J Mater Sci: Mater Electron
DOI 10.1007/s10854-015-4147-0
Diffusion phase transition and impedance spectroscopy
of Bi2O3/CuO co-doped BCZT lead-free ceramics
Xiaofang Wang1,2 • Pengfei Liang1 • Lingling Wei1 • Xiaolian Chao1
Zupei Yang1
Received: 19 August 2015 / Accepted: 26 November 2015
Ó Springer Science+Business Media New York 2015
Abstract Perovskite type (Ba0.85Ca0.15-2xBi2x)(Zr0.1
Ti0.9-xCux)O3 lead-free ceramics were prepared via a
conventional solid-state reaction method. The phase
structure, dielectric, ferroelectric properties and complex
impedance were investigated in detail. XRD and dielectric
measurements determined that single orthorhombic phase
displayed in (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 at room tempera-
ture. With the introduction of Bi2O3/CuO, the phase
structure exhibited the mixture of orthorhombic and
tetragonal phases, and then turned to single tetragonal
phase. In contrast to the sharp dielectric transition of
(Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 ceramics, a broad dielectric
peak coupled with a slight decrease in Curie temperature
was observed in (Ba0.85Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3
ceramics with increasing x. The observed diffuse phase
transition behavior was further confirmed by a couple of
measurements with polarization loops and polarization
current density curves. The structural and the composition
fluctuations induced by ions doping should be responsible
for the diffuse phase transition behavior. Furthermore,
physical mechanisms of the conduction and relaxation
processes were revealed by using impedance spectroscopy
analyses. It was concluded that the conduction and relax-
ation processes were thermally activated, which was
& Zupei Yang
yangzp@snnu.edu.cn
1
Key Laboratory for Macromolecular Science of Shaanxi
Province, School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710062, Shaanxi, People’s
Republic of China
2 PNRs and correlations among them should be closely
College of Chemistry and Chemical Engineering, Xianyang
Normal University, Xianyang 712000, Shaanxi, People’s
Republic of China
•
closely linked with the singly and doubly ionized oxygen
vacancies.
1 Introduction
In the past few years, there has been considerable interest
in the perovskite phase (Ba,Ca)(Zr,Ti)O3 (BCZT) as a
promising lead-free piezoelectric material due to its high
piezoelectric response [1–3]. Extensive researches have
proposed that the excellent piezoelectric performance was
attributed to a triple point morphotropic phase boundary
state (MPB), a coexistence of tetragonal, orthorhombic,
and cubic phases close to room temperature [4–7]. How-
ever, it is a remarkable fact that this transition corre-
spondingly results in strong temperature dependence due to
the coexistence of tetragonal and orthorhombic phases near
room temperature for BCZT materials, which has become
the main key problem currently.
Recently, some attempts have been performed to adjust
the structure and electrical properties of BCZT ceramics in
order to widen their practical applications, such as the ions
doping, the optimization of BZT–xBCT composition and
the construction of MPB. The relaxor behavior, which is
usually observed in complex perovskites by ions doping,
could effectively improve the dielectric properties in piezo
ceramics [8, 9]. Further research demonstrates that the
disordered distribution of different ions at one or more
equivalent crystallographic sites is an essential character-
istic of relaxors. This disorder distribution induces local
random fields which are responsible for the growth of the
polar nanoregions (PNRs) [10]. The presence of these
associated with the evolution of relaxor behaviors [11]. For
BaTiO3 ceramics, it is well-known that A-site or B-site
123

substitution can lead to significant changes in structure and
properties of piezoelectric ceramics. Bahri et al. [12] have
found that the substitution of A site with Bi3? can trigger
the relaxor behavior in BaTiO3. This phenomenon has also
been observed in Bi3? doped Ba(Zr,Ti)O3 system [13].
Similarly, Chen et al. [14] reported that Bi doped SrTiO3
could show a crossover from normal ferroelectric to relaxor
behavior. Now, a widely accepted viewpoint is that the
random field induced by domain state should be responsi-
ble for the relaxor behavior for Bi3? doped BaTiO3-based
ceramics [15].
In this work, Bi2O3 was incorporated in BCZT ceramics
with the purpose of adjusting the dielectric behavior.
Simultaneously, it was worth noting that the introduction of
Bi3? in A-site could induce charge imbalance, which might
be compensated by A-site cation vacancies. In order to
compensate the charge imbalance in BCZT ceramics, CuO
was introduced in B-site to further create a local hetero-
geneity with valence fluctuations. The possible charge
compensation mechanisms could be defined by Kroger–
Vink notation given as follows:
Bi2 O3 þ VO ! 2BiBa 
þ 3O ð1Þ
CuO ! Cu00Ti þ O þ VO ð2Þ
Bi2 O3 þ CuO ! 2BiBa þ Cu00Ti þ 4O ð3Þ
The introduction of Bi2O3/CuO to BCZT ceramics could
be expected to increase the disordered degree of (Ba0.85
Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 solid solutions, induced a
diffuse phase transition and then improved the dielectric
properties. This paper investigated the structure, dielectric
and ferroelectric properties of the (Ba0.85Ca0.15-2xBi2x)
(Zr0.1Ti0.9-xCux)O3 ceramics. In order to pinpoint the effect of
Bi3? and Cu2? substitution on the overall electrical properties,
the impedance spectroscopy technique was used to separate
out the contribution of grain and grain boundary effects.
2 Experimental procedure
(Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 (x = 0.00, 0.005,
0.01, 0.015 and 0.02) lead-free ceramics were prepared by
solid-state reaction method. Reagent-grade powders,
BaCO3, CaCO3, ZrO2, TiO2, Bi2O3 and CuO were used as
the starting materials. The powders were mixed by ball
milling in alcohol for 16 h. After drying, the mixtures were
calcined at 900 °C for 6 h. Then the powder was mixed
with 5 wt% polyvinyl alcohol (PVA) solution and then
pressed uniaxially into disk specimens with a diameter of
15 mm and a thickness of *2 mm under 100 MPa. After
burning out PVA at 500 °C, the disks were sintered at
1220–1400 °C for 6 h in N2 atmosphere, depending on the
Bi2O3 and CuO content.
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J Mater Sci: Mater Electron
The phase structures were identified by X-ray power
diffraction (XRD, D/max-2550/PC, Rigaku, Japan) with Cu
Ka radiation. The microstructures were observed with the
scanning electron microscope (SEM, Quanta 200, FEI Co.,
Eindhoven, Netherlands). To measure the electrical prop-
erties, silver paste was coated on both sides of the sintered
pellets and fired at 840 °C for 30 min to form electrodes.
Temperature-dependent of dielectric constant was obtained
by the LCR meter (Hioki, 3252-50, Cryo Industries, USA)
connected to a computer-controlled temperature chamber.
The polarization and strain hysteresis as a function of
external electric field were measured at 1 Hz with a 30 kV/
cm using a high voltage amplifier (Model 610E, Trek,
USA) for the electrical loading. Complex impedance were
measured by Agilent 4294A (Palo Alto, CA) impedance
analyzer.
3 Results and discussion
3.1 Microstructure and phase transition
Figure 1a shows the XRD patterns of the (Ba0.85Ca0.15-2x
Bi2x)(Zr0.1Ti0.9-xCux)O3 powders by crushing the samples.
It can be seen that all compositions exhibit a pure per-
ovskite structure (PDF#79-1482) and no secondary phase is
observed in the investigated range. To survey the phase
evolution, further observation on the XRD patterns is car-
ried out in the diffraction angle range of 44°–47°, and the
results are displayed in Fig. 1b. The diffraction peaks are
separated by fitting the Gaussian–Lorentz line shape, and
the positions of the reflections are fixed using the least
square method. The results reveal obvious changes in
diffraction peaks near 2h = 45°, indicating that Bi2O3/CuO
substitution can induce a structural phase transition from
the single orthorhombic phase of pure BCZT ceramics to
the mixture of orthorhombic and tetragonal phases, and
then to single tetragonal phase with further increasing x. To
further verify the effect of Bi and Cu additions on the phase
transition, the lattice constant a, b were calculated using the
least square method from XRD data, which are displayed in
the inset of Fig. 1a. It can be seen that the lattice constants
a, b keep subtle changes in all specimens. For the samples
of 0.00 B x B 0.005, the values of a, b have a slight dif-
ference. While for the samples of 0.01 B x B 0.02, the
values of a, b are almost the same. The variation of lattice
constant further confirms the phase transition from O to
O ? T, then to single T phases with increasing of Bi, Cu
addition in (Ba0.85Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 speci-
mens. In addition, it can be observed that the peaks near
45° shift slightly to lower angle, then to higher angle with
increasing x. The result is probably due to smaller ionic
radii of Bi3? (1.17 Å) compared with Ba2? (1.61 Å) and
J Mater Sci: Mater Electron
Fig. 1 XRD pattern of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics between the 2h range of 20°–80° (a); expanded XRD patterns in the 2h
range of 44°–47° of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics (b)
Ca2? (1.34Å) at A-site, and the relatively larger ionic radii
of Cu2? (0.73 Å) compared with Ti4? (0.605 Å) and Zr4?
(0.72 Å) at B-site, and the disordered distribution of dif-
ferent ions at one or more equivalent crystallographic sites
can lead to the structural fluctuation.
Figure 2a–e shows the typical microstructure of pure
BCZT sintered at 1400 °C and Bi2O3/CuO co-doped BCZT
specimens sintered at 1220–1250 °C, respectively. All
samples show high density with low porosity, and the
samples with different compositions exhibit completely
different grain size. With the addition of small amount of
Bi2O3/CuO, the grain size decreases sharply and becomes
uniform. The measured density with Archimedes method
and relative density of Bi2O3/CuO co-doped specimens are
shown in Fig. 2f. It can be seen that the measured density
and the relative density increases firstly, and then decreases
with further increasing Bi2O3/CuO amount. Both the
measured and relative densities reach the maximum values
of 5.34 g/cm3 and 97 % at x = 0.010, respectively. The
variations trend of SEM and density can be attributed to the
low melting points of Bi2O3 (825 °C) and CuO (1026 °C)
additives, a liquid phase should be formed in the early
stage of the sintering process, so as to promote the grain
uniform and the densification behavior by facilitating the
dissolution and migration of the species [16, 17]. In the
later stage, Bi3? and Cu2? ions will enter into the BaTiO3
lattice to substitute the ions at A or B sites and modify the
properties of ceramics. However, when the doping content
increases, the liquid phase will be separated out and form
glass phase, which will deteriorate overall performance of
samples. Therefore, it can be concluded that the proper
amount of Bi2O3/CuO addition can act as the grain
refinement and sintering aids in BCZT ceramics.
3.2 Dielectric properties
The temperature dependence of dielectric properties for
(Ba0.85Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 specimens are
shown in Fig. 3a–e. Firstly, it can be seen that the Curie
temperature drops gradually to low temperature with
increasing the addition of Bi2O3/CuO. Secondly, the
maximum dielectric constant depresses with increasing the
Bi2O3/CuO content. Thirdly, it is worth noting that the
studied compositions exhibit the diffuse phase transfor-
mation (DPT), and the DPT behavior enhances with
increasing the Bi2O3/CuO content, meaning that the sub-
stitution of Bi2O3/CuO can enhance the degree of dielectric
diffuse. In order to further testify the diffuse degree, the c
value, which is considered as the degree of diffuse degree
ranging between 1 and 2 for a normal ferroelectric and an
ideal relaxor ferroelectric, is calculated from the modified
Curie–Weiss law [18], and the result is displayed in Fig. 3f.
It is obvious that c values increase monotonously with
increasing the Bi2O3/CuO content, and the maximum value
of 1.970 is obtained at x = 0.020. Previous research has
shown that the disordered distribution of different ions at
one of more equivalent crystallographic sites is an essential
characteristic of relaxor behavior in complex perovskites
ceramics [19, 20]. For (Ba0.85Ca0.15-2xBi2x)(Zr0.1Ti0.9-x
Cux)O3 ceramics, Bi3? locates at A-site with Ba2? and
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 J Mater Sci: Mater Electron

Fig. 2 SEM micrographs of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics: a x = 0.00; b x = 0.005; c x = 0.01; d x = 0.015; e x = 0.020;
f the measured density and relative density of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics

Fig. 3 Temperature dependence of the dielectric constant and d x = 0.015; e x = 0.02; f plots of ln(1/er - 1/emax) as a func-
dielectric loss tangent at 1, 10, 100 kHz of (Ba0.85C0.15-2xBi2x)(Zr0.1- tion of ln(T - Tmax) at 10 kHz for (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-x
Ti0.9-xCux)O3 ceramics: a x = 0.00; b x = 0.005; c x = 0.01; Cux)O3 ceramics

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J Mater Sci: Mater Electron
Ca2? ions, and Cu2? locates at B-site with Ti4? and Zr4?
ions. The variation of ionic size and ions charge at one or
more equivalent crystallographic sites will lead to disor-
dered distribution, resulting in the formation of random
local fields and the enhanced DPT behavior. In addition,
according to the electronic configurations of
4f 145d106s26p3 for Bi and 3s23p63d104s1 for Cu, it can be
deduced that Bi3? ion with the 6s2 lone pair has the large
stereochemical activity, similar to the neighbor element of
Pb2?. Considering the stereochemical activity of the Bi
lone pair and the large difference of ionic radii between
host Ba2?, Ca2? and added Bi3? ion, Bi3? can drive the
large displacement at the off-centered A position, resulting
in the formation of the polar clusters, which give rise to the
transformation from normal ferroelectric to relaxors [21].
On the other hand, for the similar ionic radii of Cu2? and
Ti4?, Zr4?, both Ti, Zr and Cu ions occupy the B sites of
BCZT perovskite structure. Based on the concept of the
‘‘active Ti ions’’ proposed by Slater [22], the chemically
inert Cu ions are at central position with no displacement,
which handicaps the Ti, Zr ions to participate in ferro-
electricity and decreases the Curie temperature. Further-
more, the dielectric behavior in (Ba0.85Ca0.15-2xBi2x)
(Zr0.1Ti0.9-xCux)O3 ceramics could be explained by defect
complexes, which generate from the acceptor impurity of
Cu2? for Ti4? at the B site of BCZT. Defect complexes
with a net dipole moment can effectively impede polar-
ization reversal, and the defect dipole is an acceptor with a
negative local charge with respect to the site of substitution
and a charge compensating positively charged defect,
typically an oxygen vacancy [23]. Aligned defect dipoles
generate an internal bias field, which strongly affects the
dielectric and ferroelectric behavior. Therefore, the DPT
behavior in (Ba0.85Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3
ceramics can be attributed to the introduction of co-doped
Bi2O3/CuO.
3.3 Ferroelectric properties
In order to further explore the DPT behavior in (Ba0.85
Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics, Fig. 4a–e
depicts the room-temperature P–E hysteresis loops for all
compositions, as well as the corresponding current density
loops (J–E) to provide a more detailed picture to the
switching processes. The corresponding variation trends of
the remanent polarization (Pr) and coercive field (Ec) are
also summarized in Fig. 4f. It is obvious that for the sample
with x = 0.00, a saturated P–E loop is obtained with a
relatively large Pr value, and Ec remains a low value. At the
same time, a single sharp polarization current peak is
appeared, which can be ascribed to the domain switch. This
is typical for normal ferroelectric materials with a long-
range ferroelectric ordering [24]. While, for the sample
with Bi2O3/CuO substituted, slim and unsaturated P–
E loops are acquired with a relatively lower Pr and a rel-
atively higher Ec values. At the same time, gradual changes
with a broad and flat current platform are obtained in
current peaks. All these features are typical for ergodic
ralxors [10, 25]. The different ferroelectric behavior
between pure BCZT and the substituted samples may be
associated with the emergence of diffuse phase transition
around Curie temperature with the introduction of Bi2O3/
CuO. With increasing x, the domains in this compositions
are frozen, which will prevent to destroy the long-range
polar [26], so the values of Pr decreases and Ec increases.
3.4 Impedance spectroscopy
In order to carry out a more detailed analysis of dielectric
properties, it is necessary to understand the contribution of
grain and grain boundary effects, which could greatly
influence the properties. Figure 5a–e illustrates the Nyquist
plots for all specimens at various temperatures. It can be
seen that the diameter of the impedance plots becomes
smaller with increasing temperature for all samples,
demonstrating a decrease in impedance. In addition, two
clear semicircles are emerged at x = 0.00 in Fig. 5a. The
high-frequency semicircle can be attributed to an intrinsic
grain effect, whereas the low-frequency semicircle is due to
the grain boundary effect. This result indicates that pure
BCZT ceramics are electrically heterogeneous in the
measurement temperatures, which consist of grain and
grain boundary response. Moreover, two unnoticeable
semicircles can be observed in Fig. 5b, c if a careful
examination is taken. Interestingly, only one semicircle is
presented in Fig. 5d, e at x = 0.015 and x = 0.020, sug-
gesting that the electrical properties arise mainly due to the
bulk effects. The transition from two semicircles to single
semicircle induced by Bi2O3/CuO content indicates that the
substituted BCZT ceramics become more electrically
homogeneous compared with pure BCZT ceramics.
The variation of dc conductivity with inverse of tem-
perature is shown in Fig. 6. It can be seen that the con-
ductivity for all the samples was found to increase linearly
with temperature. The curve was fitter with the Arrhenius
equation for conduction given by [27]
 
Ea
r ¼ A exp ;
KB T
where Ea is the activation energy, KB is the Boltzmann’s
constant and A is pre-exponent factor. The obtained values
of activation energies for conduction are 1.10, 1.29, 1.31,
1.55 and 0.98 eV, respectively. It is well known in a per-
ovskite system, oxygen vacancies play an important role in
conduction process. The activation energy for conduction
for oxygen in these systems is about 1–2 eV, the result is
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 J Mater Sci: Mater Electron

Fig. 4 P–E hysteresis loops and J–E curves of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics: a x = 0.00; b x = 0.005; c x = 0.01;
d x = 0.015; e x = 0.02 at room temperature, and f composition of the remnant polarization Pr and coercive field Ec

Fig. 5 Complex impedance plots of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics at various temperatures: a x = 0.00; b x = 0.005;
c x = 0.01; d x = 0.015; e x = 0.020

similar to the La-doped Ba(Zr0.9T0.1)O3 ceramics [28]. Figure 7a–e displays the plots of real part (Z0 ) of
Therefore the activation energy is associated with the impedance as a function of frequency for the samples with
energy barrier for the long-range motion of charge carriers different Bi2O3/CuO contents at several temperatures. It is
which could be electrons/holes or vacancies. well known that the value of Z0 is related to the sample

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J Mater Sci: Mater Electron

electric resistance [29]. As shown in Fig. 7, Z0 is almost
independent with frequency in the low-frequency range at a
certain measuring temperature, and then Z0 suddenly
decreases with further increasing the frequency and tem-
perature. At higher frequencies, the Z0 value seems to
merge for all temperatures, indicating that a possible
release of the space charge will have induced a reduction in
barrier property of the material with increasing tempera-
ture, which may be a responsible factor for the enhance-
ment in high-frequency ac conductivity of the material with
-8
x =0.000, Ea=1.10eV
x =0.005, Ea=1.29eV
x =0.010, Ea=1.31eV
x =0.015, Ea=1.55eV
-10 x =0.020, Ea=0.98eV
Fitting lines
lnσ (Ω⋅cm)
temperature [30]. At low frequency, the higher Z0 value can
be obtained at each temperature, which is an indication of
the space charge polarization of the materials. The decrease
in the Z0 value at low frequencies with increasing tem-
perature is due to the increase in the mobility of the charge
carriers or the decrease in the density of the trapped
charges. In addition, it can be seen that two step-like
decreases appear in Fig. 5a–c with increasing temperature,
while only one step-like decrease is found in Fig. 5d, e.
The result is well consistent with that of Fig. 5a–e, in
which two semicircles changes to single semicircle when
incorporated with Bi2O3/CuO.
Figure 8a–e illustrates the imaginary (Z00 ) part plotted
against log of frequency at various temperatures. This plot
is suitable to evaluate the mechanism of relaxation process.
As shown in Fig. 8, the impedance peaks in each fig-

ure move toward higher frequencies with increasing tem-

-12 perature, indicating the appearance of relaxation behavior.
As mentioned above, the peak at lower frequencies is
-14
attributed to the relaxation process associated with the
grain boundaries, and the other peak at higher frequencies
is associated with the bulk. With increasing Bi2O3/CuO
-16 content, the relaxation peaks for the GB response gradually
weaken and finally disappeared, and only one relaxation
1.35 1.40 1.45 1.50 1.55
1000/T (K)
peak is observed in low frequency range for the samples
with x = 0.015 and x = 0.020. The results are well con-
Fig. 6 Variation of dc conduction with inverse of temperature for sistent with the impedance plots in Figs. 5 and 7. The
pure and Bi2O3/CuO doped BCZT ceramic transition behavior from electrical heterogeneity to

Fig. 7 Frequency dependences of real Z0 of impedance of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics at various temperatures

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Fig. 8 Frequency dependences of real Z00 of impedance of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics at various temperatures
homogeneity with additive may be attributed to that Bi2O3/
CuO will melt at high temperature sintering process, which
would in turn improve the transfer of mass and energy
between reactants. Therefore, increasing of Bi2O3/CuO
content could give rise to an improvement of electrical
homogeneity, and only bulk response could be observed in
impedance spectroscopy at high level of Bi2O3/CuO.
To get a broader understanding of the relaxation process
of grains, the activation energy of the relaxation process
was evaluated. And the relaxation frequency associated
with these peaks follows the Arrhenius law in the tem-
perature range and the expression can be described [31],
 
Ea
fmax ¼ f0 exp ð4Þ
KB T
where fmax is the peak frequency, f0 is the pre-exponential
term, Ea is the relaxation activation energy, and KB is the
Boltzmann constant. A plot of ln fmax versus 1000/T is
shown in Fig. 9. It can be seen that linear relations are
achieved in ln fmax versus 1000/T plots for all samples. For
the sample with 0.00 B x B 0.010, the activation energy of
grain boundary is 1.31, 1.27 and 1.43 eV, respectively.
While for the sample of x = 0.015 and x = 0.020, the
activation energy of bulk is 1.51 eV and 1.12 V. It is well
known that the oxygen vacancies can be easily introduced
at high temperature sintering process, which will produce
the conducting electrons. The activation energies for oxy-
gen-vacancy-related relaxations are widely reported to be
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J Mater Sci: Mater Electron
in the range of 0.1–0.5, 0.6–1.2, and *1.0 eV for the
single-ionized, doubly-ionized, and diffusion of oxygen
vacancies, respectively [32, 33]. The values of activation
energy in (Ba0.85Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceram-
ics is similar to the double-ionized. Therefore, it can be
concluded that the observed dielectric response is closely
linked with the ionized oxygen vacancies in (Ba0.85
Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics.
4 Conclusions
(Ba0.85Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 lead-free ceram-
ics were fabricated by a solid-state reaction method. The
effects of Bi2O3/CuO co-doped on the phase structure,
microstructure and electrical properties were investigated.
X-ray diffraction revealed that the introduction of Bi2O3/
CuO induced the phase transition from orthorhombic phase
to coexistence of orthorhombic and tetragonal phases
firstly, then to single tetragonal phase with increasing the
Bi2O3/CuO content. The SEM displayed that the adoption
of Bi2O3/CuO could decrease the grain size sharply and
lead to uniform microstructure in (Ba0.85C0.15-xYx)(Zr0.1
Ti0.9)O3 system. Dielectric measurement showed that the
diffuse phase transition behavior appeared in (Ba0.85
C0.15-xYx)(Zr0.1Ti0.9)O3 system, and the degree of diffuse
phase transition was enhanced with the content of Bi2O3/
CuO. The bipolar P–E and J–E curves indicated that the
J Mater Sci: Mater Electron
Fig. 9 Arrhenius plots of (Ba0.85C0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics and the fitted activation energy (Ea) values
ferroelectric properties reduced in some degrees due to the
introduction of Bi2O3/CuO, and the result could be attrib-
uted to the frozen domains in substituted compositions,
which would prevent to destroy the long-range polar. The
impedance spectroscopy indicated that the BCZT ceramics
became electrically homogeneous by Bi2O3/CuO co-doped.
The activation energies linked with bulk response were
1.12–1.51 eV, confirming that the singly and doubly ion-
ized oxygen vacancies played an important role in in
(Ba0.85Ca0.15-2xBi2x)(Zr0.1Ti0.9-xCux)O3 ceramics.
Acknowledgments This work was supported by National Science
Foundation of China (NSFC) (Grant Nos. 51172136, 21401123 and
51107077), the Fundamental Research Funds for the Central
Universities (Program Nos. GK201403006, GK201402061,
GK201301002, GK201101003 and GK201101004), the Science and
Technology Program of Shaanxi Province (Grant Nos. 2013K09-26
and 2013JM2013), education department of Shaanxi Provincial
Government (Grant No. 12JK0631), Scientific and Technology
Research Project in Xi’an [Program No. CXY1342(4)].
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