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Investigation on the dielectric properties of Mg-doped (Ba0.95Ca0.05)

(Ti0.85Zr0.15)O3 ceramics
Jiyuan Miaoa,b, Zhiqiang Zhanga,b, Zhifu Liua,n, Yongxiang Lia,c,nn
a
CAS Key Lab of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, PR China
b
The University of Chinese Academy of Sciences, Beijing 100049, PR China
c
School of Electrical and Computer Systems Engineering, RMIT University, Melbourne 3001, Australia
Received 26 October 2014; accepted 14 March 2015

Abstract

Mg-doped Ba0.95Ca0.05Ti0.85Zr0.15O3 ceramics were prepared through a solid-state reaction method and their dielectric relaxation behavior was
investigated. All of compositions exhibit perovskite strucutre with acceptor-Mg in the B-sites. The grain size was reduced and homogenized by
Mg doping. The Tc and the magnitude of diffusion change regularly in the studied compositional ranges. The relaxor diffuseness from
ferroelectric phase transition reached maximum at x ¼0.01. The impedance study showed that the conductance activation energy of grain (Ea-g) is
higher than that of grain-boundary (Ea-gb). And Ea-gb varies with Mg concentrations, which is more stable than Ea-g. These results were explained
by oxygen vacancies generated and gathered as cluster rotate around the Mg″Ti in the grains.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Dielectric properties; Ceramics; Phase transition; Mg doping

1. Introduction
As derivative of BaTiO3, (Ba1 xCax)(Ti1 yZry)O3 (BCTZ)
dielectric materials have been extensively studied for its excellent
dielectric and piezoelectric properties. The high dielectric constant
and relative low dielectric loss make BCTZ an appropriate
candidate of energy storage dielectric materials for ceramic
capacitors [1,2]. However, the dielectric properties of BCTZ are
sensitive to the change of temperature and electric field. Research
work has been carried out to improve the dielectric stability of
BCTZ by adjusting the ratios of Zr and Ca contents, by coupling
with simple metal oxides MOx (M is aliovalent metal ions or rare
n
Corresponding author.
nn
Corresponding author at: CAS Key Lab of Inorganic Functional Materials
and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences,
Shanghai 200050, PR China.
E-mail addresses: liuzf@mail.sic.ac.cn (Z. Liu),
yxli@mail.sic.ac.cn (Y. Li).
earth ions, such as Ce, Ga) [3,4], or complex oxides (such as Bi-
based perovskite), or by doping. For instance, Chou studied the
influence of doping barium zirconium titanate with several rare
earth ions and indicated that the phase transition diffuseness is
enhanced [5].
Mg doping in BaTiO3 ceramics has been extensively studied and
showed large effects on the microstructure and dielectric behavior
of the BaTiO3 ceramics. The ceramic grain size became smaller and
Tc shifted to lower temperature with introduction of Mg2 þ in
BaTiO3 [6,7]. Ba0.95Ca0.05Ti0.85Zr0.15O3 ceramics with high Zr
contents show a broad dielectric constant–temperature curve near
Tc, which is caused by the inhomogeneous distribution of Zr4þ on
the Ti4 þ sites [2]. It is not clear whether the Mg doping effects on
the phase transition, dielectric behavior, conduction mechanism,
remain similar or not to that of Mg-doped BaTiO3 ceramics due to
the disordered doping sites of Zr4 þ /Ca2þ and the distortion of
long-range ferroelectric order. In the present work, Mg-doped
BCTZ ceramics were fabricated by the conventional solid-state

http://dx.doi.org/10.1016/j.ceramint.2015.03.302
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: J. Miao, et al., Investigation on the dielectric properties of Mg-doped (Ba0.95Ca0.05)(Ti0.85Zr0.15)O3 ceramics, Ceramics International
(2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.302
 2 J. Miao et al. / Ceramics International ] (]]]]) ]]]–]]]
reaction method. The effects of Mg doping on the microstructure,
dielectric properties and the mechanisms were investigated.
2. Experimental
The solid-state reaction method was applied to prepare the
samples. BaCO3 (99.8 wt%), CaCO3 (99.9 wt%), TiO2 (98.7 wt%),
ZrO2 (99.4 wt%), and (MgCO3)4  Mg(OH)2  5H2O (MgO at 40 wt
% content) were used as the starting materials. The source materials
were weighed according to the designed ratio, ball milled, dried,
sieved, and then calcined at 1150 1C for 2 h in air. After 6 h ball
milling, the powders were pressed into disks of 13 mm in diameter,
1.5 mm in thickness. Finally, these pellets were sintered at 1400 1C
for 2 h in air, and followed by a furnace cooling.
Sintered samples were ground into powder in agate mortar,
and then mixed with 30 vol% Si (99.999 wt%) for X-ray
diffraction measurements. Scanning electron microscope
(SEM, JSM-6700F, Japan) was used to observe the nature
surface morphology of samples. Impedance analysis facility
(6500B, Wayne-Kerr Electronic, England) equipped with a
temperature controlling system was applied to measure the
dielectric properties (Whpusite Instruments, GWM-200,
Wuhan, China). The impedance data were also collected in
the mode of impedance analyzer by LCR meter in the
frequency range from 20 Hz to 1 MHz and in the temperature
range of 20–550 1C.
3. Results and discussion
3.1. Structural analysis
The XRD patterns of xMg–Ba0.95Ca0.05Ti0.85Zr0.15O3 (x¼ 0,
0.002, 0.004, 0.006, 0.008, 0.01, 0.012, 0.014, 0.016, 0.018, and
0.02) are shown in Fig. 1. The Si (99.99%) was added into the
powder of BCZT ceramics to calculate the shift of the peaks. The
XRD peaks of all the samples could be indexed with a perovskite
structure similar with BaTiO3 (JCPDS card no. 31-0174). The right
side of Fig. 1 is the magnified peaks in the 2θ range of 44.5–45.51.
The (200) peak has no position shift with the increase of Mg
Fig. 1. XRD patterns of Mg-doped BCZT ceramics with different doping
contents.
Please cite this article as: J. Miao, et al., Investigation on the dielectric properties of Mg-doped (Ba0.95Ca0.05)(Ti0.85Zr0.15)O3 ceramics, Ceramics International
(2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.302
doping, implying that Mg2þ may mainly occupy the B-site in the
ABO3 perovskite structure. This can be understood that Mg2þ has
similar radius with Ti4þ (R(Mg2 þ )¼ 0.067 nmER(Ti4 þ )¼
0.0605 nmoR(Ba2þ )¼ 0.135 nm) [8]. The appearance of the
shoulder peak (002) indicates that the BCZT samples is that
mixture of a major R phase and a smaller amount of a pseudocubic
form related to local tetragonal (T) and/or orthorhombic (O)
distortions [2].
Fig. 2 shows the grain size dependence on the Mg doping
concentration in the doped BCZT. Insets of the figure are the
SEM micrographs of un-doped BCTZ ceramic and x ¼ 0.008
Mg-doped BCTZ ceramics, respectively. It can be seen the
pure BCTZ ceramics possessed bimodal grain microstructure
with very large grain size of up to 120 μm. With the increase
of MgO content, the grain size becomes smaller. At high Mg
doping concentrations, the grain size reduced to about 1–2 μm.
This result indicated that the doping of MgO inhibited the
growth of ceramic grains. The formation of the oxygen
vacancies induced by Mg doping and their motion may
suppress the grain growth of BCZT ceramics during the
sintering process [6,9].
3.2. Dielectric study
Fig. 3 shows the temperature dependences of the dielectric
constant and dielectric loss of the Mg-doped BCTZ ceramics with
different MgO contents measured at the frequency of 10 kHz. As
shown in Fig. 3a, the dielectric constant of each sample increases to
a maximum value (εmax) due to the crossover of phase transition
[2]. The dielectric peak εmax and the corresponding temperature
Tmax are related to the MgO contents. With the increase of the MgO
contents, the peak of εmax increased gradually to 16,803 (x¼ 0.006,
10 kHz), and then decreased, accompanied with peak broadening.
Since oxygen vacancies can reduce the mobility of ferroelectric
domains and pin the ferroelectric domain walls, and thus diminish
the dielectric constant and dielectric losses of ferroelectric ceramics
[10]. The increased amount of oxygen vacancies with Mg doping
into BCTZ resulted in the reduction of the dielectric constant.
Fig. 2. Grain size of Mg-doped BCZT ceramics with different MgO doping
contents. Insets show SEM micrograph.
 J. Miao et al. / Ceramics International ] (]]]]) ]]]–]]]
Moreover, the interspace charges between two neighboring [BO6]
octahedrons may lead to composition inhomogeneity in the BCTZ
ceramics, and consequently helped to broaden the dielectric constant
peaks [6]. From another perspective, the grain size reduction may
also have contribution to the dielectric behavior of Mg-doped
BCTZ ceramics [7,11,12]. Fig. 3b presents the dielectric loss of the
Mg-doped BCTZ as a function of measuring temperature. Except
for the dielectric loss peak appearing at high temperature range
(200–500 1C), a small loss peak at low temperature range
( 25 50 1C) can also be observed. All the dielectric loss peaks
move monotonically to low temperatures with increasing Mg
contents. But, the peak of dielectric loss became inconspicuous at
the range of xZ0.01 in the low temperature range. In the higher
temperature range of 200–500 1C, high dielectric loss peak may be
induced by the polarization of free space charge associated with a
thermally activated relaxation process [13].
Fig. 4 shows the MgO content dependence of Tmax (the
temperature of peak dielectric constant) and Tc (Curie temperature),
which was obtained from fitting the curve of 104/ε-Temp. The
curve could be divided into two regains based on MgO doping
contents as shown in Fig. 4. Tc decreased with the increasing
content of MgO. But in regain II, the slope of the curve became
Fig. 3. Temperature dependence of dielectric constant and dielectric loss for xMg–BCTZ
ceramics measured at the frequency of 10 kHz.
Please cite this article as: J. Miao, et al., Investigation on the dielectric properties of Mg-doped (Ba0.95Ca0.05)(Ti0.85Zr0.15)O3 ceramics, Ceramics International
(2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.302
3
smaller as compared with that in regain I, and reached to zero at
xZ0.016. Tmax decreased with the increasing of MgO contents
monotonously in regain I. It then increased slightly in regain II and
kept roughly stable from 19.6 1C at x¼ 0.014 to 12.1 1C at x¼ 0.02
approximately. The change of Tmax can be attributed to the
distortion of macro domains and the grain size variation caused
by different Mg-doping contents [11,14]. The grain size decreased
to a few microns at x=0.008, and then kept unchanged in the range
of xZ0.01. While the change of Tc might attribute to the distortion
of macro-domain and oxygen vacancies introduced by Mg-doping
as acceptor [12].
The effects of MgO doping on the dielectric properties are
also presented in Fig. 5, which demonstrate the diffuseness of
phase transition with different MgO contents. The dielectric
permittivity of a normal ferroelectric follows the Curie–Weiss
law above the Curie temperature. A modified Curie–Weiss law
[15] has been proposed to describe the diffuseness of a phase
transition, as described by
1=εr  1=εmax ¼ ðT  T max Þγ =C ð1Þ
where γ and C are constants. The parameter γ gives information
on the character of the phase transition. For γ¼ 1, a normal
Curie–Weiss law is obtained; γ¼ 2 describes a completely
diffuse phase transition. The γ values were obtained from the
plot of ln(1/εr  1/εmax) versus ln(T Tmax), observed at 10 kHz,
as shown in Fig. 5. The curve could also be divided into two
regains as Fig. 4. The γ value increases from 1.77 to 1.95 with
the increasing of MgO contents in regain I (xr0.01). This result
demonstrated that the diffuseness of the phase transition in this
range was enhanced. The regain II corresponds to the range of
0.010oxr0.016. The γ value decreased from 1.94 to 1.85 with
rising of MgO contents, which means the diffuseness of phase
transition was weakened. The increase of γ value in regain I
should be caused by the increasing of oxygen vacancies [16]. At
a high MgO doping concentration, the oxygen vacancies could
be increased enough to form oxygen vacancy cluster rotated
around Mg″Ti so that the short range motion of oxygen vacancies,
which was related to the dielectric relaxation, was reduced. The
following impedance analysis provides a further proof of this
Fig. 4. MgO contents dependence of Tmax and Tc.
4 J. Miao et al. / Ceramics International ] (]]]]) ]]]–]]]

Fig. 5. MgO contents dependence of exponent γ.

mechanism. While in the range of 0.018rxr0.020, γ keeps

invariant at about 1.89. This indicates that phase transition
diffuseness is stabilized at xZ0.018, which might be explained
by the solubility limit of Mg2 þ in the BCZT ceramics, although
no conspicuous second phase was found from the XRD patterns.

3.3. Impedance study

Fig. 6 shows the complex impedance spectra and normalized

Z″ peaks as a function of frequency measured at 350 1C and
450 1C with different MgO contents. The inset in Fig. 6a
shows the equivalent circuit. Two groups of RC components
are the simplest equivalent circuits. A compacted semi-circle
can be described by replacing the capacitance element (C) with
a constant phase angle element (CPE) for the relaxation
corresponding to grain boundary deviating from the Debye
model [17]. Fig. 6a and b shows that there are two semicircles
at different test temperatures. The large semicircle at lower
frequency range corresponds to the behavior of ceramic grain
boundary. The small semicircles at high frequency reflect the
properties of inner grain. Intercept of each semicircle with Z0
indicates the resistance of each element. From the size of
semicircle, it can be roughly deduced that the resistance of the
ceramics decreased with rising temperature. Fig. 6c shows that
two kinds of electrical elements clearly exit in the samples. In
the low MgO content range, the peak in the high frequency
range decreased, which was an indication of the accumulation
of free charges in the grains [18]. The distributions of Mg2 þ
and oxygen vacancies formed by the Mg2 þ substitution of
Ti4 þ might segregate in the grain and gathered as clusters Fig. 6. The complex impedance spectra and normalized Z″ peaks as a function
of frequency measured at 350 1C and 450 1C for the specimens with different
centered on Mg″Ti with different Mg2 þ concentrations [10]. MgO contents. Inset in (a) shows the equivalent circuit.
Therefore, the free charges may gather to balance the inner
electrical field in ceramic grains. The conductance activation
energy Ea shown in Fig. 7 provides another support of this
conclusion.
The relationship between activation energy Ea and DC where σ ¼ 1/R, kB is Boltzmann constant (J/K), σ 0 is intrinsic
conductivity σ (s cm  1) can be expressed using Arrhenius law: factor (s cm  1), Ea is conductance activation energy (J). The

Ea was obtained by fitting ln R  (1000/T), as shown in the
σ ¼ σ 0̇ EXP  Ea =kB T ð2Þ inset of Fig. 7. Rg and Rgb were obtained by fitting impedance

Please cite this article as: J. Miao, et al., Investigation on the dielectric properties of Mg-doped (Ba0.95Ca0.05)(Ti0.85Zr0.15)O3 ceramics, Ceramics International
(2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.302
 J. Miao et al. / Ceramics International ] (]]]]) ]]]–]]]
Fig. 7. MgO contents dependence of Ea.
data. The results show that Ea-g 4 Ea-gb with all MgO contents.
Ea-gb varies from 0.79 eV to 0.89 eV for xr 0.016 and keeps
stable at higher MgO contents. However, Ea-g increases and
then decreases until x ¼ 0.01 at low MgO contents. But it
increases from 0.87 eV to 1.03 eV monotonously at high MgO
contents. This corresponds to the activation energy of conduc-
tion caused by oxygen vacancies, which is around 1 eV [7].
The acceptor Mg-doped BCZT generated lots of oxygen
vacancies, which is the main reason for the Ea-g and Ea-gb
variations in all the samples [10]. The increased oxygen
vacancies induced by Mg″Ti were long range motion at low
MgO contents. Consequently, Ea-g got minimum value at
x ¼ 0.01. For x Z 0.012, the oxygen vacancies formed clusters
rotate around the Mg″Ti and became shot range motion, which
reduced the diffuseness of the Mg-doped BCZT. For
x Z 0.018, Mg might reached solubility limit in the ceramics
and Ea-g increased slightly with the increase of MgO contents.
Therefore, more free charges exit in the grain boundary giving
rising to the interfacial dipoles [13]. This might explain the
dielectric behavior at higher MgO contents with εmax increas-
ing slightly at xZ 0.018.
4. Conclusions
Mg2 þ ions mainly occupied B-site of perovskite structure
and substituted for Ti4 þ in all the doping concentrations. The
grain size was reduced and Tc shifted to low temperature with
the increasing of MgO contents. The Mg–BCZT ceramics
undergo a diffuse type ferroelectric phase transition with a
maximum diffuseness. All these dielectric behaviors were
mainly ascribed to the oxygen vacancies in the grains, which
underwent long-range motion at low Mg concentrations, and
pinned by Mg″Ti and formed oxygen vacancy cluster at high
Mg concentrations.
Conflict of interest
The authors declare no competing financial interest.
Please cite this article as: J. Miao, et al., Investigation on the dielectric properties of Mg-doped (Ba0.95Ca0.05)(Ti0.85Zr0.15)O3 ceramics, Ceramics International
(2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.302
5
Acknowledgment
This work is supported by the National Natural Science
Foundation of China (Grant no. 51172257), National Basic
Research Program of China 973-Projects (2015CB654604 and
2015CB654605), and the CAS-SAFEA International Partner-
ship Program for Creative Research Teams.
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