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PII: S0022-3697(19)31205-3
DOI: https://doi.org/10.1016/j.jpcs.2019.109217
Reference: PCS 109217
Please cite this article as: P. Gupta, P.K. Mahapatra, R.N.P. Choudhary, Structural, dielectric,
impedance, and modulus spectroscopy of BaSnO3-Modified BiFeO3, Journal of Physics and Chemistry
of Solids (2019), doi: https://doi.org/10.1016/j.jpcs.2019.109217.
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Abstract
structure was checked by the Rietveld refinement method using the X-ray diffraction
data. The analysis of Fourier transform infrared (FTIR) spectra reconfirmed the formation
of the compound. The temperature-dependent dielectric spectrum for the sample exhibits
a broad anomaly at 190°C, which seems to be the superposition of three Gaussian peaks
Fe2+/Fe3+ and Sn2+/Sn4+ redox mechanism. A sharp peak at 350°C corresponds to the
along with modulus analysis confirmed the deviation from Debye-type behavior. The
Cole–Cole model was used to resolve the components contributing to the loss tangent.
Different models of electrical conduction were used to explain the conduction mechanism
in the material. The existence of ferroelectricity in the sample was confirmed from the
study of the room-temperature P–E loop. The addition of 5% BaSnO3 to BFO resulted in
a 10-fold increase in the dielectric constant and the polarization accompanied by reduced
1. Introduction
In the present technology-driven century, there is a quest for new material with improved
material properties tailored for various device applications [1]. Perovskites, which have
the general formula ABO3, have the flexibility in providing the A and B sites for
substitution/doping with iso- and non-isovalent elements; they therefore have the
compound among all the perovskites, in which the 6s lone pair electrons of bismuth
induce ferroelectricity in the compound, and the exchange interaction between Fe3+ ions
through O2− induces anti-ferromagnetic ordering [6–7]. Its high Curie temperature (TC =
830°C) makes it a promising candidate for actuators, data storage, and sensor
applications [8]. However, the presence of oxygen vacancies and leakage current, which
arises because of the volatile nature of bismuth and variable oxidation states of Fe, limits
its potential as a material of choice for device applications. Further, the synthesis of
single phase BFO via the conventional mixed-oxide reaction method is very difficult
percentage of these phases in BFO. To address these problems, several methods have
been adopted, for example, (i) using a different synthesis method, (ii) substitution at the
A or/and B site by rare-earth and other elements, and (iii) making a solid solution with
B sites, some of the reported works pertain to the substitution of La3+ and Nb5+ [12], La3+
and Zr4+ [13], Na+ and Nb5+ [14], etc. However, the substitution of an alkaline-earth
element at the A site and a tetravalent atom at the B site seems to be a better option for
candidate. Alkaline-earth stannates have wide applications in the scientific and industrial
sectors, such as a signal sensors for detecting humidity, temperature, and gas; glass
enamels for enhancing the resistance of alkali; the fabrication of ceramic boundary-layer
capacitors; as well as photo catalysis, batteries, etc. [15–18]. Of all the stannates (MSnO3,
M = Ba, Ca, Sr, etc.), BaSnO3 is the most promising candidate from both elemental and
technological points of view because of its semi-conducting and dielectric properties [19-
21]. Addition of BaSnO3 in BFO is likely to enhance the dielectric constant because of
the ionic character of the Ba–O bond, with an electronegative difference of 2.55, greater
than that of the covalent Bi–O bond, with an electronegative difference of 1.42.
Furthermore, both Fe and Sn have two stable oxidation states, +2 and +3, and +2 and +4,
respectively. The oxygen vacancy created during high-temperature synthesis forces some
of the Sn and Fe ions to +2 states. Thus, the addition of Sn at Fe sites reduces the number
of Fe2+ ions by compensating through a small number of Sn2+ ions. Such a process is
expected to reduce the loss tangent in the compound. Keeping all these points in mind,
we were motivated to synthesize a compound of BFO with the addition of BaSnO3. For
this purpose, we synthesized compounds with 5%, 10%, and 15% added BaSnO3 to
BiFeO3 using a standard and cost-effective mixed-oxide reaction method. The X-ray
diffraction spectrum of the compound with 10% and 15% addition exhibits many
relatively intense impurity peaks, indicating that the compound did not form in the single
phase. However, the X-ray diffraction spectrum and the Rietveld refinement of the X-ray
diffraction spectrum of the compound with 5% addition (i.e., Bi0.95Ba0.05Fe0.95Sn0.05O3)
indicate the single-phase formation of the compound. As such, we studied the structural
The present work covers structural and micro structural analyses, compositional
mechanism associated with different models and polarization of the prepared sample.
AR-grade ingredients Bi2O3 (99.0%, CDH), Fe2O3 (98.0%, Loba Chemie), BaCO3
(99.0%, CDH), and SnO2 (99.9%, Loba Chemie). All of these raw materials (in
stoichiometric ratio) were mixed homogenously for 3 h in an agate mortar and pestle
under dry conditions. To achieve better uniformity of the mixture, we added ethanol to
this mixture and mixed it thoroughly for another 3 h. The obtained mixture was then
furnace. Ethanol, the boiling point of which is 78.24 ± 0.09°C, completely vaporized
during the high-temperature calcination conducted at 850°C for 4 h. The lump formed on
diffractometer with CuKα incident radiation (λ = 1.5406 Å) was carried out on the
calcined powder to check the phase formation of the compound. After the formation of
the compound was confirmed, the calcined powder was sieved into green pellets of 12
mm diameter using a KBR hydraulic press under a pressure of 4 MPa. To reduce the
brittleness of the pellet, we used polyvinyl alcohol as the binding agent [22]. The green
pellets were sintered in an alumina boat at 900°C (optimized) for 4 h. During the high-
temperature sintering, the binding agent evaporated. The surface morphology and the
composition of the sample were studied by field emission scanning electron microscopy
(FESEM) using a Zeiss Supra 40. For different characterizations, both sides of the pellet
were then polished with fine emery paper followed by silver coating and then subjected
to heat treatment at 100°C for 45 min in an oven [23]. The data for the electrical
holder. To determine the temperature of the furnace, a K-type thermocouple was inserted
into the sample holder. The infrared absorption and emission spectra was obtained on a
Perkin Elmer Fourier transform infrared spectrometer. The ferroelectricity of the sample
In Fig. 1(a), we have stacked the JCPDS data of the BiFeO3 compound with our studied
compound. We analyzed the impurity peak between 20° and 30°. The studied compound
matches well the JCPDS data for the compound BiFeO3 (JCPDS: 01-071-2494). The two
impurity peaks with nominal intensity in this region correspond to Bi2Fe4O9 and
Bi25FeO40 confirmed from the JCPDS file numbers 00-025-0090 and 01-078-1543,
respectively.
Fig. 1(b) represents the Rietveld refinement plot of our room-temperature XRD data
recorded for the final calcined powder. In the refinement graph, the blue line and the
black line represent the experimental and the computed data, respectively. The Bragg
positions are marked by the red lines, and the graph within the bottom box with the black
solid line represent the difference between the observed and the calculated intensities.
The Rietveld refinement was done by using the software MAUD. It is observed that all of
the diffracted peaks are different from its constituent compounds and match very well the
CIF data of BiFeO3 (ICSD 186955). The lattice parameters and the Rietveld scale factors
were refined by using the various options of Refinement Wizard. The refined lattice
with those of reported ones, i.e., a = b = 5.604 Å, c = 13.952 Å. The Rietveld parameters
goodness of fit (2.066), reliability factor (Rw = 5.166%), and pattern R factor (Rexp, % =
2.501%) indicate that the addition of 5% BaSnO3 (which crystallizes in the cubic
structure with the space group Pm3m) to BiFeO3 (which crystallizes in the rhombohedral
structure with the space group R3c) does not affect the structural properties of the host
material. It also shows that it is completely soluble in the structure of BiFeO3, with the
structure with the space group R3c. To gain a better idea of the strain due to doping with
The lattice strain, є, and the crystallite size, D, were calculated by using the relation
full width at half maxima of the corresponding XRD peak. The obtained values of є and
D are as 0.003 and 45.9 nm, respectively. The microstructure of the sample is presented
in Fig. 1(d). As visualized by the graph, grains of different shapes and sizes confirm the
polycrystalline nature of the compound. Further, the grains are densely packed and have
fitting.
EDAX spectra shown in Fig. 1(e). The EDAX spectra confirm the emission count rates of
the constituent elements (Bi, Ba, Fe, Sn, and O) of our compound. To obtain better
insight, we also calculated the elemental atomic ratio of each element using the data
obtained from the EDAX spectra; the findings are given in Table 1. It is observed that the
each element atomic ratio obtained from EDAX data matches well the stoichiometric
The room-temperature FTIR pattern of the sample is depicted in Fig. 2. The absorbance
modes within the range 400–600 cm−1 are the characteristic modes of the compound
bismuth ferrite. The three peaks at 443, 537, and 576 cm−1 are consistent with earlier
reported data [24, 25]. The modes at 443 and 576 cm−1 are due to the bending vibration
of the O–Fe–O bond and stretching vibration of Fe–O bond, respectively. Because of the
presence of Bi/Ba–O in the Bi/BaO6 octahedral unit, there exists an absorbance band at
537 cm−1 [24, 26, 27]. As the precursor sample contains carbonate, we obtained the small
absorbance peak at 814, 1085, 1119, and 1180 cm−1, as well as a broad peak at around
1429–1507 cm−1. The presence of these carbonate phases cannot be detected in the XRD
spectrum. The presence of these organic impurities has a significant effect on the
nanosample, whereas it gradually vanishes for the bulk samples [25]. All of these peaks
correspond to the coupling motion of the C=O and C–O bonds [28]. It may be predicted
that during FTIR characterization, a small amount of CO2 might have been absorbed from
the atmosphere, which gives rise to these vibration modes. At 1629 cm−1, a small peak
arises, and at 3334–3436 cm−1, a broad peak arises; these peaks are due to the vibration of
an O–H bond [28]. The presence of water may be due to the adsorption by the pellets
The variation of dielectric parameters with temperature and frequency is discussed in this
section. As depicted in Fig. 3(a), the dielectric constant for all of the studied frequencies
exhibits a broad anomaly at around 190°C and a sharp one at 350°C [9]. For better
resolution, the variation of dielectric constant with temperature at the two higher
frequencies of 500 kHz and 1 MHz is shown as an inset in Fig. 3(a). The dielectric
maxima at 350°C in the vicinity of the Neel temperature correspond to the dipole
ordering induced by magnetic reordering [29]. The broad anomaly at 190°C seems to be
the superposition of three Gaussian peaks. The multi-peak (three peaks) Gaussian fitting
of the broad peak corresponding to six frequencies in the range 500 Hz–1 MHz is
presented in Fig. 3(b). The multiple-peak Gaussian fitting (software Origin) was used to
deconvolute the apparently overlapped peak into three peaks. The superposed Gaussian
( #
!)
peaks are represented by ε ′ = ∑2 exp[− # ], where Ai is the amplitude, Bi is the
1 $%!
Fig. 3(a) Variation of the dielectric constant with temperature at different frequencies.
The peak position (temperature) and the amplitude of the three peaks corresponding to
the various frequencies as obtained from Fig. 3(b) are provided in Table 2. The three
peaks are centered at 124, 174, and 199°C. For better comprehension, the variation of
peak temperature and the amplitude of the peaks with frequency are depicted in Fig. 3(c)
amplitude of the peak continuously decreases with the increase in frequency. The origin
suggests a more resistive grain boundary than that of the grain/bulk. This contribution is
at low frequency [30-31]. The effective temperature of exciting the grain boundary
Wagner contribution (amplitude) drastically decreased between 10 kHz and 100 kHz. We
may infer that the contribution from the electrode and grain boundary decreases fast with
the increase in frequency from around 10 kHz. At 100 kHz, this peak corresponding to
the Maxwell–Wagner mechanism becomes very broad with a decrease in amplitude and
for the second and third peaks follow the same trend, indicating similar reasons behind
their occurrence. It is worth mentioning here that Fe and Sn both have stable multiple
valence states. The stable oxidation states of Fe are +2 and +3, and those of Sn are +2 and
+4. A chemical formula of the compound favors Fe3+ and Sn4+ at the B site, but during
synthesis of the compound at 900°C, some oxygen vacancies form; thus, for charge
balance, some of the Fe and Sn ions shift to the lower oxidation state of +2. Furthermore,
donors, and Fe3+ captures the electron released in the process, forming Fe2+ and
converting Sn4+ to Sn2+ ions. The second and third peaks centered at 174 and 199°C most
likely correspond to the transient interaction between oxygen ion vacancies and the
Fe2+/Fe3+ and Sn2+/ Sn4+ redox mechanism [32, 33]. Fig. 3(d) shows the steep decrease in
the peak value of the dielectric constant for both these cases with the increase in
frequency.
The dielectric constant vs. frequency graph in Fig. 3(e) depicts the usual trend of decrease
in dielectric constant with the increase in frequency due to cessation of some space
charge, as well as dipolar modes of polarization owing to the inertia in the subsequent
field variation. This aspect is evident in Fig. 3(d). It is worth pointing out here that the
space charge polarization, which arises because of the presence of oxygen vacancies and
defects and the Maxwell–Wagner effect, is most effective in the temperature range of 90
to 215°C (represented by the width at half maximum of the broad combined peaks in
Fig. 3(b)). As such, the dielectric constant in this temperature range is higher than those
at other temperatures. In this temperature range, the dielectric constant for the low
frequencies, i.e., up to 1 kHz, is much higher since the amplitude of the peaks
Fe and Sn ions due to oxygen vacancies are dominant. From 25 to 100°C, the dielectric
constant gradually decreases with frequency, for which there are two regions with
different slopes corresponding to the grain boundary and the grain effect. Further, the
100°C curves exhibit a small contribution for the electrode effect. However, for
temperatures between 150 and 200°C, we observed that the dielectric curves can be
broadly divided into three regions, with each one exhibiting a different slope (dispersion).
Variation of the dielectric constant in these three regions corresponds to the electrode
effect, grain boundary effect, and the grain effect. At higher temperature (≥250°C), the
dielectric constant decreases. It may be recalled that a plateau region is observed between
240 and 300°C in the dielectric constant-temperature graph of Fig. 3(a). To compare our
results with those of pure BFO, we present in the inset of Fig. 3(e) the dielectric constant
of our compound with that of pure BFO synthesized under similar conditions. As can be
ascertained from the inset of Fig. 3(e), the studied compound exhibits a dielectric
constant of 5360 at 25°C and 100 Hz, which is very much higher than that of pure BFO
(ε ′ = 1076) prepared and measured under identical conditions. It is worth pointing here
that for the same temperature and frequency, the reported values of the maximum
dielectric constant of BFO based on fabrication methods vary widely, between 81 [9, 34]
and 1000 [35]. Moreover, at the higher frequency of 1 MHz, the sample possessed a
dielectric constant of 366 at room temperature, which is also higher than that of pure
complex relative permittivity plot, which is also known as the Cole–Cole plot with the
semicircular fittings, is depicted in Fig. 3(f). For this purpose, the value of ε′′ was
obtained by using the relation &′ = ()* + +,′′. The value of Gdc was obtained from the
intercept of the Y′–ω graph (plotted from the data taken from the phase-sensitive meter)
[36]. The values of ε′ were obtained from the relation &′′ = +,′. The Cole–Cole plot
for the sample at room temperature is found to possess two semicircular arcs, which
indicate the presence of both grain and grain boundary contributions to the polarization
Fig. 3(c, d) Frequency variation of peak temperature and amplitude of the three Gaussian peaks of
the dielectric constant curves at 25°C for pure BiFeO3 and the studied compound.
Fig. 3(f) Cole–Cole plot and its inset representing the verification of our experimental data at room
temperature.
These semicircles are depressed (Fig. 3(f)), indicating a distribution of the relaxation time
for the ceramic sample. In an ideal Debye case with single relaxation time, the complex
/0 /1
-(+) − -. = 23( 45)
………… (1)
represents the characteristic relaxation time. However, in our sample, the complex
/0 /1
-(+) − -. = … … … … ……… (2)
23( 45)789
parameter is equal to the ratio of the angle made by the tangent to the semicircle at the
position corresponding to ε∞ with the real axis and π/2. This parameter bears an inverse
relation with grain inhomogeneity. Thus, the tilted angle below the real axis, φ, is related
$φ
to the relaxation distribution parameter by the relation (1 − α) = 1 − . Circular arcs
<
were obtained for the experimental permittivity data by taking three pairs of ε′ and ε′′
and fitted with the equation of the circle. This process was done frequently in
Mathematica software to find the best fit of the semicircle. The fitting provides the radius
of the circle, the values of -6 and -. from the intersection of the circle on the real axis,
and the depression angle, φ, which is a measure of deviation from the Debye behavior. It
is observed that in our sample, the grain and grain boundary are respectively tilted at
angles of φg = 22.53° and φgb = 22.90° to the real axis. On the basis of eqn. (2), the real
(εr′) and imaginary part (εr′′) of the permittivity for the sample exhibiting both grain and
78α? 78α?F
>/0? /1? @A23>4τ? @ BCD φ? E >/0?F /1?F @A23>4τ?F @ BCD φ?F E
ε ′ = -.= + #8#α? 78α? + #8#α?F 78α?F ………(3)
23>4τ? @ 3$>4τ? @ BCD φ? 23>4τ?F @ 3$>4τ?F @ BCD φ?F
and
78α? 78α?F
>/0? /1? @>4τ? @ >/0?F /1?F @>4τ?F @
ε ′′ =
cos φ? cos φ?F
#8#α? 78α? + #8#α?F 78α?F
23>4τ? @ 3$>4τ? @ BCD φ? 23>4τ?F @ 3$>4τ?F @ BCD φ?F
………………. (4)
Where the subscript G and GH stand for the grain and grain boundary effect respectively.
The values of -6= , -.= , -6=J , -.=J determined from the Cole–Cole plot are 2599.2,
254.867, 8586.27, and 2145.87 respectively. The angular frequency ωp, which
corresponds to the peak of both grain and grain boundary in the Cole–Cole plot is found
the Debye-type relaxation process is the inverse of the angular frequency ωp of the
corresponding peak and amounts to 3.26 × 10−6 and 1.03 × 10−3 s for the grain and grain
boundary contributions, respectively. Putting all of these values into eqn. (3) and (4), we
calculated the values of ε ′ and ε ′′ . In the inset of Fig. 3(f), we have plotted the
experimental data for ε ′ and ε ′′ and the theoretically calculated values of the
corresponding quantities. The graphs in the inset of Fig. 3(f) exhibit excellent agreement
between the experimental and calculated data and thus confirm the contribution of both
grain and grain boundary to the polarization mechanism and the diffusion of thermally
capacitor, is one of the important factors that determine the application potential of the
4 % NN 3OPQ
KL M = . In terms of dielectric constant, it is expressed as
4% N
SPQ
KL M = +
ε′′R
……………. (5)
ε′R 4ε0 ε′R
where the first term represents the Debye-type dipolar relaxation, and the second term
represents the DC conductivity contribution to the tangent loss. As visualized from the
graph (Fig. 3(g)), the loss tangent follows the usual trend of dielectrics. To verify our
experimental data, we have calculated the value of loss tangent at room temperature
(Fig. 3(h)) by substituting the data obtained from the Cole–Cole plot and eqns. (3) and (4)
in eqn. (5). It is observed that the experimental value (black dots) matches very well with
the calculated value (red dots) in Fig. 3(h). We also resolved the components of loss
tangent in Fig. 3(h) for the Debye contribution of grain (green dots), which is effective at
high frequency, the Debye contribution of the grain boundary (blue dots) dominant at
lower frequency, and the DC-conductivity-based loss component (pink dots), which
decreases rapidly with frequency. All of these curves together with the Cole–Cole
The temperature dependence of the loss tangent is depicted in Fig. 3(i). For all the
frequencies, the general trend in the variation of tanδ is that it increases with the rise in
temperature. The feature is more visible at low frequencies because of enhancement of the
conductivity of the sample with the increase in temperature, which is the major contributor
to the tangent loss at low frequencies. However, a broad peak like the anomaly at around
190°C and another sharp peak at 350°C are observed in the tanδ vs. temperature variation
for all the frequencies. This feature is akin to that observed in the dielectric constant vs.
temperature graph presented in Fig. 3(a) and 3(b). The broad peak seems to be the
superposition of the three peaks corresponding to the three mechanisms mentioned and
explains the dielectric vs. temperature variation. For better resolution of the broad peak,
the variation of tan δ is shown for the temperature range of 20 to 260°C for some
frequencies between 500 Hz and 1 MHz. The tangent loss of the sample for frequencies
above 100 kHz in the temperature range of 240 to 320°C is found to be extremely small.
Fig. 3(i) and its inset represents the temperature dependence of loss tangent at different frequencies.
For the studied sample, the value of loss tangent at 25°C in the frequency range of
100 Hz to 10 kHz is found to remain between 1.28–0.28, which is smaller than that of
2.9–0.62 reported for BFO under similar conditions [35]. This reduction in the value is
most likely due to the fact that with the addition of BaSnO3, there is a reduction of Fe2+
ions (Fe3+ → Fe2+). This is despite the creation of a relatively small number of Sn2+ ions
(Sn4+ → Sn2+) induced by oxygen vacancies produced during high-temperature synthesis
of the compound, which ultimately reduces the value of conductivity and loss tangent.
Impedance studies are a promising non-destructive testing method for analyzing the
compounds such as the one under study, impedance studies help to identify the
grain/bulk, grain boundary, and electrode interface contribution to the circuit elements
such as the resistance, capacitance, and the relaxation distribution parameter. The
equivalent electrical circuit for the sample having all three contributions is generally
The complex impedance (Z) for the equivalent circuit takes the form [39]
2
1
T = T + T = V + X+,Y
U UU
W
2 2 2
1 1 1
= V + X+,J Y +Z + X+,=J [ + V + X+,\ Y
WJ W=J W\
]F ]?F ]^
where T U = + +
234# %F # ]F # 234# %?F # ]?F # 234 # %^ # ]^ #
Nyquist plot. In our ceramic sample, each of the grain, grain boundary, and electrode
semicircular arcs. The depressed semicircles point at the distribution of relaxation times
due to inhomogeneity in size and distribution of grains in the ceramic sample [40]. To
take account of this effect, one needs to introduce a constant-phase element (CPE) Q
along with the elements R and C in the equivalent circuit for each of the contributions.
We have plotted the Nyquist plot for different temperatures in Fig. 4(a). All of the
experimental data are fitted with the equivalent electrical circuit by ZSIMPWIN software.
All of the parameters obtained from this fitting are listed in Table 3. It is observed that at
25°C, only grain and grain boundary effect contributes to the electrical response. At
higher temperatures (≥100°C), the electrode interface effect also contributes in addition
Fig. 4(a) and its inset representing Nyquist plots at different temperatures.
Fig. 4(b) and its inset represents the disparity of the resistive part, Z', with frequency at
selected temperatures. From the graphical representation, it is observed that for all the
temperatures, the graphs exhibit inverse dependence on frequency until 100 kHz and
then merge to a constant value. This is due to the inertial reluctance of the space charge
the applied field. On increasing the temperature, Z′ decreases to 200°C and then
increases at 250°C, and then again decreases with further rise in temperature. It is worth
pointing out here that the sample exhibits a dielectric peak at around 190°C, and there is
a decrement in the dielectric constant in the range between 200 and 250°C.
have plotted Z′′ as a function of frequency for different temperatures in Fig. 4(c). The
inset of this figure represents a close view of Z′′ at higher temperature. A single
relaxation peak shifts to a higher frequency with the rise in temperature except for the
one at 200°C. This feature points to relaxor behavior in the sample. The left shift of the
peak at 200°C can be explained by the dielectric peak at around 190°C. At each
temperature, there exists a particular frequency, ωabc , called the relaxation frequency,
where the reactive component achieves the maximum value, i.e., T′′abc . It is observed
that the peak value decreases to 200°C and then increases at 250°C and again decreases
The presence of asymmetry in the characteristic broad peak at all of the temperatures
indicates non-Debye-type relaxation process [41]. The process of broadening and shifting
of peak with increasing temperature is different in the temperature zones ≤ 200°C and ≥
200°C, indicating the existence of two types of relaxation mechanism in the material. To
(+abc (d)) with respect to temperature in Fig. 4(d) and calculated the activation energy
εf
of the relaxation process using the relation +abc (d) = +6 e gh . All of the symbols used
in this relation have their usual definitions. The slope obtained from the linear fitting of
the plot gives the activation energy for the relaxation process [42]; for our sample, it
amounts to 0.23 eV at low temperature and 0.85 eV at high temperature. The different
activation energies also have their imprint on the conduction process of the grain, which
by Hodge to study the properties of solid electrolytes [43]. Modulus spectroscopy has its
own significance, enabling the differentiation of components having the same resistance
capacitance for the material. This also distinguishes the electrode polarization and the
respectively. As visualized from the graph, the value of M' for all of the temperatures
increases with the increase in frequency. The negligible or zero value of M' in the low-
frequency region indicates that the ions vibrate within the confinement of their potential
energy wells and do not diffuse to the boundary. In addition, the inertial reluctance of
ions follow the rapid variation of the electric field at high frequency, leading to the
convergence of M' curves for temperatures beyond 240°C [46]. The corresponding
curves in the low-temperature region (25 to 75°C) exhibit an increase with frequency
and a tendency to merge with those of high-temperature curves (250 and 300°C) at a
frequency greater than 1 MHz. However, the curves between 100 and 240°C, which
correspond to the temperature range wherein the dielectric constant in Fig. 3(a) exhibits
anomaly at 1 MHz and above. Keeping all of these behaviors in mind, we can predict
that the conduction mechanism in our sample is due to the short-range motion of charge
carriers. Furthermore, the value of M' decreases with the increase in temperature;
The imaginary component of the modulus has a direct dependence on the resistive part
of impedance through the relation M" = ωCoZ'. The presence of an asymmetric peak for
all of the temperatures supports the deviation of the relaxation process in the sample
from the Debye type, as discussed in the impedance section. To examine the short-range
and modulus with frequency in Fig. 5(c). It has been reported that if the peaks of both
the components Z′′ and M" occur at the same frequency, long-range-type charge carriers
are involved; if it does not occur, then it is due to short-range-type charge carriers [47].
As seen from the graph, both peaks slightly depart from each other, indicating short-
where the first and second terms respectively represent the DC conductivity and the
absorptive component of displacement current. As is evident from the curves in Fig. 6(a),
corresponds to the increasing portion of the broad dielectric anomaly in Fig. 3(a), which
includes the peak excitation temperature for all of the three dielectric polarization
processes discussed in the dielectric section. In the temperature range of 190 to 240°C,
side of the dielectric anomaly in Fig. 3(a). PTCR behavior implies no more excitation of
charge carriers in this temperature range. The temperature range of 240 to 300°C, which
conductivity with the increase in temperature. Beyond 300°C, the conductivity exhibits a
temperature of 350°C, as seen in Fig. 3(a). For ready reference, we provide Table 4,
It can be seen from the graph of Fig. 6(a) that the activation energy decreases with the
increase in frequency, i.e., from 0.72 eV at 1 kHz to 0.48 eV at 1 MHz. The decrease in
activation energy with frequency in the experimental range is due to increased hopping
analyzed by the Jonscher’s equation: σ (ω) = σ)* + ωa , where all the symbols have
their usual meanings. For a non-Debye case, the value of the frequency exponent (m) lies
between 0 and 1. The value of m was calculated from the slope of log σac ≈ log ν graph.
As visualized from the graph, there appear two different regions having different slopes
Fig. 6(a, b) Variation of AC conductivity with inverse temperature and frequency at different
temperatures.
The conductivity curves in the entire frequency range increases with temperature up to
190°C and then decreases up to 240°C. For temperatures more than 240°C, the
conductivity again increases. The different values of m suggest two different conduction
mechanisms in the sample, one in the lower frequency, associated with the grain
To have a detailed illustration about the charge carriers, which are involved in the
conduction process, we have plotted the variation of the frequency exponent (m) of both
grain boundary and grain effect with temperature in Fig. 6(c) and its inset, respectively.
These curves explain the conduction mechanism associated with different models [48].
overlapping large-polaron tunneling (OLPT) model, where the exponent m first decreases
with the increase in temperature, attains a minimum, and then increases again. Here, the
overlapping of potential wells of the neighboring sites takes place because of the long-
range nature of the Coulombic interaction exhibited by the large polarons [49]. As a
result, the polaron hopping energy is reduced and is given by kl = klm (1 − ), where
n
]
\#
klm = ,α is the inverse localization length, qr is the polaron radius, and klm is the
oεp n
Where •(€• ) is the energy level density of the Fermi level, Wω is the tunneling distance,
The conduction mechanism associated with the grain effect follows the correlated barrier
hopping (CBH) model. It may be worth mentioning here that our sample possesses two
different values of activation energy for the relaxation process of grain in the two
temperature ranges, the first being room temperature to 190°C and the second being a
temperature higher than 240°C. It can be seen that the value of m decreases with the
increase in temperature [50]. Here, the transfer of electrons is possible via thermal
excitation over the barrier between the two sites. Mathematically, it can be written as [51]
πƒ
‚b* (ω) = • $ εε6 ωWω „ …………….(7)
$o
where N is the concentration of pure states, Wω is the hopping distance, and the rest of the
symbols have their usual definitions. The hopping distance Wω at frequency + can be
expressed as
\#
Wω = 7 …………….(8)
πεε0 […† z ‡ˆA E]
‰Š‹
where e is the electronic charge, s is the Boltzmann constant, k• is the barrier height,
and Ž• is the relaxation time. The frequency exponent m in this case is given by
„ z
• =1− ………………(9)
…† z ‡ˆ(2/45‹ )
6s d
• =1−
k•
Using the above relation and the linear fitting of the experimental data, we found the
values of k• for both temperature ranges to be 97 and 87 meV. We also calculated the
hopping distance and the concentration of pure states at 20 kHz, 4.02 Å and 1.71 ×
To show the ferroelectric behavior of the compound, we have plotted the room
the sample shows a saturated loop with a remnant polarization (Pr) of 1.14 µC/cm2 and
coercivity (Ec) of 3.58 kV/cm. The reported values of BFO by Deng et al. for Pr and Ec
are 0.3 µC/cm2 and 3 kV/cm [36], respectively; and 0.1 µC/cm2 and 4 kV/cm,
respectively, as reported by Zhang et al. [35]. The measured value of Pr for our sample
BFO. The ferroelectricity of the sample was enhanced by doping with 5% BaSnO3 as the
recalled here that the studied compound exhibits a dielectric constant of 5360 at 25°C and
100 Hz, which is very much higher than that of pure BFO (ε ′ = 1076) prepared and
measured under identical conditions. It is worth mentioning here that the P–E
measurement was carried out with a field frequency of 100 Hz. The Ba2+ ions at Bi3+ sites
act as acceptor centers and are associated with the hardening effect with the increase in
coercive field [53, 54]. The higher-valence Sn4+ ion can act as donor center and may even
cause some cation vacancies, leading to dipolar defects and helping to suppress oxygen
vacancies. The random field around these defects is expected to lower the barrier required
for nucleation of new domains, which thus lower the value of the coercive field and help
domain motion and consequently increase the ferroelectric properties [55, 56].
confirmed from the EDAX spectrum. Rietveld refinement of the room-temperature XRD
rhombohedral structure with a crystallite size of 45.9 nm. FESEM confirmed densely
packed grains in the sample with an average grain size of 5.83 µm. The occurrence of
characteristic modes in the FTIR spectrum supports the formation of the compound. In
the studied range of temperature and frequency, the sample exhibited a broad anomaly at
around 190°C and a sharp one at 350°C. By Gaussian fitting, we found the broad peak at
190°C to be the superposition of three peaks centered around 124, 174, and 199°C. These
had their origin in the Maxwell–Wagner effect, and the oxygen vacancy mediated
transient interaction between the Fe2+/Fe3+ and Sn2+/Sn4+ redox mechanisms. The sharp
peak of the dielectric at 350°C corresponds to magnetic ordering around the known Neel
temperature. A Cole–Cole plot and the modified Debye model were used to verify our
experimental dielectric data and to resolve the components of loss tangent to the Debye-
like contribution of the grain and grain boundary and the DC-conductivity-based loss
and grain boundary effect in the sample. The Nyquist plot reveals that at high
temperature (≥100°C), the electrode interface effect also contributes in addition to the
grain and grain boundary effects. The frequency dependence of Z′′ suggests that the grain
itself follows two types of relaxation mechanism in the temperature range of ≤200°C and
≥200°C, with activation energies of 0.23 and 0.85 eV, respectively. These relaxation
mechanisms were supported by the conduction mechanism of the grain associated with
the CBH model with different barrier height. OLPT model was used to explain the
conduction mechanism associated with the grain boundary. The P–E loop confirms the
resulted in a nearly 10-fold increase in the dielectric constant, and the remnant
polarization accompanied a reduction in the loss tangent. The effect might have been
caused by a relatively large reduction in the oxygen-vacancy-mediated Fe2+/Fe3+ redox
increased dielectric constant, the broad dielectric peak with significantly higher half
width, and the reduced loss tangent of the (Bi0.95Ba0.05)(Fe0.95Sn0.05)O3 compound give it
more potential for device application as compared with BFO and hosts of other known
dielectric materials.
REFERENCES
1. J.. Gao, Y. Wang, Z. He, Y. Liu, D. Wang, L. Jin, T. Zhao, L. Zhong, and
(2000) 35-37.
5. S. Hajra, A. Tripathy, B. K. Panigrahi, and R. N. P. Choudhary, Development and
7. G. Chen, J. Chen, W. Pei, Y. Lu, Q. Zhang, Q. Zhang, and Y. He, Bismuth ferrite
materials for solar cells: Current status and prospects, Materials Research
12. L. Zhai, Y. G. Shi, S. L. Tang, L. Y. Lv, and Y. W. Du., Large magnetic coercive
17. M. J. Madou and S. R. Morrison, Chemical Sensing with Solid State Devices
electrolyte secondary battery, U.S. Patent 6,423,448, issued July 23, 2002.
of MSnO3 (M: Ca, Ba, Sr) stannates for photoreduction of 4-nitrophenol and
hydrogen production under UV light irradiation, Journal of Photochemistry and
(2011) 535–539.
23. Y. Liu, X. M. Chen, X. Q. Liu, and L. Li., Giant dielectric response and relaxor
diss., 2011.
30. J. Wang, Z. Lu, and Z. Chen, The novel effects of Cu-deficient on the dielectric
(B1− xLax) FeO3 solid solutions, Physica Status Solidi (a) 23 (1974) 567–574.
34. Z. Jiaping, X. Zhao, Z. Suo, and H. Jiang, A finite element method for transient
5 (2018) 045905.
1983.
43. I. M. Hodge, M. D. Ingram, and A. R. West, A new method for analysing the ac
253104.
(2016) 148–157.
51. G. E Pike, AC conductivity of scandium oxide and a new hopping model for
(2009) 166–173.
(2007) 274–280.
Figure Captions
compound (Bi0.95Ba0.05)(Fe0.95Sn0.05)O3.
peaks of the broad dielectric anomaly. (e) Frequency variation of the dielectric
constant at different temperatures. Its inset depicts the dielectric constant curves at
25°C for pure BiFeO3 and the studied compound. (f) Cole–Cole plot and its inset
4. Fig. 4(a) Nyquist plots at different temperatures. (b, c) Frequency variation of Z'
and Z'' at different temperatures. (d) Calculation of activation energy for the
5. Fig. 5 (a, b) Frequency variation of M' and M'' at different temperatures. (c)
(m) for grain boundary effect. Its inset represents the grain effect.
Tabulation
different frequencies.
1. The addition of 5% BaSnO3 to BFO results in a nearly 10-fold increase in the dielectric
constant with a reduction of the loss tangent.
2. By employing Cole–Cole model, the loss tangent is resolved to identify the contributions
from the Debye-type relaxation for both grain and grain boundary effects and that of the
DC conductivity.
3. The impedance and modulus analysis confirms the non-Debye response of the sample.
4. Nyquist plot reveals that at high temperature (≥100°C), the electrode interface effect also
contributes in addition to the grain and grain boundary effects.
All the authors have read and approved the manuscript and have agreed for submission to this
journal.