
TheThe
relaxation
relaxation timetime
is theis time required
the time for the
required forrecombination
the recombination of charges till the till
of charges capacitor is fully is
the capacitor
discharged
fully during which
The discharged
relaxation during
time isthe field
timeisthe
which
the no longer
field for
required isapplied.
no
thelonger As can be seen
applied.
recombination fromcan Table
ofAscharges 2,
thethe
betillseen activation
from Table
capacitor is 2,
energy and
thedischarged
fully correspondingly
activation energy
during and whichthe time required
correspondingly
the field is no for dielectric
thelonger
time required relaxation
applied.for is higher
Asdielectric for
can be relaxation oxygen
seen from isTablevacancy
higher2, for
defects andvacancy
thus thedefects
hopping 2+ 3+ . While the 2+
theoxygen
activation energy andfromthusFe
and correspondingly the /Fe
hopping
the time Fe dielectric
fromrequired /Fe3+for relaxation
. While time for
the dielectric
dielectric relaxation the composite
relaxation
is higher time
for for
is 10
thetimes higher
composite as
is 10 compared
times to
higher single
as phase
compared Bi to Fe O
single , implying
phase Bi
oxygen vacancy defects and thus the hopping from Fe /Fe . While the dielectric relaxation time for
2 42+ 9 3+ 2 that
Fe 4 O the
9 , composite
implying thatshows
the better
composite
capacitive
theshows
compositeeffect
better and hencehigher
iscapacitive
10 times charge
effect asstorage
and henceeffects
compared charge [27].
to singlestoragephase effects [27].
Bi2Fe 4O9, implying that the composite

shows The normalized

The
better normalized
capacitive plot of of
plot
effect M”
andM”as well
as
hencewellasasZ”Z”isstorage
charge isshown
shown ininFigure
effects [27].9,9,which
Figure whichshows showsaa non-coincident
non-coincident of
of frequency
frequency of
of occurrence
occurrence ofofmaxima,
maxima, which
which implies
implies two
two different
different
The normalized plot of M” as well as Z” is shown in Figure 9, which shows a non-coincident phenomena
phenomena contributing
contributing forfor
the
ofthe
relaxation
relaxation
frequency in the
of in modulus
the modulus
occurrence and impedance,
and impedance,
of maxima, respectively.
respectively.
which implies This indicates the
This indicates
two different phenomenanon-Debye
the non-Debye type
contributing behavior
typefor of
behavior
the
theofsystem ininthe
the system
relaxation theintemperature and range
the temperature
modulus of 423of
range
impedance, K–623
423 K–623K [28].KThis
respectively. [28].indicates the non-Debye type behavior
of the system in the temperature range of 423 K–623 K [28].
Condens.
Condens. Matter
Matter 2018,
Matter 2018, 3,
2018, 3, 44
44
44 11
11of
11 of 15
of 15
15

1.5
1.5 423
423KK
1.0
1.0
0.5
0.5
0.0
0.0

max
473
473K

max
K

M"/M"
M"/M"
Z"/Z"
Z"/Z"

max
max
1.0
1.0 523 K
523 K
0.5
0.5
0.0
0.0
573
573KK
Z"/Z"max
Z"/Z"max
M"/M"max
M"/M"max

1.0
1.0 623
623 K
K
0.5
0.5
0.0
0.0
-1 1 3 5 7
10
10
-1 10
10
1 10
10
3 10
10
5 10
10
7

ff (Hz)
(Hz)
Figure
Figure 9.
Figure 9. Variations
Variationsofof
9.Variations Z”Z’’
of andand
Z’’ M” M’’
and M’’ normalized
normalized with
with respect
with respect
normalized to theirto
respect their
their maximum
maximum
to values
values with
maximum with
with the
the frequency
values the
frequency
at at
differentat
frequency different
temperaturestemperatures are shown.
are shown. are shown.
different temperatures

2.4.3. Conductivity
2.4.3. Conductivity
Conductivity Analysis
Analysis
Conductivityof
Conductivity offerroelectric
of ferroelectricmaterial
ferroelectric materialisis
material anan
is important
an important
important phenomenon
phenomenon
phenomenon to understand
to
to understand
understand for its
forpiezo
for its and
its piezo
piezo
pyroelectric
and
and pyroelectricbehavior
pyroelectric behavior as well
behavior as as the
as well
well as conductivity
as the which
the conductivity
conductivity which in turn
which in depends
in turn upon
turn depends the
depends upon dielectric
upon the behavior
the dielectric
dielectric
of
behavior of the sample. Further, there is a strong coupling between the temperature anddependent
the
behaviorsample.
of the Further,
sample. there is
Further, a strong
there coupling
is a strong between
coupling the temperature
between the and frequency
temperature and frequency
frequency
behavior
dependent
dependent of behavior
the conductivity.
behavior of
of the The ac conductivity
the conductivity.
conductivity. The
The acac(σconductivity
ac
conductivity ((σσacac))the
) study signifies studypresence
study of single
signifies
signifies the or multiple
the presence
presence of
of
relaxation
single or in the
multiple material.
relaxation In this
in case,
the the
material.ac conductivity
In this case, plot
the with
ac respect
conductivity
single or multiple relaxation in the material. In this case, the ac conductivity plot with respect to to frequency
plot with at different
respect to
temperatures
frequency
frequency at at (cf Figure temperatures
different
different 10) can be divided
temperatures (cf into a low
(cf Figure
Figure 10) frequency
10) can
can be plateauinto
be divided
divided governed
into lowby
aa low random hopping
frequency
frequency plateau
plateau
of electrons
governed by contributing
random to
hopping dc conductivity
of electrons and a high
contributing frequency
to dc dispersive
conductivity
governed by random hopping of electrons contributing to dc conductivity and a high frequency region
and adependent
high upon
frequency
n
ω (where ω
dispersive is the dependent
region angular upon ω
frequency
upon and
ωn (where ω
n is a constant
ω isis thedependent
angular upon
angular frequency
frequency and and
and istemperature)
nn is aa constant
n
dispersive region dependent (where the frequency constant
and
dependent upon frequency and temperature) and defines the type of conductivity [28]trap
defines
dependent the
upon type of
frequency conductivity
and [28]
temperature) related
and to the
defines hopping
the type of electrons
of conductivitybetween [28] levels
related
related to
to
situated
the in
hopping the bandgap
of electrons [25].
between trap levels situated
the hopping of electrons between trap levels situated in the bandgap [25]. in the bandgap [25].

Frequency
Frequency (Hz)
(Hz)
Figure 10. Conductivity fitted plots (inset shows the variation of n with respect to 1000/T (K− 1
−1 ).
Figure
Figure 10.
10. Conductivity
Conductivity fitted
fitted plots
plots (inset
(inset shows
shows the
the variation
variation of
of nn with
with respect
respect to
to 1000/T
1000/T (K
(K−1).).
Condens. Matter 2018, 3, 44 12 of 15

Conductivity plots are fitted well with Joanscher’s power law, σac = σdc + Aω n [29]. In general,
the term, Aω n , is defined by any of the following two mechanisms as dictated by the values of exponent
n viz.: (i) Quantum mechanical tunneling (QMT) through barriers separately localized sites and (ii)
Correlated Barrier Hopping (CBH) over the same barrier [30]. n has two different trends with respect
to frequency and time. If n is T independent and decreases with ω then σac originates from QMT
while n decreases with increasing T for CBH. Funke et al. reported for n ≤ 1 that hopping involves
translational motion and for n > 1 there occurs localized hopping of charges without the charges leaving
the neighborhood [31]. Hopping conduction is consistent with the fact that high density of states (DOS)
in the material having a bandgap similar to that of a semiconductor, which can be understood as an
increase in temperature of the delocalization of charge carrier support polaron formation and hopping
occurs between neighboring sites [32].
The n values throughout the T range from 373 K onwards is observed to be < 1, implying that our
results are correlating with the CBH model in the mentioned T range and the hopping involves
translational motion with sudden jumps. The variation is shown in the plot. The significance
of the plot further confirms the sum property of the conductive behavior due to which there are
two slopes corresponding to the constituent phases of the composite. From the fitted parameter in
the given temperature range, the height of the potential well can be calculated using the formula,
n = 1 − 6kB T/Wm , where kB and T are the Boltzmann constant and absolute temperature respectively,
and Wm is the depth of the potential well [33].
The non-dispersive dc conductivity with respect to 1000/T is plotted as shown in Figure 10
and could be fitted with a straight line of an Arrhenius type with two slopes very close by. The dc
conductivity increases with T, which in turn implies the decrease in Rb, and thus the material exhibits
a negative temperature coefficient of resistance (NTCR) similar to a semiconductor [34,35].
The presence of two multiferroic phases in this case is understood to be contributing to the total
dielectric properties. In addition, the resistance of the composite particles is observed to be much higher
than the typical value of resistance corresponding to individual multiferroic phases, which implies that
the dielectric properties of the combined phases is enhanced. Two different mechanisms are understood
to be involved in the relaxation of dielectric and impedance behavior of BiFeO3 -Bi2 Fe4 O9 -α-Fe2 O3
composite particles (Cf. Table 2).

3. Materials and Methods

Laboratory grade starting oxides, Bi2 O3 and Fe2 O3 , in the ratio of 1:3 are taken towards the
formation of required composite in the Fe2 O3 matrix. The oxides are taken for high energy ball milling
using stainless steel balls of different sizes in isopropanol medium for efficient milling for 4 h with
30 min heating and subsequent cooling process. Prior to ball milling, only Fe2 O3 was milled for 3 h
to reduce its grain size as well as to improve the surface for reaction to form the required composite.
The obtained milled powder was converted into pellets of 10 mm diameter and ~2 mm thickness using
hydraulic press and sintered for 12 h at 1073 K and 10 h at 1123 K with intermittent grindings and
further sintered at 1073 K for 24 h and will be henceforth referred to as ball milled and annealed (BMA)
sample. The resulting mixture was powdered and characterized by means of XRD (Inel 2000 X-Ray
Diffractometer with Cu kα source in Bragg-Brentano geometry) for phase analysis.
57 Fe Mössbauer spectroscopy studies have been done in constant acceleration mode and in

transmission geometry of the spectrometer (Wissel make) using 57 Co dispersed in the Rh matrix for
phase and magnetic analysis. Mossbauer studies have also been carried out in pure Bi2 Fe4 O9 in order to
delineate the defect components associated with composite of BiFeO3 and Bi2 Fe4 O9 . Dielectric studies
have been carried out in a detailed manner on the composite sample using a high resolution Alpha
Analyzer (Novocontrol GmbH make). Since the main component of the composite of the present
study is Bi2 Fe4 O9 (which is the most stable oxide of bismuth and iron based oxides), structural and
Mossbauer results on Bi2 Fe4 O9 prepared by the solid state reaction route are also discussed.
Condens. Matter 2018, 3, 44 13 of 15

4. Conclusions
This work discusses in a detailed manner the results of complex impedance spectroscopic
studies carried out in a composite of Bi2 Fe4 O9 -BiFeO3 particles as separated by Fe2 O3 .
Impedance spectroscopic results showing the occurrence of a single semicircle corresponding to that of
the composite system consisting of Bi2 Fe4 O9 -BiFeO3 might be occurring in core-shell configurations,
which is consistent with TEM results. The dielectric properties of the composite system are understood
in a detailed manner. Temperature dependence of dielectric properties of the composite has been
observed to be superior as compared to a single system of either Bi2 Fe4 O9 or BiFeO3 . The composite
material exhibits a transition temperature around room temperature (≈300 to 500 K), which is much
higher than the ferroelectric transition temperature of Bi2 Fe4 O9 and lower as compared to that of
BiFeO3 . This result provides the scope for its enhanced and superior applications in the electronic
industry as compared to individual phases by discarding the issues related to cryogenic or the need
of high temperatures for exhibiting multiferroicity behavior. Further, a much higher value of the
dielectric constant with a low loss factor of the composite as compared to pure BiFeO3 . In addition,
this value of the giant dielectric constant is stable over a wide temperature and frequency ranges.
This establishes that the composite could be extensively used as a high temperature capacitor (in the
interval ≈ 300 to 500 K, wireless communications, and microwave and RF applications in electrical
systems [36–38]. Electron hopping across Fe2+ /Fe3+ and oxygen vacancies are deduced to be playing
an important role in conduction mechanisms based on activation energy analysis of the complex
impedance spectroscopy results.

Author Contributions: Conceptualization—R.G.; Methodology, Validation, Formal Analysis, Investigation,

Writing-Original Draft Preparation, Writing-Review & Editing—R.G. and A.P.
Funding: This research received no external funding.
Acknowledgments: Authors are thankful to G. Amarendra, Director, MSG for his support and encouragement.
Alaka acknowledges DAE for support of her fellowship. Also we thank P. Magudapathy for XRD measurements
and broadband dielectric spectrometer central facility in IITB for dielectric measurements.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Wang, J.; Neaton, J.; Zheng, H.; Nagarajan, V.; Ogale, S.; Liu, B.; Viehland, D.; Vaithyanathan, V.; Schlom, D.;
Waghmare, U. Epitaxial BiFeO3 mutliferroic thinfim heterostructures. Science 2003, 299, 1719–1722. [CrossRef]
[PubMed]
2. Erenstein, W.; Mathur, N.; Scott, J. Multiferroic and magnetoelectric materials. Nature 2006, 442, 759–765.
[CrossRef] [PubMed]
3. Hill, N.A. Why are there so few magnetic ferroelectrics? J. Phys. Chem. B 2000, 104, 6694–6709. [CrossRef]
4. Singh, K.; Negi, N.S.; Kotnala, R.K.; Singh, M. Dielectric and magnetic properties of (BiFeO3 )1−x(PbTiO3 )x
ferromagnetoelectric system. Solid State Commun. 2008, 148, 18–21. [CrossRef]
5. Uniyal, P.; Yadav, K.L. Synthesis and study of multiferroic properties of ZnFe2 O4 -BiFeO3 nanocomposites.
J. Alloy. Compd. 2010, 492, 406–410. [CrossRef]
6. Sahu, T.; Behera, B. Investigation on structural, dielectric and ferroelectric properties of samarium-substituted
BiFeo3 -PbTiO3 composites. Adv. Dielectr. 2017, 1, 1750001–1750006. [CrossRef]
7. Bajpai, O.P.; Kamdi, J.B.; Selvakumar, M.; Ram, S.; Khastgir, D.; Chattopadhyay, S. Effect of
surface modification of BiFeO3 on the dielectric, ferroelectric, magneto-dielectric properties of
polyvinylacetate/BiFeO3 nanocomposites. Express Polym. Lett. 2014, 8, 669–681. [CrossRef]
8. Adhlakha, N.; Yadav, K.L. Structural, magnetic, and optical properties of Ni0.75Zn0.25Fe2 O4 -BiFeO3
composites. J. Mater. Sci. 2014, 49, 4423–4438. [CrossRef]
9. Ryu, J.; Priya, S.; Uchino, K.; Kim, H. Magnetoeelctric effect in composites of magnetostrictive and
piezoelectric materials. J. Electroceram. 2002, 8, 107–119. [CrossRef]
10. Rao, C.N.R.; Sundaresan, A.; Saha, R. Multiferroic and magnetoelectric oxides. J. Phys. Chem. Lett. 2012, 3,
2237–2246. [CrossRef]
Condens. Matter 2018, 3, 44 14 of 15

11. Varshney, D.; Kumar, A.; Verma, K. Effect of A site and B site doping on structure, thermal and dielectric
properties of BiFeO3 ceramics. J. Alloy. Compd. 2011, 509, 8421–8426. [CrossRef]
12. Pélaiz-Barranco, A.; Gutierrez-Amadon, M.P.; Huanosta, A.; Valenzuela, R. Phase transition in ferromagnetic
and ferroelectric ceramics by ac measurement. Appl. Phys. Lett. 1998, 73, 2039–2041. [CrossRef]
13. ELmezayyen, A.S.; Reicha, F.M. Preparation of Chitosan Copper Complexes: Molecular Dynamic Studies of
Chitosan Copper Complexes. Open J. Appl. Sci. 2015, 5, 415–421. [CrossRef]
14. Arrhenius, S. Über die Reaktionsgeschwindigkeit bei der Inversion von Rohrzucker durch Säuren.
Z. Phys. Chem. 1889, 4, 226–248. [CrossRef]
15. Gheorghiu, F.; Calugaru, M.; Ianculescu, A.; Mustcate, V.; Mitoseriu, L. Preparation and functional
characterization of BiFeO3 ceramics: A comparative study of the dielectric properties. Solid State Sci.
2013, 23, 79–87. [CrossRef]
16. PŁcharski, J.; Weiczorek, W. PEO based composite solid electrolyte containing nasicon. Solid State Ion. 1988,
28–30, 979–982. [CrossRef]
17. Singh, H.; Kumar, A.; Yadav, K.L. Structural, dielectric, magnetic, magnetodielectric and impedance
spectroscopic studies of BiFeO3 -BaTiO3 ceramics. Mater. Sci. Eng. B 2011, 176, 540–547. [CrossRef]
18. Satpathy, S.; Mohanty, N.; Behera, A.; Behera, B. Dielectric and electrical properties of
0.5(BiGd0.05Fe0.95O3 )-0.5 (PbZrO3 ) composite. Mater. Sci. 2014, 32, 59–65. [CrossRef]
19. Victor, P.; Bhattacharrya, S.; Krupanidhi, S.B. Dielctric relaxation in laser ablated polycrystalline ZrTiO4 thin
films. J. Appl. Phys. 2003, 94, 5135–5142. [CrossRef]
20. Kolte, J.; Daryapurkar, A.S.; Gulwade, D.D.; Gopalan, P. Microwave sintered Bi0.90La0.10Fe0.95Mn0.05O3
nanocrstal ceramics: Impedance and modulus spectroscopy. Ceram Int. 2016, 42, 12914–12921. [CrossRef]
21. Pradhan, D.K.; Choudhary, R.N.P.; Samantaray, B.K. Studies of structural, thermal and electrical behavior of
polymer nanocomposite electrolytes. Express Polym. Lett. 2008, 2, 630–638. [CrossRef]
22. Yakuphanoglu, F.; Senkal, B.F. Electronic and thermoelectric properties of polyaniline organic semiconductor
and electrical characterization of Al/PANI MIS diode. J. Phys. Chem. C 2007, 111, 1840–1846. [CrossRef]
23. Angell, C.A. Dynamic processes in ionic glasses. Chem. Rev. 1990, 90, 523–542. [CrossRef]
24. Pribosic, I.; Makovec, D.; Drofenic, M. Electrical properties of donor and acceptor doped BaBi4 Ti4O15 .
Eur. Ceram. Soc. 2001, 21, 1327–1331. [CrossRef]
25. Anand, K.; Ramamurthy, B.; Veeraiah, V.; Vijaya Babu, K. Effect of Magnesium substitution on structural and
dielectric properties of LiNiPO4 . Mater. Sci. 2017, 35, 66–80. [CrossRef]
26. Dutta, A.; Sinha, T.P.; Jena, P.; Adak, S. AC conductivity and dielectric relaxation in ionically conducting
sodalime-silicate glasses. J. Non-Cryst. Solids 2008, 354, 3952–3957. [CrossRef]
27. Baral, A.; Meher, K.R.S.P.; Varma, K.B.R. Dielectric behavior of Sr2 SBMnO6 ceramics fabricated from
nanocrystalline powders prepared by molten salt synthesis. Mater. Sci. Bull. 2011, 34, 53–60. [CrossRef]
28. Mohapatra, S.R.; Sahu, B.; Badapanda, T.; Pattanaik, M.S.; Kaushik, S.D.; Singh, A.K. Optical,
dielectric relaxation and conductivity study of Bi2 Fe4 O9 ceramic. J. Mater. Sci. Mater. Electron. 2016,
27, 3645–3652. [CrossRef]
29. Mariyappan, C.R.; Govindaraj, G.; Ramya, L.; Hariharan, S. Synthesis, Characterizationand electrical
conductivity studies on A3 Bi2 P3 O12 (A-Na.K) materials. Mater. Res. Bull. 2005, 40, 610–618. [CrossRef]
30. Joanscher, A.K. A new understanding of the dielectric relaxation of solids. J. Mater. Sci. 1981, 16, 2037–2060.
[CrossRef]
31. Behera, A.K.; Mohanty, N.K.; Satpathy, S.K.; Behera, B.; Nayak, P. Effect of rare earth doping in
impedance modulus and conductivity properties of multiferroic composites: 0.5 BiLaxFe1−x O3 −0.5 PbTiO3 .
Acta Metall. Sin. 2015, 28, 841–857. [CrossRef]
32. Funke, K. Jump Relaxation in Solid Electrolytes. Prog. Solid State Chem. 1993, 22, 111–195. [CrossRef]
33. Behera, B.; Nayak, P.; Choudhary, R.N.P. Impedance spectroscopy study of NaBa2 V5 O15 ceramic.
J. Alloy. Compd. 2007, 436, 226–232. [CrossRef]
34. Dridi, R.; Saafi, I.; Mhandi, A.; Matri, A.; Yumak, A.; Lakhdar, M.H.; Amlouk, A.; Boubaker, K.; Amlouk, M.
Structural, optical and AC conductivity studies on alloy ZnO-Zn2 SnO4 (ZnO-ZTO) thin films. J. Alloy. Compd.
2015, 634, 179. [CrossRef]
35. Ranjan, R.; Kumar, P.; Kumar, N.; Behera, B.; Choudhary, R.N.P. Impedance and electrical modulus analysis
of Sm modified Pb(Zr0.55Ti0.45)1−x/4 O4 ceramics. J. Alloy. Compd. 2011, 509, 6388–6394. [CrossRef]
Condens. Matter 2018, 3, 44 15 of 15

36. Jia, W.; Hou, Y.; Zheng, M.; Xu, Y.; Zhu, M.; Yang, K.; Cheng, H.; Sun, S.; Xing, J. Advances in lead free
high-temperature dielectric materials for ceramic capacitor application. JET Nanodielectr. 2018, 1, 3–16.
[CrossRef]
37. Lanbing, F.; Danping, S.; Yanming, H.; Laijung, L. Low dielectric loss and good thermal stability of Eu and Ti
codoped K0.5Na0.5NbO3 ceramics. J. Mater. Sci. Mater. Electron. 2015, 26, 7159–7164. [CrossRef]
38. Sebastian, M.T.; Ubic, R.; Jantunen, H. Low loss dielectric ceramic material and their properties.
Int. Mater. Rev. 2015, 60, 392–412. [CrossRef]

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