Journal of Alloys and Compounds 762 (2018) 950e956

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Effects of sintering temperature on microstructure and dielectric

properties of Sr0.985Ce0.01TiO3 ceramics
Junlei Qi a, Minghe Cao a, *, Yiying Chen a, Ying Fang a, Wengao Pan a, Hua Hao a,
Zhonghua Yao a, Zhiyong Yu a, Hanxing Liu b
a
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, PR China
b
International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The effects of sintering temperature on microstructure and dielectric properties of Ce doped SrTiO3 were
Received 27 February 2018 investigated. The dielectric properties are strongly depend on sintering temperature, the sample sintered
Received in revised form at 1520  C exhibits a colossal permittivity about 7000 at 1 kHz while relative permittivity of the sample
8 May 2018
sintered at 1380  C is 770. Further investigations demonstrate that all the samples belong to Pm3m space
Accepted 12 May 2018
Available online 25 May 2018
group and without secondary phase. The lattice parameter decrease with the increase of sintering
temperature while the mean grain size of SCT (Sr0.985Ce0.01TiO3) ceramics are increased. Higher sintering
temperature helps to improve the dielectric properties which can be attribute to defect clusters (e.g.
Keywords:
Colossal permittivity
oxygen vacancies, Ti3þ/Ti4þ etc.), however the defects are more likely to become carriers in high electric
Dielectric materials field which can increase the conductivity and leakage current. With the increase of sintering tempera-
Sintering temperature ture, the conductivity activation energies, breakdown strength and energy storage density of the samples
Defect clusters are decreased.
Oxygen vacancies © 2018 Elsevier B.V. All rights reserved.
Ti3þ/Ti4þ

1. Introduction
High permittivity dielectric materials have attracted much
attention due to their potential energy storage applications [1].
Strontium titanate (ST) ceramics exhibit good dielectric properties
of high constant (~250) and low dielectric loss (~0.005) at room
temperature and 1 kHz, which have been applied in many fields as
dielectric materials. The perovskite structure of cubic SrTiO3 is
normally defined by cations at corners (A site), body center (B site)
and by the anions occupying face centers (O). The structure of ST is
susceptible to distortion which can be caused by the structure
adaptation of different atomic species [2].
Many methods such as doping has been comprehensively
studied to improve the dielectric permittivity or electric properties
of materials [3e5]. The work on the modification and regulation of
ST ceramics with expectation of obtaining better dielectric prop-
erties or higher energy storage density have attracted a large
number of researchers. Usually, the dielectric permittivity of doped
materials are several times or even higher than that of undoped
* Corresponding author.
E-mail address: caominghe@whut.edu.cn (M. Cao).
based. Many mechanisms have been used to explain this phe-
nomenon, such as boundary barrier layers [6,7], surface-layer effect
[8], nanoscale disorder [9] and variable-range-hopping [10] etc.
In general, the increase of the dielectric permittivity caused by
doping can be attributed to the polarization mechanism formed by
the broken of symmetry of crystal lattice when introducing defects.
The polarization can mainly act on grain boundaries that results in
the difference of conductivities between grain boundaries and
grains, thus forming the interfacial polarization [11]. Taking this
polarization mechanism into consideration, the dielectric permit-
tivity or other electric properties of the materials is directly related
to grain sizes [12]. With increasing grain size, the grain boundary
density was decreased so that the dielectric permittivity was
increased [13]. In addition, high dielectric permittivity also origi-
nate from ionic spontaneous polarization caused by the phase
transition of the material [14,15], however this mechanism is not
suit for paraelectric SrTiO3-based ceramics. Moreover, from the
micro perspective of defects, the polarization can act on the inter-
nal lattice of the crystal thus forming intrinsic point defects (such as
oxygen vacancies) or defects clusters [16].
Sintering conditions such as sintering temperature [12,13],
thermal treatment [17,18] and sintering atmosphere [19e22] can
not only effectively influence the structure, microstructure and

https://doi.org/10.1016/j.jallcom.2018.05.140
0925-8388/© 2018 Elsevier B.V. All rights reserved.
 J. Qi et al. / Journal of Alloys and Compounds 762 (2018) 950e956 951

formation of defects but also can adjust the electric properties of Aglient, USA). P-E hysteresis loops were examined using a ferro-
materials. However, the mechanism for the change of dielectric electric polarization loop and dielectric breakdown test system
properties or electrical properties caused by sintering temperature (PolyK technologies, PK-CPE1701) at room temperature and 10 Hz.
is still unclear. On the one hand, the change of dielectric properties The energy storage density was evaluated by integrating the area
is directly attributed to the interfacial polarization effect [23] or between the polarization axis and the discharge curve.
grain size [24], which does not apply to all phenomena. For
example, the dielectric permittivity did not decrease with the 3. Results and discussion
decrease of average grain size, and the sample with medium grain
size exhibited the highest dielectric permittivity in this study. On 3.1. Phase characterization and microstructure observation
the other hand, to the best of our knowledge, the influence of
sintering temperature on the structural characteristics and defects XRD patterns of SCT ceramics with different sintering temper-
of Ce doped ST ceramics have not been systematically studied. ature are shown in Fig. 1. All samples are consistent with the cubic
Herein, we described our systematic investigations of the effect perovskite structure of undoped ST (space group Pm3m) without
of sintering temperature (from 1380  C to 1580  C) on the structure, secondary phase. Previous literature reports that the solid solubility
microstructure, electric and energy storage properties of Ce-doped limit of Sr1-3x/2CexTiO3 ceramics even exceeded x ¼ 0.4 [25e28]
SrTiO3 ceramics. Detailed investigations of crystal structure and which is 40 times higher than the doping concentration in this
microstructure for SCT were explored with the help of XRD study. Therefore, it is reasonable to believe that all the samples are
refinement, SEM and Raman spectra. Meanwhile, different electric homogeneous. The standard lattice parameters of undoped ST is
properties were obtained at various sintering temperatures for SCT, 3.9034 Å (ICSD-94573). Owing to the fact that radius of Ce3þ ion
making it better to understand the effect of defect mechanism on (1.34 Å) is less than that of Sr2þ (1.44 Å) ion for the coordination
dielectric properties. number of 12 [29], the decrease of lattice parameters can be
explained by the substitution of Sr2þ by Ce3þ ions. It can be seen
2. Experimental procedure from the refinement results (Fig. 2a) that with the increase of sin-
tering temperature the lattice parameters decrease which can be
Sr0.985Ce0.01TiO3 ceramics were prepared by solid-state method. explained that high temperature can contributed to Ce3þ ions
SrCO3 (AR), TiO2 (CP) and CeO2 (99.99%) (Sinopharm Chemical substitute for Sr2þ ions of A site to form homogeneous solid solu-
Reagent Co., Ltd) were used as the initial materials. Stoichiometric tion structure. Ce3þ ions successively enter into the lattice and
amounts of powder mixtures were ball-milled in ethanol medium substitute for Sr2þ with increasing temperature, and the high sin-
using yttria-stabilized zirconia balls in a plastic container for 24 h. tering temperature contributes to the formation of homogeneous
The ball/powders mass ratio is about 20:1. There are 4 kinds of solid solution. In Ce doped SrTiO3 system, the Ce3þ ions dopants
zirconium balls with different sizes (diameter ~2 mm, 5 mm, 8 mm occupying Sr2þ sites and creating A-site vacancy to charge
and 10 mm) and the mass ratio of each size is 1:1:1:1. The rotating compensation, the reaction equation is follow:
speed of ball mill is about 200 r/min. Then the slurry was dried,
ground, sifted (100 mesh) and calcined at 1180  C for 2 h. The
calcination temperature was based on the TG-DSC results and our
experimental experience. Then the calcined powders were ball-
milled again, dried and ground into fined powder and then a so- SEM images of SCT ceramics with various grain sizes obtained at
lution of 3 wt% poly (vinyl alcohol) 1799 (PVA) (alcoholysis different sintering temperature are shown in Fig. 3 and the insert
99.8e100% (mol/mol), Aladdin Industrial Co.) was added dropwise figures are the distribution of grain sizes. It can be seen that all the
to the dried powders. Cylindrical pellets with a height of 1e2 mm samples show uniform and compact morphologies and the distri-
and a diameter of 12 mm were made applying a pressure of bution of grain sizes conforms to the normal distribution. The grain
120Mpa. These compacts were heated at 600  C for 2 h in the air to size strongly depends on sintering temperature. With sintering
burn the binder out before sintering. Pellet of different samples
were sintered in the air at 1380e1580  C for 3 h.
The crystalline structure of each samples was performed by an
X-ray diffractometer (X'Pert PRO, PANalytical, Holland) and using
Cu Ka radiation. The XRD pattern was measured from 10 to 90 2q
degree and 0.02 per step. The Rietveld refinement results were
calculated by Maud software. The microstructure and morphology
of each samples were measured by SEM (JEOL JSM-6700F). Raman
spectra were recorded at room temperature in the range of
100e1200 cm1 by confocal micro-Raman spectrometer (INVIA
Renishaw) with internal Ar ion laser source of excitation wave-
length 633 nm and each sample was scanned 10 times. Average
grain size and distribution were statistically calculated by Digital
Micrograph software, that is, all grains in the vision field of 500
times magnification except the sample sintered at 1580  C is 200
times magnification (about 100e200 measured grains) were
counted. The size of each grain is determined by the average value
of the horizontal and vertical lines through the center of grains.
For the measurements of temperature and frequency de-
pendences of the permittivity, ceramic samples were polished to a
thickness of ~0.6 mm and coated with fire-on silver electrodes for
measurement. The dielectric properties and complex impedance Fig. 1. XRD patterns of Sr0.985Ce0.01TiO3 ceramics sintered at different temperature for
3 h.
spectra were measured by a precious LCR meter (Agilent 4980A,
952 J. Qi et al. / Journal of Alloys and Compounds 762 (2018) 950e956
Fig. 2. Lattice parameters (a) and average grain size (b) of Sr0.985Ce0.01TiO3 ceramics
sintered at different temperature for 3 h.
temperature from 1380  C to 1580  C, the average grain size in-
crease from 12.11 mm to 41.76 mm. However, at intermediate tem-
perature (from 1460  C to 1520  C), no obvious changes in average
grain size (from 20.15 mm to 26.30 mm) are observed. It can be seen
that the growth of grain size increase nonlinearly with the sintering
temperature. The corresponding temperature at different growth
stage is also different. The growth of grain at low temperature stage
is a slow process with the main behavior of concentrating Ce ions
into the lattice and substituting for Sr ions, and the lattice param-
eter decrease gradually. The high temperature stage at 1580  C
corresponds to the abnormal growth of individual grains and fusion
of small grains. At this stage, the difference of grain size increases
obviously.
Fig. 3. SEM images of the fractured cross section for Sr0.985Ce0.01TiO3 ceramic samples sintered at 1380  C (a) 1460  C (b) 1520  C (c) 1580  C (d) for 3 h. Insert images are the grain
size distribution of each samples.
Fig. 4. Room temperature Raman spectra of Sr0.985Ce0.01TiO3 ceramics sintered at
1380  C, 1460  C, 1520  C, 1580  C. Insert is the enlarged scale of LO4 mode (~790 cm1)
of Raman spectra.
3.2. Raman spectra analysis
Fig. 4 presents the Raman spectra of Sr0.985Ce0.01TiO3 ceramics
for sintered at 1380  C, 1460  C, 1520  C, 1580  C. The Raman
spectra of all the samples show similar vibrational characteristics,
indicating that all the samples belong to the same crystal space
group (Pm3m). 1%mol Ce doped content is not enough to change the
crystal structure so that the Raman spectra of the samples are
similar to those of undoped strontium titanate [30,31]. In the cubic
phase neither Flu nor F2u modes are Raman active, and no first-
order Raman lines are expected at room temperature. In second
order Raman process, two phonons are available for originate
 J. Qi et al. / Journal of Alloys and Compounds 762 (2018) 950e956
anywhere in the Brillouin zone so that the second order Raman
spectra tend to be continuous [32]. As indicated 2nd in Fig. 4, two
broad scattering bands appeared in the region of 240e400 cm1
and 600 to 820 cm1 which is consistent with the behavior of the
classical cubic second-order Raman mode. Moreover, the broad
feature located around 543 cm1 and 790 cm1 can be assigned to
TO4 and LO4 modes. Because of the macroscopic electric-field ef-
fect associated with the polar LO modes, LO vibrational modes are
found at a higher energy than TO modes derived from the same Flu
species. The LO4 mode soften with presence of such defects in high
sintering temperature which shows a strong electrostatic interac-
tion between the polar defects and the longitudinal polar phonon
branch linked to TieO stretching mode [33]. With the increase of
sintering temperature, defects (such as oxygen vacancy, Ti3þ/Ti4þ
etc.) produced at high temperature break the local symmetry of
TieO octahedral and increase disorder of the system, leading to the
broaden of modes. It is worth noting that, the TO4 mode shows a
blue shift toward the 794 cm1 in the sample of sintered at 1520  C,
underlying that the TieO octahedral distortion and disorder in
system increased due to higher Ti3þ content.
3.3. Temperature dependence of the dielectric properties
The temperature dependence of dielectric properties for SCT
ceramics sintered at various temperature is shown in Fig. 5. It can
be seen that there is a significant difference of permittivity when
the sintering temperature rise from 1380  C to 1580  C, exhibiting
permittivity of 776, 1120, 7000 and 6580 measured at room tem-
perature and 1 kHz, respectively. Contrasting to the difference of
the grain size of the samples with different sintering temperature,
permittivity of the samples with sintering temperature from
1460  C to 1520  C significant increased about 6 times and reached
the maximum value. With the sintering temperature further in-
crease, the permittivity decrease slightly. That is to say, it can be
excluded that the increase of permittivity can be only attributed to
the interfacial polarization effect caused by the electrical difference
between grain boundaries and grains, and it is more likely that the
high permittivity is due to the change of defect concentration (such
as , Ti3þ and etc.) during high temperature sin-
tering process. The chemical equations are shown as follow:
Fig. 5. Temperature dependence of permittivity (a) and loss tand (b) measured at 1 kHz frequency for Sr0.985Ce0.01TiO3 ceramics sintered at 1380  C (squares),1460  C(circles),
1520  C(up-triangles), 1580  C(down-triangles) sintering temperature. Insert is the enlarged scale of low temperature area of dielectric loss.
953
All the samples can maintain low dielectric loss (mostly<0.03)
at a wide temperature range from room temperature to 200  C.
However, with increasing sintering temperature, the thermal sta-
bility of dielectric loss decrease. The activation energies of the
dielectric loss relaxation peaks were calculated by Arrhenius law:
fr ¼ f 0 eðEa =kTÞ
Where f 0 is relaxation frequency at an infinite temperature, Ea is
dielectric loss relaxation activation energy, k is the Boltzmann
constant and T is absolute temperature (K). According to the
calculation of the activation energy of the dielectric loss relaxation
peak corresponding to about 110  C (as shown in insert of Fig. 5b),
Ea ¼ 0.75, 0.72, 0.76, 0.75eV for Sr0.985Ce0.01TiO3 sintered at 1380  C,
1460  C, 1520  C and 1580  C respectively. It has been proved that
the dielectric loss relaxation activation energy ~0.74eV is related to
the motion of and associate defects [11].
3.4. Frequency dependence of the dielectric properties
Fig. 6 shows the frequency dependence of permittivity and loss
for Sr0.985Ce0.01TiO3 ceramics measured from 100 to 500  C. It can
be seen from that all the samples have a similar dielectric response
with frequency. However, great difference of permittivity of each
samples, especially at high temperature and low frequency, is
obvious. For instance, the permittivity measured at 500  C and
20 Hz frequency of the samples sintered at 1380  C, 1460  C,
1520  C, 1580  C is 4330, 11000, 94800, 65100, respectively. Various
defects begin to form in the 1460  Ce1520  C stage, including ox-
ygen vacancies, Ti3þ ions. Therefore, there is a great difference in
dielectric properties but no obvious changes in the microstructure
and lattice parameter can be observed in the stage. Further in-
creases the sintering temperature to 1580  C, the grain size
increased significantly, while the corresponding dielectric proper-
ties decrease.
Moreover, each group of samples also has a good frequency
stability with variation less than ±35% of permittivity under 340  C.
The variation tendency of dielectric loss with frequency of each
samples is similar. As it is shown above, the samples sintered at
1520  C have more Ti3þ defects and it can form a more stable defect
dipoles which can depressed the dielectric relaxa-
tion peaks. In general, the samples sintered at 1520  C have smaller
and stable dielectric loss with frequency characteristics.
3.5. AC impedance characteristics and defect carriers mechanism
analysis
Impedance spectroscopy was used to analyze the electrical
954 J. Qi et al. / Journal of Alloys and Compounds 762 (2018) 950e956

Fig. 6. Frequency dependence of permittivity (a~d) and loss tand (e~h) measured at given temperature for Sr0.985Ce0.01TiO3 ceramics sintered at 1380  C,1460  C, 1520  C, 1580  C.

microstructure of SCT ceramics at the measured temperature of
420  C and in the frequency range of 20e2 MHz. As shown in
Fig. 7a, only one semicircular plot with different sintering tem-
perature was observed in the impedance spectroscopy, indicating
that the insulation property of grain and grain boundary cannot be
distinctly distinguished from the AC impedance spectroscopy.
Ideally, the center of semicircle should be located on the abscissa of
impedance and the semicircular arcs in the AC impedance spec-
trum can be simulated by a parallel R-C equivalent circuit. However
due to the inhomogeneous surface of electrode, the response time
of double layer on the electrode surface to u are different, causing
the dispersion effect of the double layer capacitance. Therefore, CPE
(constant phase element) is introduced in the ideal R-C equivalent
circuit to modify the fitting results [34]. The CPE is defined by two
values, CPE-T and CPE-P. If CPE-P equals 1 then the equation is
identical to that of a capacitor. If CPE-P equals 0.5, a 45 line is
produced on the Complex-Plane graph. When a CPE is placed in
parallel to a resistor, a Cole-Element (depressed semicircle) is
 J. Qi et al. / Journal of Alloys and Compounds 762 (2018) 950e956 955

Fig. 7. (a) Complex impedance plots [Z0 (u)-Z’’(u)] of Sr0.985Ce0.01TiO3 ceramics at different sintering temperature. Insert is the equivalent circuit for SCT ceramics. (b) Arrhenius plots
of the conductivities of lns versus 1000/T functions of Sr0.985Ce0.01TiO3 ceramics. The activation energy Ea for each circuit element is calculated from the slopes of the plots. 1380  C
(squares),1460  C(circles), 1520  C(up-triangles), 1580  C(down-triangles) measured at 420  C.

produced [35,36]. The equivalent circuit is shown in insert of Fig. 7a dielectric properties. However, the defects are more likely to
and the fitting results are shown in Table 1. With the increase of become carriers in high electric field, deteriorating breakdown
sintering temperature, the resistance reduced. We use the same strength and energy storage density.
fitting method to calculate the resistance value at 260e420  C,
converting it into electrical conductivity (s ¼ R1). The activation
4. Conclusions
energies of the conductivity were calculated by Arrhenius law:
Structural and dielectric properties of Sr0.985Ce0.01TiO3 (SCT)
s ¼ s0 eðEa =kTÞ
ceramics prepared at various sintering temperatures from 1380  C
Where s0 is a constant related to temperature, Ea is conductivity to 1580  C via conventional solid state method have been investi-
activation energy, k is the Boltzmann constant and T is absolute gated in this work. The XRD results show that all the samples were
temperature (K). The temperature dependence of the conductivity not detected secondary phase. With the increase of sintering
activation energy is shown in Fig. 6b. It can be seen that with the temperature, the lattice parameters decrease gradually and the
increase of sintering temperature the conductivity activation en- average grain size increase from 12.11 to 41.76 mm. Dielectric
ergy was reduced. The material will possess a high permittivity spectroscopy analysis of the samples sintered at various tempera-
with the increase of defect concentration and the conductivity of tures have shown a remarkable dielectric permittivity difference
the material will also be enhanced with increasing defect concen- (from 770 to 7000 measure at room temperature and 1 kHz). The
tration. In other words, concentration and types of defects (such as
oxygen vacancy, Ti3þ etc.) in samples can be increased under high
sintering temperature. On the one hand, these defects contribute to
the increase of polarization. On the other hand, the defects will
become carriers at high temperature, thereby increasing the elec-
trical conductivity of materials.

3.6. PE loops and energy storage properties

The PE loops for Sr0.985Ce0.01TiO3 ceramic samples sintered at

various temperature are shown in Fig. 8. All the samples exhibit
linear dielectric features. The Pmax at 1 kV/mm of Sr0.985Ce0.01TiO3
sintered at 1380  C, 1460  C, 1520  C and 1580  C are 0.3, 0.8, 2.5,
2.2 mC/cm2, respectively. Although the samples sintered at high
temperature showed higher polarization, the leakage current also
increased. The energy storage density and efficiency of
Sr0.985Ce0.01TiO3 ceramics sintered at various temperature are
shown in Table 2. The sample sintered at 1380  C exhibits the
highest effective energy density of 0.92 J/cm3 and a maximum ef-
ficiency of 90.2%. The higher sintering temperature increases the Fig. 8. Hysteresis loops of Sr0.985Ce0.01TiO3 ceramics sintered at various temperature at
polarization caused by defects and therefore improves the 1 kV/mm electric field.

Table 1
Electrical parameters at 420  C of SCT ceramics at different sintering temperature.

Resistance (kU) (error %) Capacitor (pF) (error %) CPE-T (error %) CPE-P (error %)

1380  C 1110 (0.55) 627 (0.63) 5.05E-9 (3.61) 0.71 (0.71)

1460  C 586 (0.41) 1060 (0.39) 1.25E-8 (2.47) 0.68 (0.49)
1520  C 180 (1.36) 4590 (0.90) 7.52E-8 (5.59) 0.65 (1.14)
1580  C 140 (0.50) 3330 (0.57) 5.60E-8 (2.49) 0.68 (0.48)
956 J. Qi et al. / Journal of Alloys and Compounds 762 (2018) 950e956
Table 2
Energy storage density and efficiency.
Maximum energy storage Effective energy storage Efficiency
density (J/cm3) density (J/cm3) (%)
1380  C 1.02 0.92 90.2
1460  C 1.27 0.90 70.9
1520  C 0.02 0.01 50.0
1580  C 0.26 0.05 19.2
dielectric properties are associated with defect clusters (e.g. oxygen
vacancies, Ti3þ/Ti4þ etc.) rather than grain sizes. The impedance
spectroscopy and PE results demonstrate that the formation of
defects clusters at high temperature sintering process play an
important role on the electric properties, defects clusters are more
likely to become carriers in high electric field that increase the
conductivity, leakage current and deteriorating breakdown
strength.
Acknowledgements
This work was supported by the NSFC-Guangdong Joint Funds of
the Natural Science Foundation of China (No. U1601209), National
Key Basic Research Program of China (973 Program) (No.
2015CB654601), Technical Innovation Special Program of Hubei
Province(2017AHB055), Open Project of Key Laboratory of New
Electric Functional Materials of Guangxi Colleges and Universities
(DGN201505), State Key Laboratory of Advanced Technology Ma-
terials Synthesis and Processing (Wuhan University of Technology)
(2018-KF-11).
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