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Ceramics International ] (]]]]) ]]]–]]]
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Fabrication of high-performance Ba0.95Ca0.05Ti0.85Zr0.15O3 ceramics

by aqueous chemical coating method
Zhengbo Shen, Xiaohui Wangn, Huiling Gong, Longwen Wu, Longtu Li
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

Received 26 October 2014; accepted 14 March 2015

Abstract

Al2O3-coated Ba0.95Ca0.05Ti0.85Zr0.15O3 dielectric ceramics with excellent performance were fabricated by a novel aqueous chemical coating
method. With this method, Al2O3 was well coated on the surface of Ba0.95Ca0.05Ti0.85Zr0.15O3 powders, resulting in homogenous microstructure,
excellent dielectric and electrical properties. The specimen with an appropriate coating amount of 0.4 wt% Al2O3 exhibited the most outstanding
properties. The dielectric constant at room temperature could reach
13,600, with low dielectric loss (
0.5%) and high insulation resistivity
(
6.2  1011 Ω  cm). DC breakdown strength was also improved to
12.5 kV/mm because of Al2O3 coating.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Dielectric properties; Aqueous chemical coating; Breakdown strength; Resistance degradation

1. Introduction increasingly deteriorating energy crisis. In general, energy density

Barium titanate (BaTiO3) is a well-known ferroelectric perovs-
kite material. Due to their high dielectric constant, low dielectric
loss and excellent electrical properties, BaTiO3-based ceramics are
universally used for multilayer ceramic capacitors (MLCCs) [1–3].
The excellent dielectric and electrical properties of (Ba1 xCax)
(Ti1 yZry)O3 ceramics fabricated by the substitution of the divalent
Ca2 þ at A sites and the isovalent Zr4 þ at B sites, have aroused
many researchers' interests [4–11]. As well known, the properties
of BaTiO3-based ceramics can be tailored to a large extent by
different dopants [12–16]. According to the Electronic Industries
Association (EIA) standards, the Y5V specification requires that
the capacitance must be within  82% or þ 22% of the value at
25 1C in the temperature range from  30 1C to 85 1C [17]. In our
previous study, we developed Y, Mn-codoped Ba0.95Ca0.05-
Ti0.85Zr0.15O3 (BCTZ) system, which satisfied Y5V specifications
[18]. Furthermore, the BCTZ ceramics possess high permittivity
(over 10,000).
Recently, more and more interests have been attracted to
improving the energy storage density of MLCCs, because of the
n
Corresponding author.
E-mail address: wxh@mail.tsinghua.edu.cn (X. Wang).
is proportional to the dielectric constant and the square of the
dielectric breakdown strength. Therefore, it is important for a
candidate material to achieve a compromised state where relative
high permittivity and high breakdown strength coexist concur-
rently. Due to the compact structure, which can block the motion
of charge carriers, Al2O3 is an effective additive to improve DC
breakdown strength [19,20]. Hence, if Al2O3 is added into the
BCTZ powder, the compromised state may come true.
Although the conventional solid-state method is convenient and
low-cost, it is very difficult to achieve a uniform distribution of the
additives. However, the distribution of additives becomes critical
since the additives are coarse and of very small amount.
Consequently, various chemical techniques have been proposed
to maximize the homogeneous distribution of additives, such as
sol–gel, heterocoagulation and homogeneous precipitation coating
[21–25]. Aqueous chemical coating method is considered to be a
promising solution because of low-cost, good coating uniformity
and smoothness, facilitating the formation of core–shell structure.
In this study, high performance Al2O3-coated BCTZ ceramics
meeting Y5V specifications were fabricated by the aqueous
chemical coating method. The influence of Al2O3 coating on the
microstructure, dielectric and electrical properties were investi-
gated systematically.

http://dx.doi.org/10.1016/j.ceramint.2015.03.264
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Z. Shen, et al., Fabrication of high-performance Ba0.95Ca0.05Ti0.85Zr0.15O3 ceramics by aqueous chemical coating method, Ceramics
International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.264
2 Z. Shen et al. / Ceramics International ] (]]]]) ]]]–]]]
2. Experimental procedure
2.1. Preparation of Y, Mn-codoped Ba0.95Ca0.05Ti0.85Zr0.15O3
powders by conventional solid-state reaction method
The dopant amount of Y2O3 and MnO2 of the BCTZ powder
is 1.0, 0.2 wt%, respectively. BaCO3 (Electronic Grade, Kaimao
Wuxi), CaCO3 (Photoelectronic Grade, Chuangshiji Dongying),
TiO2 (Electronic Grade, Zhongxing Electronic Xiantao), ZrO2
(Electronic Grade, Shengquan Zibo), Y2O3 (99.99%, Rare-
chem. Hi-Tech. Co., Ltd) and MnO2 (Analytical Reagent,
Sinopharm Chemical Reagent Co., Ltd) were used as the
starting materials. The raw materials were weighed according
to their stoichiometric ratios and then ball milled in deionised
water using zirconia balls for 24 h. Then, the mixed powder was
dried and calcined at 1150 1C for 2 h. The average grain size of
the BCTZ calcined powder was approximately 560 nm as
shown in Fig. 3(a).
2.2. Al2O3 coating on BCTZ powders using aqueous coating
method
Al(NO3)3  9H2O (Analytical Reagent, Sinopharm Chemical
Reagent Co., Ltd) was used as the precursor of Al2O3, and was
dissolved to make 0.08 mol/L aqueous solution. The BCTZ
powders were ball milled in deionised water for 8 h to obtain the
well dispersed suspending slurry. Then, the pH value of the
slurry was adjusted to below 3.5 with acetic acid. After that, the
Al3 þ -containing solution was then added into the suspending
slurry. The nominal amount of Al2O3 addition was 0.0, 0.2, 0.4,
0.6, 0.8 wt% respectively. Then, ammonia solution was added
dropwise to adjust the pH value of the mixed slurry, which
caused co-precipitation. The pH rose up gradually until pH¼ 4.5
to ensure the sufficient precipitation of Al3 þ . When the co-
precipitation process ceased, the doping elements were coated
on the surface of BCTZ particles in the forms of aluminum
hydroxides. After drying the slurry and calcining the powders at
600 1C for 3 h, Al2O3 coated BCTZ powders were obtained.
The Al2O3-coated powders were granulated with PVA
binder and pressed into disks (10 mm in diameter and 1 mm
in thickness), followed by sintering in air at 1300 1C for 2 h.
2.3. Characterization
The morphology of the chemical coating powders was
characterized by a field-emission transmission electron micro-
scopy (FE-TEM, HT-7700, Hitachi Ltd., Tokyo, Japan) with
operating voltage of 100 kV, and energy-dispersive spectro-
scopy (EDS) microanalysis was performed as well. The micro-
structures of the ceramics were observed using a scanning
electron microscope (SEM, Leo-1530, Oberkochen, Germany)
with an accelerating voltage of 10 kV. The phase structures of
ceramics were detected using an X-ray diffraction meter (XRD,
D8 Advance, Bruker Inc., Germany, λ¼ 1.54178 Å) with a Cu
Kα radiation in the 2θ range from 101 to 901 with a scanning
speed of 61/min in the normal routine.
Please cite this article as: Z. Shen, et al., Fabrication of high-performance Ba0.95Ca0.05Ti0.85Zr0.15O3 ceramics by aqueous chemical coating method, Ceramics
International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.264
The dielectric properties of the samples were measured from
 60 1C to 150 1C (heating rate 2 1C/min) using an impedance
analyzer LCR (Model HP4192A, Hewlett-Packard Company,
Santa Clara, California, USA) with an automatic temperature
controller at a frequency of 1 kHz and oscillation level of
1 Vrms. The electrical properties of ceramic disks were char-
acterized by a picoampire meter (Model HP4140B, Hewlett-
Packard Company, Santa Clara, California, USA) and an auto
breakdown tester (YD2013, Changzhou Electronic Co., Ltd,
Changzhou, China). Silver electrodes were coated on both sides
of the specimens before electrical measurements.
3. Results and discussion
It can be seen that the BCTZ particles are well coated by Al2O3
layers with high coverage in Fig. 1. The well dispersion and high
coverage of BCTZ powders by this coating method may be
attributed to the gradual change of pH value of slurry. In the
present study, the pH value rose up slowly, which allowed Al3 þ
precipitating more effectively in the co-precipitation process and
made the additives uniformly coating on the BCTZ particles. The
HRTEM image, Fig. 1(b), shows a part of a randomly selected
BCTZ particle on the micro-grid. It was found that the coating
layer was non crystalline before calcination, while the BCTZ
particles were crystallized very well, then the crystal lattices of the
BCTZ matrix were visible. From the EDS analysis, in which the
electron beam spot focused on the edge of the particle, except for
the elements for the BCTZ compound, the coating element Al was
detected as well, as shown in Fig. 1(c). It is confirmed that the Al
coating layer has been successfully obtained. Cu was also detected
because copper screen was used to support the sample powder.
The XRD patterns of the Al2O3-coated BCTZ ceramics with
different coating contents are shown in Fig. 2. The results indicate
all samples exhibited a pseudo-cubic perovskite structure. When
the coating content increased to 0.6 wt%, small amount of Al-rich
secondary phase was found, such as BaAl2O4. The microstruc-
tures of the Al2O3-coated BCTZ ceramics with different coating
Fig. 1. (a) TEM micrograph of the coated BCTZ powders with 0.4 wt% Al2O3
before calcination; (b) high-resolution TEM (HRTEM) image of BCTZ particle
with Al2O3 coating layer before calcination; (c) EDS analysis of the coating layer.
 Z. Shen et al. / Ceramics International ] (]]]]) ]]]–]]] 3

content are shown in Fig. 3. The samples coated with 0.2 wt% and
0.4 wt% Al2O3 presented regular morphology and uniform grain.
However, it can be observed that abnormal growth appeared and
Fig. 2. XRD patterns of the Al2O3-coated BCTZ ceramics with different
coating contents.
the density also became worse when the coating content increased
to 0.6 wt% as shown in Fig. 3(e), and (f). Furthermore, small
quantity of rodlike phase marked with red circle was found in
Fig. 3(e), and (f). This result is consistent with the XRD analysis.
The inhomogeneous microstructure may be relative with the
appearance of secondary phase.
The temperature dependence of dielectric constant, loss tangent
and TCC curves for aqueous chemical coated BCTZ ceramics with
different Al2O3 contents are shown in Fig. 4. It is clear that the
permittivity was enhanced drastically because of Al2O3 coating.
With increasing the coating content, dielectric constant increased
firstly and then dropped down. The systematic variation of
permittivity is relative to the microstructure as shown in Fig. 3.
All samples can almost satisfy EIA Y5V standards. Dielectric
properties at room temperature of the samples are shown in Table 1.
The dielectric constant at room temperature increased by about
3000 because of Al2O3 coating, and the electrical resistivity of the
coated samples was nearly twice larger than that of the uncoated
ones. The best dielectric properties is obtained for the 0.4 wt%
Al2O3-coated samples, with a dielectric constant of
13,600, tan δ

Fig. 3. The microstructures of the (a) BCTZ powders before coating and Al2O3-coated BCTZ ceramics with different coating contents: (b) Al2O3 ¼ 0.0 wt%;
(c) Al2O3 ¼0.2 wt%; (d) Al2O3 ¼0.4 wt%; (e) Al2O3 ¼ 0.6 wt%; (f) Al2O3 ¼ 0.8 wt%.

Fig. 4. Dielectric properties of Al2O3-coated BCTZ ceramics with different Al2O3 contents: (a) dielectric constant and loss tangent versus temperature;
(b) temperature coefficient of capacitance (TCC) versus temperature. The dashed box in (b) shows the EIA Y5V specifications window.

Please cite this article as: Z. Shen, et al., Fabrication of high-performance Ba0.95Ca0.05Ti0.85Zr0.15O3 ceramics by aqueous chemical coating method, Ceramics
International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.264
4 Z. Shen et al. / Ceramics International ] (]]]]) ]]]–]]]

Table 1 more Al2O3 show more defects, such as pores, where the samples
Dielectric and electrical properties for the samples at room temperature at the are easily breakdown, resulting in a lower value of breakdown
frequency of 1 kHz.
strength. But anyway, the breakdown strength of the chemical
Content of Al2O3 (wt%) εr tanδ (%) Resistivity (1011 Ω  cm) coating specimens with various amounts of Al2O3 is larger to
different degrees than that of uncoated ones due to the existence of
0.0 10,672 0.74 3.39 Al2O3 coating layer.
0.2 13,416 0.56 5.32
Fig. 6 shows the insulation resistivity versus time of the
0.4 13,613 0.53 6.17
0.6 12,477 0.69 5.82 Al2O3-coated BCTZ ceramics at high temperature of 185 1C
0.8 11,828 0.64 5.61 under a DC electrical field of 1 kV/mm. The insulation
resistivity of the uncoated specimens displayed a large
fluctuation versus time, whereas the Al2O3-coated samples
took on a smooth and steady variation. The stability of
insulation resistivity was improved greatly because of coating,
and Al2O3-coated samples could maintain a high level for even
several days. The samples coated with 0.4 wt% Al2O3 have
homogenous microstructure as shown in Fig. 3(d), and this
would result in an increase in the proportion of grain
boundaries, which have a double Schottky barrier with higher
potential energy and greater width to restrict the transport of
the defects across each boundary [26]. In addition, the well-
coated chemical layer can also block the motion of charge
carriers [20]. Consequently, the resistance degradation is
effectively inhibited. Although the insulation resistivity of
samples with higher concentration of Al2O3 declined, the trend
Fig. 5. DC breakdown strength of Al2O3-coated BCTZ ceramics with different
in the course of time was still placid.
contents.

4. Conclusions

In summary, a novel, low-cost and convenient aqueous

Fig. 6. Insulation resistivity of Al2O3-coated BCTZ ceramics with different
Al2O3 contents versus time at high temperature of 185 1C under a DC bias of
1 kV/mm.
chemical coating method for preparation of BaTiO3-based
MLCC powders has been successfully developed. Well Al2O3-
coated BCTZ particles with a high coverage were obtained.
Although electrical and dielectric properties can be improved
because of Al2O3 coating, the coating content should be
controlled in a certain scale. The 0.4 wt% Al2O3-coated
ceramics showed excellent properties: high dielectric constant
(
13,600), low dielectric loss (
0.5%), high insulation
resistivity (
6.2  1011 Ω  cm), improved breakdown strength
(
12.5 kV/mm) and better insulation degradation behavior,
which is a very promising for material with higher perfor-
mance and lower cost in MLCC applications.
Conflict of interest

of 0.53%, and electrical resistivity of 6.17  1011 Ω  cm at room
temperature at the frequency of 1 kHz.
In order to improve the energy storage density, ceramic
capacitors must withstand higher voltage. Hence, it is essential
to carry out DC breakdown strength test, and the results are shown
in Fig. 5. The results suggest that DC breakdown strength can be
improved to about 12.5 kV/mm from 9.3 kV/mm by aqueous
chemical coating Al2O3. The samples with lower content of Al2O3
possessed higher breakdown strength than that with higher
concentration of Al2O3. This is because that the samples with
lower content of Al2O3 had a homogenous microstructure, which
can block the motion of charge carriers [20], and then enhanced
the breakdown strength in turn. However, the samples coated by
We declare that we do not have any commercial or associative
interest that represents a conflict of interest in connection with the
work submitted.
Acknowledgments
The work was supported by Ministry of Sciences and
Technology of China through National Basic Research Pro-
gram of China (973 Program 2015CB654604), National
Natural Science Foundation of China for Creative Research
Groups (Grant no. 51221291), National Natural Science
Foundation of China (Grant no. 51272123), and also supported
by CBMI Construction Co., Ltd.

Please cite this article as: Z. Shen, et al., Fabrication of high-performance Ba0.95Ca0.05Ti0.85Zr0.15O3 ceramics by aqueous chemical coating method, Ceramics
International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.03.264
 Z. Shen et al. / Ceramics International ] (]]]]) ]]]–]]]
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