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CERAMICS
INTERNATIONAL
Ceramics International 41 (2015) 11436–11444
www.elsevier.com/locate/ceramint

Dielectric and impedance spectroscopic studies of lead-free

barium‐calcium‐zirconium‐titanium oxide ceramics
Muhammad Asif Rafiqa,n, Muhammad Nadeem Rafiqc,d, K. Venkata Saravananb,1
a
Department of Metallurgical and Materials Engineering, University of Engineering and Technology, Lahore, Pakistan
b
Department of Materials & Ceramic Engineering/CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
c
Electrical & Computer Engineering Department, NDSU, Fargo, USA
d
Department of Electrical Engineering, COMSATS Institute of Information Technology, Lahore, Pakistan
Received 16 April 2015; received in revised form 19 May 2015; accepted 19 May 2015
Available online 29 May 2015

Abstract

Dielectric properties of perovskite structured (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3; [BCZT], ferroelectric ceramics prepared by the conventional solid-
state reaction method were investigated by AC impedance spectroscopy. To obtain high density samples, the pressed pellets were sintered at
1450 1C and 1500 1C for 4 h. Polarization–Electric field (P–E) measurements of the ceramic samples sintered at 1500 1C showed higher remnant
polarization (Pr ¼12.20 mC/cm2) and coercive field (Ec ¼ 4.50 kV/cm) values when compared to Pr ¼8.02 mC/cm2 and Ec ¼3.80 kV/cm
respectively for the samples sintered at 1450 1C. In addition, BCZT sintered at 1500 1C showed higher dielectric constant as compared to the one
sintered at 1450 1C. However, the dielectric constant measured as a function of frequency for both the sintered samples showed single maximum
value at  105 1C, which is attributed to the structural phase transition (Curie temperature, TC) from ferroelectric, tetragonal phase to paraelectric,
cubic phase. AC impedance analysis over the frequency range of 100 Hz to 1 MHz for the ceramic sintered at 1500 1C, showed mainly bulk
contribution up to 250 1C while bulk and grain-boundary contributions were present above 250 1C. Activation energies for conductivity were
found to be strongly frequency dependent. The activation energy values are attributed to the conduction of oxygen vacancies via hopping
mechanism.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Dielectric properties; C. Impedance; D. Perovskite; Grain boundary; Activation energy; Hopping mechanism

1. Introduction resistivity (PTCR) sensors[6–9]. It undergoes a ferroelectric to

With the increasing environmental awareness, a large number of
Pb-free perovskite ceramics are currently under investigation to be
used for sensor and actuator applications [1–5]. Barium titanate
(BaTiO3) was developed as a piezoelectric actuator ceramic and is
one of the most widely used ferroelectric materials in the electronic
industry as capacitor, piezoelectric actuators, electro-luminescent
panels, pyroelectric detectors, positive temperature coefficient of
n
Corresponding author.
E-mail addresses: asifrafiq@uet.edu.pk (M.A. Rafiq),
venketvs@eutn.ac.in (K. Venkata Saravanan).
1
Current affiliation: Department of Physics, School of Basic and Applied
Sciences, Central University of Tamil Nadu, Thiruvarur - 610101, India.
paraelectric phase transition at around 130 1C, where permittivity
(εʹ) normally reaches to a maximum value and this temperature is
called the Curie temperature, TC. The other two phase transit-
ions are orthorhombic/tetragonal (O/T) around, T1=5 1C, and
rhombohedral/orthorhombic (R/O), T2= 90 1C [10]. Liu et al.
[11] reported a piezoelectric constant, d33 ¼ 620 pC/N in Ba
(Ti0.8Zr0.2)TO3–(Ba0.7Ca0.3)TiO3 ceramics, which is comparable
to the high end lead zirconate titanate (PZT) family [9]. It was
further claimed that morphotropic phase boundary (MPB) respon-
sible for extra ordinary properties starts from a temperature called
the triple point where the cubic paraelectric phase (C), ferroelectric
rhombohedral (R) and tetragonal (T) phases coexist.
Substitution of A- and/or B- cation sites has been used to
tailor the electrical properties of perovskites including BaTiO3

http://dx.doi.org/10.1016/j.ceramint.2015.05.107
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 M.A. Rafiq et al. / Ceramics International 41 (2015) 11436–11444
based materials [10–12]. Isovalent dopants are commonly used
to alter TC, however it affects the lower temperature phase
transition temperatures as well. This process sometimes leads to
diffuse phase transition-type behavior. In BaTiO3, Ca þ 2 -
doping has shown a very little effect on TC up to 10 at%,
(Ba0.90Ca0.10TiO3) but causes a dramatic decrease in both O/T
and R/O phase transition (TO/T and TR/O) temperatures [10].
Morphotropic phase boundary between rhombohedral and
tetragonal phase has been reported for (Ba1  xCax) (Ti0.9Zr0.1)
O3, where xZ0.10. Significant increase in ε0 max was observed
by the introduction of isovalent cations on B site. B-site dopant
such as Zr þ 4 causes a linear decrease in Tc, whereas both TR/O
and TO/T increase. The lowering in TC is accompanied by an
initial increase in εʹmax, but with higher amounts εʹmax decreases
and permittivity peak becomes increasingly broad. This beha-
vior is termed as “pinching” and is attributed to the coalescence
of the three phase transition temperatures, which means that
overlap of the three permittivity maxima associated with the
individual phase transitions and was observed at a dopant level
of around 15 at% of Zr [10,12–14]. Liu et al. reported that
morphotropic phase boundary (MPB) originated from this
tricritical triple point of cubic paraelectric phase (C), ferro-
electric rhombohedral (R), and tetragonal (T) phases in BCZT
system, where permittivity maxima occurs, and also shows extra
ordinary electromechanical properties [11]. After the report of
extra ordinary properties in the composition BaTi0.8Zr0.2O3–
50Ba0.7Ca0.3TiO3 (BCZT), effect of dopant like Pr2O3 [15],
CuO [16], CeO2 [18], solid solution of BCZT with BiFeO3 [17]
and their effect on the sintering and properties has been reported
[18,19]. Elastic, piezoelectric, dielectric properties, dependence
of the piezoelectric coefficient, ferroelectric properties on
temperature and piezo-response force microscopic studies of
BCZT ceramic has been reported [20,21].
Complex impedance spectroscopy (CIS) is a powerful non-
destructive method, widely used to characterize electrical
materials [22,23]. There are four possible ways of analyzing
the data, the impedance Zn, the Modulus Mn, the Admittance
An or Yn and permittivity εn. They are interrelated and can be
expressed as,
M n ¼ jωC0 Z n ð1Þ
ϵn ¼ ðM n Þ  1 ð2Þ
Z n ¼ ðAn Þ  1 ð3Þ
An ¼ jω0 C0 εn ð4Þ
where ω is the angular frequency 2πf, Co is the vacuum
capacitance of the measuring cell and electrodes with an air
gap in place of the sample, Co=εo/k, where εo is the
permittivity of free space (8.854  10  14 F/cm), and k=l/A,
the cell constant where I is the thickness and A is the area.
This analysis displays impedance data in different formalism
and provides us the maximum possible information. The
display of impedance data in complex plane plot appears in
the form of a succession of semicircles due to relaxation
phenomena with different time constants of grain (bulk), grain
11437
boundary, and interface/polarization in a polycrystalline mate-
rial. On these bases, it is easy to separate the contribution of
various components in the material from overall electrical
properties.
Systematic study of high temperature dielectric properties
and use of complex impedance spectroscopy is still scarce for
BCZT ceramics. In this work, we have prepared BCZT by
conventional ceramic oxide method and used different calcina-
tion temperatures to obtain mono-phasic material. Sintering
temperature of 1450 1C and 1500 1C were used to prepare the
samples. XRD analysis, polarization hysteresis loop and
dielectric properties as a function of frequency and temperature
were done and data was analyzed. Impedance studies of the
samples with better properties were conducted i.e. samples
sintered at 1500 1C. A set of material constants and properties,
which is important for both practical device design and
fundamental study, is reported.
2. Experimental procedure
Polycrystalline ceramic samples of (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3
were prepared by the conventional solid state reaction technique.
Stoichiometric amount of BaCO3, (Merck, 99%) and TiO2
(Merck, 99%), CaCO3 (Aldrich, 99%), ZrO2 (Aldrich, 99%)
were thoroughly mixed in a planetary mill in alcohol medium for
5 h using teflon jars and yttria stabilized zirconia balls. The
milled powders were dried, and then calcined at 1200–1300 1C
for 4 h in an alumina crucible. The calcined powders were re-
milled for 5 h. The pellets were prepared by uniaxially pressing
the powders in a 10 mm diameter die at 170 MPa and then
isostatically pressed at 200 MPa. The pressed pellets were
sintered in air at 1450–1500 1C for 4 h. The samples were
characterized by X-ray diffraction (XRD, Philips X’Pert, Cu Kα-
radiation) for phase identification, to determine phase purity and
crystal structure. The diffraction data were refined by the
Rietveld method using FullPROF software. To measure electrical
properties, the sintered ceramics were polished and silver paste
was applied on both sides of the pellets as electrodes and fired at
500 1C for 30 min. The polarization vs. electric field (P–E)
relation was measured at room temperature using Aixact TF
analyzer 1000 ferroelectric tester at 40 Hz. The high temperature
dielectric response was assessed as a function of frequency (from
100 Hz to 1 MHz), using a HP 4284A precision LCR Meter. The
bulk AC conductivity of the material was evaluated from the
complex impedance spectra measured at different temperatures
from 30 to 400 1C.
3. Results and discussion
The XRD patterns of the BCZT calcined powders and
ceramics sintered at different temperatures are shown in
Fig. 1a. As clearly seen from the XRD patterns, the powders
calcined at 1350 1C and higher for 2 h yielded a pure, single
phase material whereas the powders calcined at 1200 1C for 2 h
show traces of secondary phases. However, the secondary
phases diffused into the perovskite lattice during the sintering
process, thus yielding a single perovskite phase. Similar results
11438 M.A. Rafiq et al. / Ceramics International 41 (2015) 11436–11444
Fig. 1. X-ray diffraction patterns of (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 ceramics (a)
calcined and sintered at various temperatures and (b) represents the refinement
of sample sintered at 1500 1C.
have been reported by Wang et al., where the powders calcined
between 1000 1C and 1300 1C for 2 h resulted in the formation
of secondary phases but disappeared on sintering at 1520 1C
[24].The lattice parameters of tetragonal perovskite phase of the
ceramic sintered at 1500 1C calculated after refinement of the
XRD pattern by FullProf software was found to be a¼ 4.009 Å
and c¼ 4.036 Å with c/a¼ 1.007. These values are very close to
the reported values of a¼ 4.007 Å and c¼ 4.025 Å with
c/a¼ 1.005 in the literature [11]. The Rietveld refined XRD
pattern of the sample sintered at 1500 1C is shown in Fig. 1b.
Fig. 2a and b shows the SEM micrograph and the grain
size–frequency histogram of the ceramic samples sintered at
1450 1C and 1500 1C, respectively. As revealed from the
histograms in the inset, the sample sintered at 1450 1C shows
a narrow grain size distribution with an average grain size of
14.1 mm, while the sample sintered at 1500 1C exhibits a wide
distribution of grain sizes with average size of 16.6 mm. Also,
Fig. 2. SEM micrographs of ceramics sintered at 1450 1C and 1500 1C,
respectively. The inset shows the grains size distribution.
the micrographs clearly indicate that the grain size increases
with sintering temperature.
Fig. 3 shows the ferroelectric hysteresis loops of BCTZ
ceramics sintered at 1450–1500 1C, measured at 40 Hz and at
room temperature. Though both the samples exhibit fairly well
saturated P–E loops, the ceramic samples sintered at 1500 1C
show higher value of remnant polarization (Pr) and coercive
field (Ec). This could be attributed to the grain size as its effect
dominates the variation of polarization; higher grain size
results in an increase of polarization. The Pr and Ec values
of the samples sintered at 1500 1C were 12.20 mC/cm2 and
4.50 kV/cm, respectively, as compared to 8.02 mC/cm2 and
3.80 kV/cm of the sample sintered at 1450 1C. Also BCZT
ceramic samples prepared in the present study which were
sintered at 1500 1C has higher remnant polarization values of
(Pr ¼ 12.20 mC/cm2) when compared to  10 mC/cm2 [20],
 M.A. Rafiq et al. / Ceramics International 41 (2015) 11436–11444 11439

Fig. 3. P–E loops for the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 ceramics sintered at

1450–1500 1C. Sample sintered at 1500 1C showed higher remnant polariza-
tion and coercive field value.

9.0 mC/cm2 of [25], 11.69 mC/cm2 [26] and 11.05 mC/cm2 for
Pr2O3 doped BCZT [15], and slightly lower Ec ¼ 4.50 kV/cm
than  5.0 kV/cm [25], but higher than 200 V/mm (2 kV/cm)
[20], 1.9 kV/cm [24], 2.2 kV/cm of Pr2O3 doped BCZT [15].
Fig. 4a shows the variation of relative dielectric constant (εr)
with temperature (30–400 1C) of BCZT ceramics sintered at
1450–1500 1C, measured at 1 kHz. It is clear from the figure
that the value of εr at room temperature is similar for both the
samples, irrespective to the sintering temperature. However, a
huge difference in the εr value can be observed at the phase
transition temperature (TC) of samples sintered at 1450 1C
(εr ¼ 7712) and 1500 1C (εr ¼ 12,100). This massive increase/
difference in εr with increase in sintering temperature can be
attributed to increase in grain size [26].The increase in grain
size with increase in sintering temperature facilitates easier
domain wall motion [27] leading to an increase in εr. More-
over, high temperature sintering in air leads to the formation of
a strong insulating layer around the grains. These highly
insulating grain boundaries have a larger value of resistance
and capacitance when compared to that of the grain [28]. The
difference in the conductivity of the grain (bulk) and grain
boundary results in an increase in the accumulation of surface
charge resulting in the increase of interfacial polarization
which in turn results in the increase in εr.
Fig. 4b and c shows the temperature dependence of dielectric
constant and loss tangent (tan δ) measured at 100 Hz, 1 kHz,
10 kHz, 100 kHz and 1 MHz for BCZT ceramics sintered at
1500 1C. The Curie temperature (TC) was observed  105 1C,
which is higher than  95 1C [11], and 85 1C [24]. It is know
that grain size has a strong effect on Tc [29], and cell distortion Fig. 4. Dielectric constant of (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 ceramics (a) at a frequency
also plays a vital role on phase transitions as reported in BaTiO3 of 1 kHz sintered at 1450 1C, (b) at various frequencies from 100 Hz to 1 MHz
[29] and BCZT [24]ceramics. Hence, the change in Tc may be sintered at 1500 1C, and dielectric loss tan δ at various frequencies from 100 Hz to
1 MHz sintered at 1500 1C and (c) dielectric loss for the ceramic sintered at 1500 1C
attributed to the different processing conditions and cell volume and at various frequencies from 100 Hz to 1 MHz. The ceramic sintered at 1500 1C
effect, as slightly different lattice parameters of present samples showed higher dielectric constant and loss value started to increase at high
were calculated than the literature. In addition, the values of εr temperature of almost 170 1C.
11440 M.A. Rafiq et al. / Ceramics International 41 (2015) 11436–11444

and tan δ are higher at lower frequencies and decreases as the

frequency increases. The decrease in εr value with frequency can
be explained based on the decrease in polarization with the
increase in frequency as follows; for a dielectric material the net
polarization is given as the sum of contributions from dipolar,
electronic, ionic and interfacial polarizations [30]. All the
polarizations easily respond to the time varying electric field at
low frequencies, but as the frequency of the electric field
increases, the contributions of different polarization filters out
resulting in the decrease of net polarization that leads to the
decrease in the value of εr of the dielectric. The dielectric
constant values at room temperature varied between 2465
(1 MHz) and 3410 (100 Hz), which is close to the value 3060
(frequency value not reported) reported in the literature [11]. The
above analysis for BCZT ceramics is fairly standard, especially
below 200 1C and has been widely reported in the literature.
However, the difference lies in the deviation often noticed in the
electrical properties such as, TC, εr, Pr, Ec etc. from one literature
report to the other. This deviation is often ascribed to the effect
of grain size, porosity, chemical inhomogeneity, especially grain
and grain boundary impedance. In order to perform a thorough
analysis of the electrical properties and their temperature
dependence, it is essential to separate the contribution from
grain/bulk and grain boundary components. Hence, the complex
impedance spectroscopy (CIS), a non-destructive technique was
used in investigating the electrical properties of BCZT ceramics.
The analysis of the transformed dielectric data into different
formalism is very important to understand the actual picture of
the material. The use of function Zn is particularly appropriate for
the resistive and/or conductive analysis where the long-range
conduction dominates, whereas Mn functions are suitable when
localized relaxation dominates.
Fig. 5a shows complex impedance spectrum (Nyquist plot, a
plot between the real (Z0 ) and imaginary (Z00 ) of complex
impedance Zn) of BCZT ceramic sintered at 1500 1C. The
impedance data from room temperature up to about 300 1C is
not illustrated in the figure as they just showed a straight line with
large slope signifying the high insulating behavior of BCZT.
However, as the temperature increased (especially above TC) the
slope decreased and was found to curve towards the major (Zʹ) axis
forming clear semicircular arcs. The radius of curvature was found
to decrease with increasing temperature, which shows the increase
in conductivity of the sample with temperature. In general,
existence of a single semicircular arc represents the grain interior
(bulk) property of the material. However, in the present case, at
temperature of 300 1C or higher, the spectrum comprises of two
semicircular arcs. The two semi-circular arcs in the Nyquist plot are
due to contributions from the grain interior (bulk) and grain
boundary. The arc at high frequency is ascribed to the grain (bulk)
and the one at low frequency to the grain boundary contribution. Fig. 5. (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 ceramics (a) Nyquist plot at different
temperatures along with the fitting results using, electric circuit show in inset
Fig. 5a shows typical impedance plot, at temperatures between 300
of Fig. 5a (b) real part impedance and (c) imaginary part of impedance versus
and 400 1C for BCZT ceramics consisting of two semi-circular frequency from 100 Hz to 1 MHz at various temperatures along with fitting
arcs along with the fitting results of impedance data by using results.
 M.A. Rafiq et al. / Ceramics International 41 (2015) 11436–11444 11441

Table 1 region at different temperatures was observed. Further, the

Resistance, capacitance values and relaxation time determined for bulk and curves were found to merge at a specific frequency in the
grain boundary.
higher frequency region. This is due to the reduction in space
T R1 C1 Τ n R2 C2 n τ charge polarization at higher frequency. In perovskite system
(1C) kΩ pF (s) 10  5 kΩ nF (s) 10  5

300 611.71 351 21.5 0.97 658.99 2.63 0.96 173

320 512.58 264 13.5 0.98 669.18 3.63 0.95 243
340 327.12 277 9.1 0.97 493.57 7.61 0.9 376
360 214.26 278 6.0 0.96 379.39 13.9 0.86 527
380 146.94 277 4.1 0.96 291.76 23.8 0.82 695
400 103.19 298 3.1 0.95 218.18 41.2 0.78 900

Z-view software (Ver. 3.2c Scribner Associates, Inc). Fitting was

done by using an equivalent electric circuit consisting of two
resistances in series and capacitive phase element (CPE) in parallel
as shown in the inset of Fig. 5a and values of resistance and
capacitance for the bulk and grain boundary was calculated. CPE
was used for fitting instead of pure capacitor to overcome the
dispersion and non-linearties in the values, and expected to show a
more accurate representation of the dielectric properties and related
data. Fitting the data showed good agreement with the experi-
mental data in all cases. R1 in the circuit represented the bulk
resistance, C1 the bulk capacitance, R2 the grain boundary
resistance and C2 as grain boundary capacitance. From the
obtained values of resistance and capacitance for the bulk and
grain boundary, relaxation time for the bulk and grain boundary
was calculated by using the relation τ ¼ RC and is listed in
Table 1. Relaxation time was found to decrease with temperature
for the bulk and vice versa was true for grain boundary.
The variation of real part of impedance (Zʹ) with frequency
at various temperatures is shown in Fig. 5b. The magnitude of
Zʹ was found to decrease with increase in temperature which
indicated the increase in ac conduction (σac) in the sample.
This increase in ac conduction with temperature might have
appeared due to the contribution of defects like oxygen
vacancies in the sample. At elevated temperature, the con-
tribution due to oxygen vacancies is more dominant in
perovskite structures. Higher value of Zʹ at lower frequency
and temperature plus merging of Zʹ at higher frequency
(4 10 kHz) for all temperatures, clearly indicates the presence
of space charge polarization [31,32]. At higher temperature the
impedance seems to be independent of frequency and
temperature.
The variation of imaginary part of impedance (Zʺ) with
frequency at different temperatures is shown in Fig. 5c. The
Zʺmax peaks shifts and broadening was observed at higher
frequencies with increasing temperature. The appearance of
temperature dependent peaks (Zʺmax) at a characteristic fre-
quency (ωmax ¼ 2πfmax) can be related to the type and strength
of the electrical relaxation phenomena in the material. This
peak shift and broadening behavior shows the presence of
relaxation process, which is temperature dependent [33]. These
relaxation processes may be due to the presence of immobile
species at low temperature and defects at high temperature.
The shift in the peak position with temperature shows a Fig. 6. (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 ceramics (a) Mʺ vs. Mʹ at different
temperature dependent relaxation process. A clear indication temperatures along with the fitting results, (b) Mʹ vs.frequency and (c) Mʺ
of the dispersion of the resultant curves in lower frequency vs. frequency from 100 Hz to 1 MHz at various temperatures.
11442 M.A. Rafiq et al. / Ceramics International 41 (2015) 11436–11444

the major mode of charge transport is a multiple hopping

process. This hopping process normally takes place across the
potential barriers set up by the lattice structure and the local
environment of other atoms/ions.
The impedance data have been re-plotted in the modulus
formalism as shown in Fig. 6 at the same temperatures as have
been shown for the complex impedance plots. Fig. 6a shows two
semicircular arcs in the complex modulus plots with a small
semicircle at high frequency and a large semi-circular arc in the
low frequency region at all the temperatures. The modulus
spectrum shows a marked change in the shape with use in
temperature suggesting a probable change in the capacitance
value of BCZT material as a function of temperature.
Fig. 6b shows the variation of real part of electric modulus
(Mʹ) with frequency at higher temperatures (between 300 1C
and 400 1C ). It is characterized by a low value of Mʹ in the
Fig. 7. Variation of relaxation time for the bulk (grain interior) and grain
low frequency region followed by a continuous dispersion with
boundary vs. inverse of temperature for (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 ceramics
increase in frequency. It was found that Mʹ values saturated to sintered at 1500 1C.
a maximum value in the high frequency region for all
temperatures. This sigmoidal increase in the value of Mʹ
approaches to maximum value with increasing frequency, is
probably due to the short range mobility of carriers like ions.
Fig. 6c shows the plot of imaginary part (Mʺ) of dielectric
modulus at different temperatures. The peak was found to shift
towards higher frequency side with increasing temperature.
Physically, the peak in the imaginary part of the electric
modulus defines the regions where the carrier can move at long
distances (left to the peak) or confinement (right to the) peak.
Also, a peak in the Mʺ imaginary part indicates a dielectric
relaxation process in the solid, and the frequency to the
maximum indicates the mean relaxation time of this process.
As can be seen, the imaginary part of the electric modulus
exhibits a very well defined peak. In our case the peak is
relatively symmetrical in a considerable frequency range at
each measured temperature.
Fig. 7 shows the variation of relaxation time with inverse of
temperature. The relaxation time τ was calculated from the
fitting of Nyquist plot using the relation, τ ¼ RC where R is the
resistance and C is the capacitance. The plot of τ versus 1000/T
gives a straight line which can be approximated to the relation,
τ ¼ τ0exp(Ea/KBT) [34], where τ0 is the preexponential factor,
Ea is the activation energy and kB is the Boltzmann constant.
The calculated activation energy of BCZT bulk and grain
boundary is 0.69 and 1.44 eV respectively. The relaxation time
is in 10  5 s, which can be attributed to the hopping conduction
mechanism [35].
Fig. 8a shows the AC electrical conductivity (σac(ω)) as a
function of frequency at different temperatures from 300 1C to
400 1C. The analysis of the AC-conductivity shows that the
values of conductivities are in the range of (10  5–10  3) (S/m)
at frequencies of 1–106 Hz for BCZT ceramic. The plots
showed a dispersive nature at lower frequency regime which
became narrowed at higher frequencies. As it could be
observed, the slope change in lower temperature region is
more prominent. This may be the indication of maximum ionic Fig. 8. Variation of ac conductivity vs. (a) frequency at various temperatures
motion taken place, which involves localized hopping with and (b) inverse of temperature at different frequencies for BCZT ceramics
either rotation or translation of the mobile species [32]. The sintered at 1500 1C.
 M.A. Rafiq et al. / Ceramics International 41 (2015) 11436–11444 11443

behavior of the AC conductivity with temperature for BCZT Table 2

ceramics is shown in Fig. 8b. The graphs can be divided,
independent of frequency, in four regions characterized by
different slopes, as shown in the figure. According to this, one
ferroelectric region designated by FE I and three paraelectric
regions PE I, PE II, and PE III are marked out with dashed
lines. Every region is characterized by different slopes
indicating the presence of different conduction mechanisms
associated with their corresponding values of activation energy
(Ea). The AC conductivity increases with measuring frequen-
cies especially at low temperatures. As the temperature
increases, the conductivity becomes frequency independent
with a slight increase on the higher frequency side. The values
of Ea were calculated assuming an Arrhenius behavior
according to the equation;
 
Ea
σ ac ¼ σ 0  ð5Þ
KbT
where,σ 0 stands for the pre-exponential terma, σ ac is the ac
conductivity, E a is the activation energy, K b is the Boltzmann
constant, and T is the temperature in Kelvin scale. Activation
energy (Ea) values are summarized in Table 2 for various
frequencies.
The slope variations and corresponding changes of activa-
tion energy for the AC conductivity observed between FE I
and PE I regions can be of order-disorder type and attributed to
the readjustment of the lattice during the transition of crystal-
line phase going from tetragonal - cubic structure at room
temperature toward cubic structure near the ferro-paraelectric
transition temperature in agreement with the structural reports
on the BCZT ceramics [11,24,25]. The values of Ea obtained
for the FE I and PE region from 0.024–0.25 eV to 0.47–
0.62 eV are in correspondence with the hopping charge
mechanisms [36].
In the PE II and PE III, the activation energy varied from
0.80–1.10 eV to 0.69–0.75 eV at different frequencies. For
ferroelectric perovskites, values of activation energy for
conduction in the range of 0.6–1.2 eV suggest that the
electrical conduction is due to the motion of the electrons
from the second ionization of oxygen vacancies [36–38]. At
lower temperatures, the oxygen vacancies exhibit low mobi-
lity; however, with the increase in temperature they are
activated and contribute to the observed electrical behavior.
The obtained activation energy for conduction, which is very
close to the values associated with double ionized oxygen
vacancies (Vö) reported for other ceramic oxides suggests
oxygen vacancies hopping mechanism [36].
4. Conclusions
(Ba0.85Ca0.15)(Zr0.1Ti0.9)O3; BCZT lead free piezoelectric
ceramic has been synthesized by conventional solid state
reaction technique. XRD studies showed that monophasic
ceramic were formed only at a calcination temperature of
1350 1C. Samples sintered at 1500 1C showed higher remnant
polarization (Pr ¼ 12.20 mC/cm2), coercive field (Ec ¼ 4.50 kV)
and dielectric constant (εr  12,000) respectively. Detailed
Activation energy values Ea in eV for ac conduction, calculated assuming an
Arrhenius behavior for each of the marked regions in Fig. 8 for different
frequency values.
Regions 1 kHz 10 kHz 100 kHz 1 MHz
FE I 0.25 0.16 0.05 0.02
PE I 0.52 0.62 0.55 0.47
PE II 1.10 0.90 0.84 0.82
PE III 0.76 0.69 0.69 0.70
studies of dielectric and electrical properties indicate that the
material has mainly two contribution of grain (bulk) and grain
boundary. The activation energy values suggest that the
electrical conduction in BCZT is mainly due to the mobility
of the ionized oxygen defects via hopping mechanism.
Acknowledgments
Muhammad Asif Rafiq acknowledges the finanical and
infrastructure support of Department of MME, UET Lahore.
KVS acknowledges UGC, Govt. of India for providing the
Start-up Grant and other infrastructure facilities and the
Foundation for Science and Technology (FCT), Portugal for
the Grant SFRH/BPD/80742/2011SFRH/BPD/80742/2011.
The authors acknowledge Prof. Paula Vilharinho and Prof.
Elisabaete Costa, Universidade de Aveiro, for extending the
infrastructural and laboratory facilities.
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