Ceramics International 45 (2019) 12994–13003

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Origin of the temperature stability of dielectric constant in CaCu3Ti4O12 T

a,∗ a a b a a a,∗∗ c
X.J. Luo , Y.T. Zhang , D.H. Xu , S.S. Chen , Y. Wang , Y. Chai , Y.S. Liu , S.L. Tang ,
C.P. Yangd, K. Bärnere
a
Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, Shanghai, 200090, PR China
b
Faculty of Mathmatics and Physics, Hubei Polytechnic University, Huangshi, PR China
c
Nanjing National Laboratory of Microstructures, Jiangsu Provincial Laboratory for Nanotechnology and Department of Physics, Nanjing University, Nanjing, 210093, PR
China
d
Faculty of Physics and Electronic Technology, Hubei University, Wuhan, 430062, PR China
e
University of Göttingen, F. Hund Platz 1, 37077, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: The temperature and dc bias stability of the dielectric constant and loss tangent of CaCu3Ti4O12 samples sintered
CaCu3Ti4O12 under different oxygen atmospheres are discussed. The results suggest that the metal-oxygen vacancy related
Trap defect defects not only provide the charge carriers for the conduction (defect doping) but also contribute to the huge
Defect dipole permittivity in the way of defect dipoles repositioning under charge carrier hopping. The charge localization in a
Oxygen vacancy
specific copper-oxygen vacancy defect complex is the reason of the huge and stable permittivity and low di-
electric loss in the middle temperature range, 90 K-200 K (20 Hz), while the implementation of the large barrier
layer height needs a contribution by the titanium oxygen vacancy related trap charges in the grain boundaries,
which also lead to a second permittivity stable range in a higher temperature range 200 K–300 K.

1. Introduction
Recently, oxides with giant and stable dielectric constant (ε‘
≈103–106) within a wide frequency and temperature range were in-
tensely studied [1–4], and research is still going on. It seems that people
have found a way to get a giant and stable permittivity but with low
dielectric loss in titanium oxide, using co-doping of the titanium oxide.
Specifically, acceptor and donor co-doping is used. Typical work was
done by Hu and co-workers, who doped TiO2 by 10% In3++Nb5+ and
then got a high permittivity about 6 × 104 with a low dielectric loss
tanδ ≈0.02 within a temperature range 80 K–450 K [1]. The work was
followed by others and they have successfully obtained large permit-
tivities in the range of 103∼105 and low dielectric loss < 0.1 within the
temperature range of 200 K–450 K (1 kHz) by the acceptor and donor
co-doping method [5–9]. In addition, people found that the permittivity
of the co doped samples show only small changes with dc bias [6,10]. In
an attempt to further reduce the dielectric loss, similar work was done
on CaCu3Ti4O12 (CCTO) [3,11–15]. For example, Al3++ Nb5+ co-
doping of CCTO lead to a low–frequency loss tangent tanδ < 0.1, while
there is still a high permittivity in the order of 2.9–4.1 × 104 within a
wide frequency range of 40 Hz ∼105 Hz and temperature range of
200 K–450 K (1 kHz) [13]. While for pure CCTO, the value of the loss
tangent is easily up to 0.1 and the temperature stability range is lower
and of 100 K–380 K (1 kHz) [16], as shown in Table 1, which lists the
permittivity, dielectric loss and the frequency and temperature stability
range for pure and co – doped CCTO samples obtained from the lit-
erature. However, there is an argument about the mechanism of the
large and stable permittivity. In In3++ Nb5+ co-doped TiO2, Hu and
co-workers proposed an electron‐pinning defect–dipole (EPDD model)
for the underlying mechanisms of the high permittivity [1]. Specifi-
cally, they think that the donor substitution creates delocalized elec-
trons from the reduction of host cations while the acceptor provides a
local oxygen-deficient environment assisting the reduced host cations to
hold back the delocalized electrons, whereupon the dielectric loss is
decreased, and local electron-pinning defect-dipoles are created to
boost polarization [1]. However, it was also suggested that the huge
and stable permittivity originates from the interfacial (Maxwell-
Wagner) polarization, namely the internal barrier layer capacitor
(IBLC) model. The evidence for this model is seemingly provided by the
investigation of impedance spectra which are thought to unravel the
grain or grain boundary resistance, the nonlinear current–voltage be-
havior [17–23], the large breakdown voltage [18,22–25] and grain size
effect [17,19,22]. However, we should mention that no matter if we
take co-doped TiO2 or co –doped CCTO, the leaky conduction and

∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: xiaojing_luo@163.com (X.J. Luo), ysliu@shiep.edu.cn (Y.S. Liu).

https://doi.org/10.1016/j.ceramint.2019.03.229
Received 9 December 2018; Received in revised form 21 March 2019; Accepted 28 March 2019
Available online 03 April 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
X.J. Luo, et al.
Table 1
The frequency and temperature stability range of co – doped CCTO samples and the permittivity, dielectric loss in this range.
ε’
4
CaCu3Ti4-x (Nb0.5Al0.5)xO12 [13] 2.9–4.1 × 10
Ca0925Sm0.05Cu2.7Mg0.3Ti4O12 [3] 1.25 × 104
Ca0925Yb0.05Cu3-yMgyTi4O12 [15] (y = 0.05 and y = 0.3) 104
Ca0925Y0.05Cu2.95Mg0.05Ti4O12 [11] 8.6 × 103
CaCu3Ti4O12 [16] 5 × 104∼105
permittivity increase simultaneously, which throws some doubt on a
stable trap distribution, surface polarization – only model. Specifically,
from Table 1 we can see that the good performance of the stability and
low dielectric loss is always at the cost of a decrease in permittivity: a
large permittivity is always accompanied by a low stability, a large
conductance and a high dielectric loss. Thus, we should reconsider the
relation between conduction and permittivity. Actually, the permit-
tivity –conduction relation had led to many abnormal dielectric phe-
nomena in CCTO, for example, the butterfly CeV relation [26] and
hysteresis loops which are similar to the ferroelectric loop [27,28]. This
behavior cannot be explained by an interfacial polarization only. It
suggests a volume contribution, i.e. the contribution of a more or less
homogeneous distribution of trap states in the polycrystalline sample
volume.
The permittivity of pure TiO2 is small, but the permittivity of the co-
doped TiO2 could be improved by several orders of magnitudes using
only a small number of foreign ions. This indicates that the defects take
an important role in the dielectric polarization. Thus, for the in-
vestigation of the origin of the huge and stable permittivity, we should
pay attention to the conduction and polarization contributed by natural
or introduced defects. We know that without doping, CCTO has already
has a huge and stable permittivity of 104 ∼106 in a wide temperature
range from 100 K–380 K, which is strongly dependent on the sintering
conditions such as the sintering time, temperature and sintering at-
mospheres. In this work, we investigate the temperature dependent and
dc voltage dependent permittivity and dielectric loss for CCTO samples
sintered under different oxygen atmospheres, in order to understand
the relation between temperature and dc voltage stability and the de-
fects, especially to oxygen vacancies.
2. Experiment and characterization
CCTO ceramics were synthesized by the solid-state reaction method
using analytically pure raw materials of CaCO3 (99.99%), CuO (99%),
and TiO2 (99.5%). First, the raw powders were mixed and pre-sintered
at 1173 K for 10 h. Then, the pre-sintered powders were pressed into
disks, and pre-sintered at 1273 K for 10 h again. The pre-sintered pellets
were reground and pressed into a disk of 11 mm in diameter and
1.5 mm in thickness. At last, the pressed disks were sintered at 1373 K
for 12 h in vacuum (sample V), air (sample A) and oxygen atmosphere
(sample O) respectively. For the measurements of electrical properties,
sintered silver pastes (580 °C for 10 min) were coated on both sides of
the disks as electrodes. The structures of the samples were detected by
powder X-ray diffraction (XRD, DRON-3, and CuKα). The morphologies
of the samples were characterized by scanning electron microscope
(SEM, Hitachi S-5750). The dielectric response and CeV measurements
were obtained using a WK6500 (made in Taiwan, China) impedance
analyzer together with a Janis closed-cycle-refrigerator. The dc-con-
ductivity was performed by a commercial electrometer Keithley 2400
with a computer-controlled program.
3. Results
Fig. 1 shows the X-ray diffraction (XRD) spectra of the three CCTO
samples at room temperature. The XRD peaks can be identified ac-
cording to the standard JCPDS card (number: 75–2188) of pure CCTO.
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tanδ Temperature stability range Frequency stability range
0.045–0.058 200 K–450 K 10∼105
0.039 200 K–450 K 10∼105
0.018–0.028 200 K–450 K 102∼106
0.013–0.05 200 K–450 K 102∼106
0.05–0.5 100 K–380 K 102∼105
Fig. 1. Comparison of X-ray diffraction patterns of the three samples sintered
under different atmospheres.
It can be seen that the crystal phases of polycrystalline CCTO ceramics
have no obvious differences for the three samples sintered under dif-
ferent atmospheres. No obvious impurity peaks can be observed for the
three samples. The microstructures for the three samples are shown in
Fig. 2. The shape of the grains is irregular with different sizes for the
three samples. The grain size of the sample sintered under vacuum is
especially uneven, with larger grain size about 80 μm and smaller grain
size about 5 μm, as shown in Fig. 2 (a). While the grain sizes of the
samples sintered in air or under oxygen atmospheres are more uniform,
as shown in Fig. 2 (b) and (c), with an average grain size about 5 μm.
Fig. 3 shows the temperature dependent permittivity at different
frequencies for the sample sintered in air (A). As observed by many
researchers, there is a broad permittivity stable range (shown as plat-
form 1) in a temperature range 90 K–200 K (20 Hz). When the fre-
quency increases the stable range moves to higher temperatures. After a
transient permittivity rise, another small permittivity platform 2 stays
for a while from 240 K to 300 K at 20 Hz. The permittivity stable range 1
does not change much in height with frequency. However, the height is
much sensitive to the oxygen content. Fig. 4(a) shows the temperature
dependent permittivity for the samples sintered under different oxygen
atmospheres. The sample sintered under vacuum (sample V) has the
highest permittivity platform 1 while the sample sintered in oxygen
atmosphere (sample O) has the lowest one. The permittivities at 20 Hz
are about 6 × 104, 3 × 104, and1 × 104 for sample V, sample A, and
sample O, respectively. Note that over the permittivity platform 1, the
ac conductivity also stays constant, i.e. we have no relaxation peak
here, as shown in Fig. 4 (b). However, with increasing temperature, two
conductivity relaxation peaks come out, located before the permittivity
platform 1 and platform 2 respectively, indicating that the permittivity
platforms are polarization balance states that are installed after two
different thermally activated relaxation processes are initiated.
According to the research on the dielectric behavior of the acceptor
and donor co-doped titanium oxide, its permittivity also does not
change with dc bias [6,10]. Thus, in the constant permittivity region,
we measured the permittivity change under different dc bias (ε′∼U) at
a certain temperature 250 K, as shown in Fig. 5. Fig. 5 (a), (c) and (e)
show the capacitance under different dc bias for sample V, sample A,
and sample O respectively. The ε′∼ U relation was investigated at
different ac frequencies. We see that the sample O has the most stable
X.J. Luo, et al. Ceramics International 45 (2019) 12994–13003

Fig. 2. SEM images of surface morphologies of the three samples sintered (a) and (b) under vacuum, (c) and (d) in air, (e) and (f) under oxygen atmospheres.

Fig. 3. The temperature dependence of permittivity at different frequencies for

the sample sintered in air.

permittivity under dc bias, especially at higher frequencies. For samples

V and A, which may have relatively higher oxygen vacancy contents as
the lower oxygen content sintering atmospheres, the capacitance de-
creases somewhat with increasing dc bias at higher frequencies 10 kHz,
100 kHz and 1000 kHz. The dielectric losses changes with different dc
bias follow similar rules as the permittivity, as shown in Fig. 5 (b), (d)
and (f). Sample O has the stable dielectric loss at all frequencies, while
Fig. 4. Temperature dependence of permittivity (a) and conductivity (b) for the
for sample V and sample A, dielectric loss shows a small decrease with
sample sintered under different atmospheres at 20 Hz.
increasing dc bias at higher frequencies. However, at low frequencies
such as 20 Hz and 100 Hz, we can see that both permittivity and di-
electric loss rise at a larger dc bias for sample V and sample A. In

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Fig. 5. (a), (c) and (e) shows the dc bias dependence of permittivity at different frequencies for sample V, sample A and sample O, respectively. (b), (d) and (f) shows
the dc bias dependence of dielectric loss at different frequencies for sample V, sample A and sample O, respectively.
particular, the permittivity of sample V rises rather easily with dc bias:
at 20 Hz, the initial permittivity rise voltage is already at about 9 V for
sample V, and 20 V for sample A. At 100 Hz, the initial permittivity rise
voltage is at about 12 V for sample V and 28 V for sample A, while for
sample O, we only see only a small decrease of permittivity with in-
creasing dc bias at lower frequencies. The increase of the dielectric loss
with dc bias is generally called a “leaky” conduction. The simulta-
neously increasing permittivity suggests that the delocalized carriers
are polarons and as such contribute to the polarization.
While generally the ac conductivity is only proportional to the di-
electrics loss, according to the above results here we can summarize as
below: 1) permittivity and conduction decrease or increase simulta-
neously with dc bias, or both stay constant with temperature, indicating
that the polarization and the conduction processes are connected; 2) a
stable permittivity range appears at medium temperature and smaller
dc bias, where the conduction is also stable with temperature and dc
bias. This indicates specifically the connection of a hopping conduction
and a polarization, which is at least partly due to defects in the grain
boundaries that are exposed to the large barrier electrical field in the
boundaries; 3) the rise of permittivity at high temperatures or high dc
bias indicates a thermal or electrical activated polarization, which is
connected with a conduction relaxation peak and a conductivity rise
with temperature and/or dc bias. The thermal activation and electric
activation mostly easily occur in the sample sintered in vacuum at-
mosphere (sample V); sample V has the most unstable ε′∼U relation
but the largest permittivity and dielectric loss. As a vacuum un-
doubtedly would create more oxygen vacancies in sample V as in
samples A and O, we think that oxygen vacancy related defects might
contribute most to the large capacitance and instability, and also to the
high dielectric loss; 5) the unstable ε′∼ U relation appears in sample V
rather early, i.e. at low frequencies and higher temperatures, indicating
that even a dc conduction can contribute to the polarization process.
In order to compare the barrier layer height in the three samples, in
Fig. 6 we investigated the impedance spectra. These spectra yield the
resistances for the inhomogeneous regions, they can be read from the
diameter of the semicircle in Cole – Cole plot at low temperatures (LT,
Fig. 6(a)), medium temperatures (MT, Fig. 6(b)) and high temperatures
(HT, Fig. 6(c)), respectively. From Fig. 6 (a) and (b) we find that all the
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Cole – Cole plots for three samples show near linear lines that are al-
most perpendicular to the x-axis at low frequency, suggesting a large
but mainly hidden large semicircle, which we call semicircle II. At the
highest frequencies there are non-zero intercepts, which develop into
small semicircle at low temperatures (see the insets in Fig. 6 (a) ∼ (c)).
The small semicircle with a zero intercept may represent the resistance
of grains, which we call it semicircle I. At LT and MT, the diameter of
the semicircle I for the sample sintered under vacuum is smallest.
However, for the three samples we could not detect any obvious change
in the diameters of the large semicircle II, which therefore may express
the resistance of grain boundaries. Only at high temperatures we can
differentiate the diameters of the semicircle II of the three samples, as
shown in Fig. 6 (c). In previous work [29] we has shown that there is
the third semicircle at a very low frequency. The sharp change in the
diameters of the semicircle at high temperatures may be due to the
decrease of the barrier layer width in the grain boundary due to the
thermal activation of the deep energy levels in the boundaries. The
thermal activation of the charges in deep trap levels which by re-
positioning may cause also the sharp increase of the permittivity at high
temperature. The large grain boundary resistance at MT is responsible
for the MT stability of the permittivity (platform 1), with the conduc-
tion stable at MT.
4. Discussion
4.1. Barrier layer capacitance
First, we should mention the classical relation between defects and
MW polarization. We know that the defects are primarily stored at the
interfaces (inner or electrode interfaces) and form trap centers for
charge carriers in n-type grains, leading to a high double back-to-back
Schottky potential barriers [18]. In the medium temperature range, the
large difference between Rgb and Rg shown in Fig. 6 suggests this in-
homogeneity of the conductance. Thus, ultrathin grain boundaries are
present as insulating barriers and these internal surfaces are surrounded
by the charge carriers from the grains, resulting in a high capacitance,
which depends on the geometric conditions as in a standard capacitor.
Here, the capacitance of grain boundary and grain can approximately
X.J. Luo, et al.
Fig. 6. The impedance spectra for the three differently sintered samples at (a) 100 K, (b) 215 K, (c) 368 K. The insets show the magnified details at high frequencies.
εgb S εg S
be written as Cgb = and Cg = respectively, with S, tgb and d the
tgb d
extended surface area, the thickness of the boundary and grain re-
spectively. εgb and εg are the permittivity of boundary and grain
boundary, respectively. Using an equivalent circuit based on two par-
allel elements connected in series, with one Rgb and Cgb and the other Rg
and Cg , one can write the effective permittivity at low frequency by
Refs. [20,30]:
d written as [18].
ε′ = εgb
tgb
Equation (1) describes the permittivity obtained; it can also be
called a Maxwell – Wagner polarization; it depends on the size of grains
and the thickness of grain boundaries, and so the microstructure de-
termines the Maxwell – Wagner polarization. tgb is usually very small,
about several nanometers. But the grain size of CCTO polycrystal is
quite different: it may range from 1 μm–100 μm, dependent on the
sintering time [4,19,31]. In our case, there is indeed some larger grains
for sample V which has the largest permittivity. Thus, we could not
exclude the contribution of the Maxwell- Wagner polarization. How-
ever, the average grain size for sample A and sample O has no obvious
distinction and are all bout 5 μm, which cannot cause such an obvious
change of the permittivity shown in Fig. 4 (a).
If we say that the Cgb is related to the width of depletion layer in the
Schottky barrier and the layer potential height which can be char-
acterized by Rgb , since the layer is both resistive and of high capacitance
due to the thin width of the depletion region [18], tgb , εgb in eq. (1) can
be replaced by the width tb and permittivity εb of the depletion barrier
layer, and the effective permittivity can also be written as [17]:
d asymmetry in the ε′∼ U relation, as shown in Fig. 8 (a). Note that the
ε = εb
tb
At high temperuares, Rgb is indeed largest for the sample sintered
Ceramics International 45 (2019) 12994–13003
under oxygen atmoshphere, indicating the largest barrier width tb . If the
grain sizes for the three samples are almost the same, then sample O
should indeed have the smallest permittivity, and it might be a candi-
date for a classical MW-polarization. In the medium temperature range,
all three samples show large arcs, so that we could not get Rgb easily
from the diameter of the semicircle. However, the C ∼ U relation yields
some estimate of the barrier layer capacitance. According to the BLC
model, the relation between capacitance and dc external field can be
(1)
1 1 2 2
( − ) = (ϕ + U)
C 2C0 εqNd b (3)
where ϕb is the barrier layer height, Nd is the charge carrier con-
centration in the grains, ε is the permittivity of material or the grain, q
is the electronic charge. From eq. (3) we should expect the capacitance
to decease with dc bias U. As the permittivity of the ceramic is pro-
portional to the capacitance when the geometric factor of the sample
does not change, the permittivity will decrease with dc bias also. In
addition, for a symmetric space charge layer near the boundary, the
external field always adds to one side and subtracts from the other.
Then, the ε′∼ U curve should be symmetric under different voltage
signs, and the maximum C should be at U = 0. In Fig. 7 we simulate the
ε′∼ U behavior of two back to back diodes. The situation is as we said,
the symcenter or the maximum is strictly at U = 0. The ε′∼ U curves in
Fig. 5 for all the three samples shows a falling of ε′ under dc bias except
for the curves at low frequency, only with a different degree of decline.
However, if we investigate the ε′∼ U relation for sample V in a way of
sweeping voltage cycles, we find that there is an obvious hysteresis and
ε′∼ U curve is asymmetric when the voltage load changes sign. The
(2)
maximum moves to right and appears at a positive dc bias. On the other
hand, the ε′∼ U behavior for the sample sintered under oxygen, sample
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Fig. 7. The dc bias dependence of capacitance for the back to back p-n junction.
Fig. 8. The dc bias dependence of capacitance at 10 kHz for (a) sample V and
(b) sample O.
O, is consistent with the back to back diodes model, as shown in Fig. 8
(b). Thus, the BLC model alone cannot explain the abnormal ε′∼ U
behavior for sample V (sintered under vacuum). The BLC model ap-
parently works under low defect content and low temperatures, giving
no particular attention to the kind of trap. If, however, the space
charges in the boundary can position preferentially at certain lattice
defects and reposition preferentially under thermal agitation and ex-
ternal field E0 , the permittivity would be maximal for sample V-type
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samples and could even increase with the temperature, given a dipolar
character of this specific complex. It is also possible that the strong
electrical fields inside of the barrier are needed to break a zero field
dipole symmetry of those complexes, thus creating what one might call
specific space-charge dipoles [32].
4.2. The defects and their contribution to the conductance and the
permittivity
Because the simultaneous increase of capacitance or permittivity
and conduction, besides the geometrical factors, we should consider the
conduction contributed by the charge defects. Even sintered CCTO itself
is defect loaded or in short “defective” due to energetic features of its
crystal structure [33,34]. In an oxygen deficient sintering atmosphere,
oxygen vacancies are produced at high temperatures which will bring a
reduction of metal ions,
2Ti 4 + + 4O 2 − → 2Ti′Ti + VO•• + 3OO
Cu2 + + 2O 2 − → Cu′Cu + VO•• + O2 ↑
The chemical nature of the metal ions in CCTO samples sintered
under atmospheres were observed by many researchers using the X-ray
photoelectron spectroscopy measurements. Specifically, the Cu and Ti
ions for the sample sintered in air or under reducing atmospheres are
partly reduced to Cu+ and Ti3+, while the anion lattice is oxygen de-
ficient. Thus, there is a charge compensation via low valence ions,
while the sample sintered under oxygen atmosphere is almost fully
oxidized Cu and Ti ions [35,36]. Reducing or oxygen deficient atmo-
spheres always introduce the simultaneously increase of permittivity
and conductivity [37]. Our results are consistent with the results found
in most dielectric ceramics that the sample sintered under vacuum has
the largest conductance and permittivity, as the barrier height at the
interface is greatly reduced by the acceptor impurities. In addition, as
shown in Fig. 6, both the grain and grain boundary resistance are
smallest in sample V, suggesting that the acceptors not only provide
electrons to grain boundaries but also to the grains, which will explain
the increasing leaky conductance in sample V. However, the conduction
of these defect charge carriers also introduces a large permittivity in
sample V.
In our previous work [38], we found that the temperature depen-
dence of dc conduction in CCTO is similar to the conduction in classical
semiconductors, i.e. σ also show three – stage changes with tempera-
ture, just as the three – stage changes the permittivity – temperature
relation shown in Fig. 3. At low temperatures, the decrease of permit-
tivity is accompanied by the decrease of the dc conductivity and of the
ac conduction relaxation peak. At medium temperatures, both (ac or
dc) conduction and permittivity show only small changes with tem-
perature. At high temperatures, both (ac or dc) conduction and capa-
citance increase faster with temperature. The transition temperature
points of the three-stage changes of the three curves are almost the
same. The link between conduction σ and permittivity indicates a
model of thermally activated space charges. The high temperature
range is the thermal activation region of these charge carriers, in-
troducing a sharp rise of permittivity; the medium temperature range is
the charge carrier reserve or localization region, introducing a stable
permittivity; and the low temperature range is the charge carrier frozen
region which leads to the sharp drop of permittivity [38]. The high
barrier height indicated by the large Rgb may be the reason for the space
charge carrier localization. In this case, the charge carrier hopping
between defect sites contributes to the dc-conduction. The nearest-
neighbor hopping obeys an Arrhenius-like law:
σdc = σ0 exp(−Ea/ kB T ) (4)
Where σ0 is usually a constant, Ea is the thermal activation energy, T
is the absolute temperature, and kB is the Boltzmann constant.
However, Mott points out that at low temperatures the hopping
X.J. Luo, et al. Ceramics International 45 (2019) 12994–13003

Fig. 9. The temperature dependent of dc conductivity plotted according to Mott

and Arrhenius conduction for the sample sintered in air.

distance may be larger than the distance between the neighboring sites.
This kind of conduction was called the variable-range hopping (VRH)
conduction can be described by Ref. [39]:
σdc = σ0 exp(−T0/ T ) p (5)

where T0 is also a constant be dependent on the density of localized

states at the Fermi level. The exponent p is usually 1/4. Take the
logarithm we plot the ln σ ∼ T −1 and ln σ ∼ T −1/4 relation in Fig. 9 for
the sample sintered in air. We can see that both curves show linear
relations at HT and MT respectively. At low temperature, both curves
show some curving. Even for the sample sintered under vacuum which
may have larger content of oxygen vacancies, both the ln σ ∼ T −1 and
ln σ ∼ T −1/4 relations are near linear and so we could not separate the
two regimes for conduction. So while all the signs suggest that the di-
electric relaxation process is accompanied by the charge carrier hop-
ping, at present we cannot strictly point out the way charge carriers are
hopping. One hint is that, when we compare the dc ln σ ∼ T −1 relation
with ac ln σ ∼ T −1 relation (after subtracting the relaxation peak), the
slopes at HT, MT and LT are almost the same [38]. The result indicated
that the hopping conduction is accompanied by a local relaxation of
charge carriers. Actually, if we and other workers consider the HT
polarization and conduction, in the HT range, both the permittivity and
dielectric loss show a peak and then a fast rise [40,41], indicating an
additional thermal activation. This also shows that the polarization is
sensitive to any carrier hopping process, also one which occurs in a
global way (dc-conductivity). In this case the conduction can by de-
scribed by the universal relaxation law [42],
σ (ω) = σdc + A (T ) ωn
Specifically, because of the similarity with the Debye dipolar re-
laxation we may assume that the T-dependence of A reflects a thermally
activated relaxation time.
Further evidence can be obtained by a comparison of the activation
energy of the conduction and of the local relaxation process. In the
middle temperature range, because of the large barrier height of the
boundaries, the conduction has to be measured in the grains that have a
much smaller resistance. From the grain resistance obtained from the
impedance spectra we can extract the conduction activation energy
using a resistance Arrhenius law:
Rg = R 0 exp(Eg / kB T )
Where R 0 is a pre-exponential constant term, Eg is the conduction
activation energy of the grains. As shown in Fig. 10 (a), in the LT range,
Eg is in the range of 0.07–0.08 eV, i.e. changes somewhat with the
sintering atmospheres. In Fig. 10 (b), we also extracted the relaxation
Fig. 10. The Arrhenius relation of the grain resistance obtained from the high
frequency impedance spectra (a) and the Arrhenius relation of the relaxation
time obtained from the low temperature relaxation peaks of the imaginary
capacitance (b).
activation energy using a relaxation time Arrhenius law. The relaxation
time is obtained from the imaginary capacitance at low temperatures:
τ = τ0 exp(−ER/ kB T ) (8)
where τ0 is the mean relaxation time and ER is the relaxation activation
energy. The local relaxation activation energy is about 0.08–0.09 eV,
which is quite similar to the charge carrier conduction activation en-
ergy. This suggests again that the polarization is strongly correlated
(6)
with the charge carrier transport process.
4.3. The defect dipole polarization by trap charge repositioning
The basic idea is that if there is carrier hopping, defects that can
become dipolar by trapping a charge. Such defect dipoles can change
their position according to the carriers hopping but without the defect
structure of the sample being changed. Because a given trapping state
has lower or higher energy level in a given electric situation, if one
changes that situation, for example by applying an external electric
field E0 , the electrons will be retrapped at the now most favorable sites,
provided that the carrier hopping is thermally activated. That, of course
(7)
implies that not all the potential dipole centers are occupied, but only a
fraction of them. This would immediately explain why at low tem-
peratures the dielectric situation cannot be changed because there is a
carrier freezeout. First, however, these dipolar trap centers have to be
chemically identified. As discussed before, acceptor impurities such as

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X.J. Luo, et al.
Ti3+ and Cu1+, which are compensated by the oxygen vacancies VO are
easy to create in oxygen deficient or high temperature sintering atmo-
spheres. Usually, the neutral (VO ) or positively charged vacancy Vo••
(with a dot representing a positive charge) are stable in different O-
content regimes in CCTO [43], Thus, in CCTO, one may have metal-
oxygen vacancy complexes like, (CuCu ′ − Vo••)′ or (TiTi′ − Vo••)′, with a
single quote representing a negative charge. The formation of metal-
oxygen vacancy defect complexes and their contribution to the re-
laxation and conduction in ferroelectrics had been experimentally es-
tablished and theoretically calculated [44–46]. These defect complexes,
if located near the boundaries, will introduce carrier trap energy levels
in the boundaries. The synchronous change of capacitance and con-
ductivity indicates that these defect complexes possess the character-
istics of a multipole, i.e. they combine a charge and a dipole. The
hopping of the charges under an external field E0 would activate the
repositioning of defect dipoles, i.e. the defect dipoles can change site, at
the same time the polarization is rebuilt according to the repositioning
process. That was called a trap charge repositioning (TCR) process in
our previous work [47,48]. If the external electric field E0 is the re-
positioning agent, we also have to consider its directional quality.
Considering two kinds of grain boundaries, as shown in Fig. 11, we call
the grain boundary perpendicular to E0 “fs” boundary, and the grain
boundary parallel to E0 “fp” boundary. Assuming the grains are n-type,
the space charges in the boundaries construct a n-p-n junction in the
boundaries with an internal (Schottky) field Ei as also shown in Fig. 11,
with the peak like line showing the barrier height, and the ellipse
showing the defect dipole. If, for example, the optimal energetic posi-
tion of the dipole is parallel to the internal field Ei . Once we introduce
E0 , due to the external field cutting down the barrier layer on B side and
increasing the barrier layer on A side and the “fp” boundaries, we ex-
pect a repositioning of the dipoles so that the “fs” boundaries get fa-
vored at the expense of the “fp” boundaries and the A side of the “fs”
boundaries. If the dipolar center density gets high enough, such as in
sample V, we would be come close to a ferroelectric-like situation.
Ferroelectric interactions in connection with an induced ferroelectricity
would explain the off-centered ε′∼U curves as observed (Fig. 8(a)). Off-
centered hysteresis loops are often found in chemically and/or struc-
turally amorphous ferromagnets which undergo a compensation to
ferromagnetic transition. With the introduction of ferromagnetism we
generally introduce a magnetic anisotropy, too. Then, favorably with
chemically random systems, we have an interaction between the dis-
tribution of magnetic couplings with that of the magnetic anisotropy
energies which both relax only slowly. In those cases we obtain a see-
mingly asymmetric coercive field HK under a symmetric positive and
Fig. 11. The schematic diagram of the trap charge repositioning (TCR) process for the back to back n-p junction, assuming the grains are n-type. The ellipses sketch
the electric moments along the internal electric field Ei.
13001
Ceramics International 45 (2019) 12994–13003
negative applied magnetic field H0, which depends on the cycle time
[49]. In random systems (here the grain boundaries are harboring dif-
ferent chemical species) we expect to find such phenomena, too, pro-
vided that we have ferroelectric interactions and a (hidden fs/fp) ani-
sotropy. In the ε′∼U curve of CCTO, sample V, a hysteresis and an
electric anisotropy, can be observed. So sample V is very close to the
ferroelectricity. If the repositioning is complete, the polarization should
be maximal at the offset center, just as the magnetic polarization is
maximal at the offset center field value, i.e. the capacitance peak at a
positive dc voltage represents a maximal ferroelectric polarization.
4.4. The reason of permittivity stability
Dielectric materials usually have stable permittivities as all mole-
cules are polarized the same. In contrast to the standard Schottky
barrier where the space charge polarization mechanism is global, the
trap charge repositioning is local, i.e. in the molecular range. Thus, the
stability is not evident with defect dipoles providing the permittivity.
From Fig. 5 we know that the MT permittivity shows only small changes
with dc bias, in particular for sample O. We deduce that the MT stable
permittivity in sample O is based on the grain boundary polarization, as
the grain boundary resistance are insensitivity to the external field E0 .
The reason may be that the external field drops mostly across the sur-
face layers that present a global back-to-back Schottky barrier in series,
i.e. the surfaces perpendicular to the external field, only a small per-
centage of the applied dc voltage V is loaded on each of the many grain
boundaries. However, in contrast to a classical deep carrier trap, if we
lift the charges out of the defect complex via increasing the dc bias that
can worsen the permittivity stability, while the permittivity is en-
hanced. Thus, the sample V show the most obvious permittivity changes
with dc bias and also largest permittivity due to the largest amounts of
acceptors in sample V. Specifically, we think that in sample V the ex-
ternal field can be high enough for an almost complete depletion of
charge carriers in the “fs” boundaries.
As to the temperature stability, which appears in all samples but in
different orders of magnitude, we think this is due to the charge loca-
lization in the MT range, while the LT and HT relaxation peaks point to
a thermal activated defect dipole relaxation process. In the literature it
is proposed that the Ti3 + and Vo•• ions normally introduce deep donor
levels with an activation energy of about 1.0 eV [35,50], while the
acceptor level in CuO shows a shallow activation energy of about
0.073eV [51]. It is also reported that both CuO and Cu2O always show a
p-type conductivity down to low temperatures [52,53]. In CCTO, the LT
relaxation activation energy and conduction energy is in the range of
X.J. Luo, et al.
0.07–0.09 eV. The HT relaxation energy is about 0.6 eV and the con-
duction activation energy for sample V is about 0.6 eV. In the tem-
perature range measured, we could not extract the conduction activa-
tion energy for samples O. But the literature shows that the activation
energy of grain boundary for the sample sintered in the oxygen is
1.057 eV [36]. Thus, we deduce that the LT relaxation and conduction
is based on copper – oxygen vacancy related defects like (CuCu ′ − Vo••)′,
while the HT relaxation and conduction is based on the thermally ac-
tivated titanium-oxygen vacancy related defects like (TiTi′ − Vo••)′. Thus,
the permittivity platform 1 between the LT and MT relaxation peaks
may be based on the polarization of (CuCu ′ − Vo••)′ defect dipoles. This
deduction is consistent with the results found by many researchers that
the Cu content strongly influences the dielectric behavior of CCTO.
While the permittivity platform 2 may be based on the deeper energy
levels introduced by (TiTi′ − Vo••)′ defects. As the activation energy of
(TiTi′ − Vo••)′ defect is high, the permittivity platform 1 is “protected” by
the large barrier height provided by (TiTi′ − Vo••)′ defects until this deep
energy level is activated at high temperatures. In the acceptor and
donor co-doped TiO2 samples, there is also large stable permittivity
found in a wide temperature range, which is similar to that of CCTO.
We think the reason of the large stable permittivity is the same. Ros-
seinsky et al. compared the electronic structure of CaCu3Ti4O12 and that
of TiO2 [54]. They found narrow Cu 3 d and O 2p hybridization states
within the gap, creating localized states which can trap and generate
electrons by visible light absorption spectra and a LSDA + U calcula-
tion [54]. The authors think that the situation is similar to transition
metal doped TiO2, where the localized defect sites induced by the
doping can act as trapping sites and recombination centers. However,
the permittivity stable range for co-doped TiO2 is in a higher tem-
perature range, at about 80 K–450 K [55]. We think the deeper energy
level provided by Ti3+ acceptors may be the reason. For CCTO samples,
as the copper ions introduce shallow trap defect levels, the first stable
permittivity range can indeed be expected in a lower temperature
range, i.e. 90 K–200 K (20 Hz), and the second permittivity range can be
expected in a higher temperature range, i.e. 200 K–300 K (20 Hz).
Of course, a high and stable barrier layer can lead to an insulating
grain boundary and introduce a barrier layer capacitance in sample O.
But the different magnitude of the (constant) permittivity shown in the
three samples suggests that in terms of dielectric behavior the con-
tribution of (CuCu ′ − Vo••)′ related defects to the permittivity is im-
portant. Note that (CuCu ′ − Vo••)′ can be transferred under an external
field via charge carrier hopping, and so the transfer of complexes also
contributes to the conduction. The transfer of the defect dipoles, how-
ever, is accompanied by the dipole repositioning and orientation, which
will provide a large permittivity.
5. Conclusion
In summary, we think that the metal-oxygen vacancy related defect
dipoles not only contribute to the large permittivity in a way of charge
repositioning, but they are also mainly responsible for the large “leaky”
conduction or dielectric loss, at least for the permittivity observed in
the sample sintered under vacuum. As to the reason of the permittivity
stability we can conclude: 1) the large barrier height and the small dc
voltage load per grain boundary lead to a stable permittivity which
show only small changes with dc bias; 2) the charge localization in the
copper-oxygen vacancy defect complexes with a shallow energy level
lead to a first stable permittivity and low dielectric loss at middle
temperatures 90 K–200 K, while the titanium-oxygen vacancy with a
deeper energy level provide a large barrier potential which stabilizes
the middle temperature permittivity stability and lead to a second
permittivity stable range at higher temperatures 200 K–300 K.
Acknowledgments
This work is supported by the National Natural Science Foundation
13002
Ceramics International 45 (2019) 12994–13003
of China (Grant Nos. 11504227, 51502168, 11502139), and “Shu
Guang” project of Shanghai Municipal Education Commission and
Shanghai Education Development Foundation (No. 13SG52).
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