Proceedings of 2008 International Symposium on Electrical Insulating

Materials, September 7-11, 2008, Yokkaichi, Mie, Japan P1-7

Investigation on the dielectric properties of CaCu3Ti4+xO12+2x

T.W. Xu , J.Y. Li*, S.T. Li

State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University,
No.28, Xianning West Road, Xi'an, Shaanxi, 710049, China
*E-mail: lijy@mail.xjtu.edu.cn

Abstract: Investigation on the dielectric properties of were calcined for 10 h at 950℃ in air and then The
CaCu3Ti4+xO12+2x was carried out when x was altered in polycrystalline powder was pressed into the pellets of
the range from -0.5 to 0.5. For x= -0.5, it was found 12mm diameter and 1.6mm thickness at the pressure
through XRD that besides primary CCTO phase, there of 85MPa using PVA as binder. The pressed pellets
are also CuO and CaTiO3 phases. For x= 0.5, additional were slowly heated to 500℃ to get rid of the binder
TiO2 was found besides dominating CCTO phase. When and were then sintered in air at 1100℃ for 20h.
x increases from -0.5 to 0.5, it was found that dielectric Sintered pellets were polished and thermally etched
constant decreases, varistor voltage and non-linear for microstructural observation. Polished smooth
coefficient increase while the dielelctric loss decreases. parallel surfaces were sputtered with gold to carry out
According to IBLC theory, it is suggested that the electric and dielectric properties.
change of the grain boundary structure results in
different barrier height and surface state when x The formation of the compound was confirmed via
changes. X-ray powder diffraction (XRD) using Cu Ka radiation.
The microstructural features and grain size distribution
INTRODUCTION in sintered pellets were studied by OLYMPUS BX51M
Polarized light microscopy. The I-V relation was
It has been found that ACu3Ti4O12 types of oxide measured by HEWLETT-34401A multimeter and
crystals exhibit a extremely high dielectric constant WWWL-LDG precision linear high-voltage and direct
[1]
, the most notable features[2][3][4] can be current power. The dielectric properties were carried out
demonstrated by the CaCu3Ti4O12. A large number of at 1 V over the frequency range from 0.1 Hz to 10 MHz
experimental data show that the dielectric constant of using the Broadband Dielectric Spectrometer made in
CaCu3Ti4O12 will be over 10000 at 1kHz , in this Germany.
paper it reaches 28800 at room temperature when the
the frequency is 2kHz. According to pertinent RESULT AND DISCUSSION
literature it is reported that copper deficit will lead to
relatively low dielectric constant [5],but there are Structural and microstructural analyses
seldom literature involving the effect of Ti content on
the electric and dielectric properties of CCTO.
Therefore, this paper will analyse its dielectric
properties by changing the Ti content and try to make
use of IBLC theoretics to explain the experimental
result. It is well known barrier layer capacitor
production usually requires complicated technology,
if CCTO can be used as these components then it can
greatly reduce the difficulty of its production process.
However, this ultimate solution will require aborative
studies of CaCu3Ti4O12 ceramic and CaCu3Ti4O12
single crystal.

EXPERIMENT

Appropriate amounts of high-purity CaCO3
(>99%),CuO (>99%), and TiO2 (>99%) were used to
prepare CCTO with different Ti stoichiometry
according to CaCu3Ti4+xO12+2x (x = -0.5，0 and 0.5),
the solid-state reaction formula is as follows.
CaCO3 + 3CuO + (4+x)TiO2 ĺ CaCu3Ti4+xO12+2x + CO2Ĺ
These raw materials were mixed in a ball mill with
ZrO2 balls for 4 h. After drying, the mixed powders
Fig. 1. X-ray powder diffraction pattern for CaCu3Ti4+xO12+2x
The XRD powder pattern obtained for CaCu3Ti4+xO12+2x
is shown in Fig. 1. It clearly shows they all obtain the
dominating CCTO phase especially for x= 0. So it can
be considered the sintered parameter are comparatively
appropriate to let the solid-state reaction developing
much thorough. For x= -0.5, it was found through XRD
that besides primary CCTO phase, there are also CuO

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 Fig. 2. Optical micrographs of CaCu3Ti4+xO12+2x ceramics at 2000x (a) x = -0.5, (b) x = 0 and (c) x = 0.5
Table.1. Electrical characterization at room temperature
Varistor Non-linear
x voltage coefficient
E1mA(V/mm) Į Ɏ(eV)
-0.5 29.7 2.33
0 48.1 4.03
0.5 128.8 6.33
and CaTiO3 phases(which is not shown in Fig.1). For x=
0.5, additional TiO2 was found besides the dominating
CCTO phase. However, the XRD results can easily be
understood since Ti stoichiometry is altered. Fig.2(a-c)
shows the opticl micrographs of CaCu3Ti4+xO12+2x pellets
for x= -0.5, 0 and 0.5 respectively. It is evident from
these micrographs that the average grain size is
decreased when x was increased in the range from -0.5 to
0.5. For Fig.2.(a) , the larger grain size maybe due to the
excess CuO liquid phase during the sintering process.
For Fig.2.(c), the residual TiO2 may exsit at the
intergranular region and prevent the grain growth process
which lead to smaller grain size. It was reported[6]
Cu-excess CaCu3Ti4O12 ceramics will result in abnormal
grain growth (AGG) behavior. On the contrary, AGG
was primarily found from Fig.2 (b) and (c) which
indicate Ti-excess will also result in AGG. Two
important parameters should be considered in AGG are
the excess TiO2 or air hole that suppress the continuous
grain growth, and the exorbitant calcined temperature.
These two parameters have the chance to induce
recrystallization and trigger the AGG. Take consideration
of above, the microstructural differences are expected to
have significant influence on the dielectric properties, the
details of which will be elucidated in the following
sections.
I-V characteristic analysis
It is known the conductance of solid dielectric can be
divided into ion conductivity and electronic conductivity
according to the types of charged carrier. In the lower
electric filed, ion conductivity is the main manner,
Which can be described[7] as Ȗ = Ȗ0* exp (- Ɏ/țT), where
Ȗ is the conductivity, Ȗ0 the preexponential factor, Ɏ the
activation energy, and ț the Boltzmann constant.
Fig.3. shows an Arrhenius plot of conductivity data for
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Conductance Dielectric constant
barrier Tanį
50 Hz 100 kHz
at 1 kHz
0.48 56100 23700 0.196
0.58 35000 20800 0.096
0.66 24400 15700 0.074
CaCu3Ti4O12 , the fit result reveals the conductance
barrier is 0.58 eV. It can also be found two activation
energy of 0.48 eV and 0.66 eV was achieved for x = -0.5
and 0.5 samples respectively in the same way , which are
clearly shown in table.1. The larger conductance barrier
indicates the more stability of the charged carriers which
need more energy to move through the barrier . As x was
increased from -0.5 to 0.5, the conductance barrier Ɏ
become larger, so the charged carriers have more
difficulty in transporting when Ti stoichiometry is larger.
From Table.1, with x increasing it clearly exhibits that
the varistor voltage and non-linear coefficient are
behaving in the same trend as the conductance barrier
Fig.3. Arrhenius plot of conductivity data for CaCu3Ti4O12
increasing from 0.48eV to 0.66eV when x increases from
-0.5 to 0.5, the varistor voltage and non-linear coefficient
increase from 29.7 V/mm, 2.33 to 128.8 V/mm, 6.33
respectively. According to the XRD and microstructural
analyses, for x =-0.5, there will be excess-CuO
distributing along the grain boundary. Some literature
reported[8] partial CuO can be deoxidized as
semiconducting Cu2O resulting in the more conductive
carriers, therefore the conductance barrier, varistor
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 voltage and non-linear coefficient is decreased. For x =
0.5, the inverse reaction may be ascribed to the
excess-TiO2 gathering along the grain boundary and
larger number of grain boundaries that impede the
migration of the charged particles and the outcome is
well agreed with Lin’s results[9].
Dielectric property measurement
Fig.4. Frequency dependence of dielectric constant İ’ at 293K for
CaCu3Ti4+xO12+2x while inset plot indicates İ’’- f relationship
Fig.5. Frequency dependence of dielectric loss angle
The variation in the real (İ’) and imaginary parts (İ’’) of
the dielectric constant with frequency at 293K for the
CaCu3Ti4+xO12+2x samples is shown in Fig.4. All the
samples exhibited reasonably high dielectric constants
and its value maintains a good stability during the
frequency range from 0.1 Hz to 100 kHz. The detailed
data at certain frequency are shown in Table.1. The
sample for x = 0.5 shows the lowest value of about
15700 (at 100 kHz), and the one for x = -0.5 shows the
highest value of about 23700, while the sample for
normal CCTO sample has an intermediate value. From
the inset of Fig.4 it can easily be illustrated that the
dielectric relaxation is visible with x increasing and for x
= 0.5 the dielectric loss is much smaller which are clearly
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showed in Fig.5. Now we consider the BLC structured
CaCu3Ti4+xO12+2x ceramics consisting of semiconducting
grains and insulating grain boundaries[10]. According to
the IBLC theory【11】，the effective dielectric constant İeff
can be expressed as İeff § İgb tg / tgb, here tg is the
grain size, tgb is the boundary-layer thickness, and İgb is
the dielectric constant of the boundary layer. As for the
optical micrographs of Fig.2, for x=0.5, the tg is much
smaller thus its dielectric constant is at the lower value .
Therefore, the IBLC mode can be successfully used to
explain the law the dielectric constant altered when x
changes.
Fig.6. Equivalent circuit used to represent the electrical properties of
grain and grain-boundary effects.
Fig.7. Frequency dependence of conductivity at 293K
To analyze the conduction , data usually are modeled by
an ideal equivalent circuit consisting of a resistor R and
a capacitor C. The circuit consists of a series array of
two subcircuits, one represents grain effects and the
other represents grain boundaries. Each subcircuit is
composed of a resistor and capacitor joined in parallel.
Let (Rg, Rgb) and (Cg, Cgb) be the resistances and
capacitances of grains and grain boundaries respectively,
then the impedance Z* for the equivalent circuit[12] in
Fig. 6 is shown above. From the above analysis, it is
reasonablely considered that Rg<<Rgb and Cg<<Cgb, so it
is concentrated expression of the grain boundary
impedance Rgb when the frequency is low enough and
the main performance is occured in the grain when the
frequency is much high. Therefore, from Fig.7, it can be
considered that the conductivity of grain boundary
distinctly decreases and the value of grain almost
unchanged when x increases from -0.5 to 0.5 for
CaCu3Ti4+xO12+2x ceramic. When an electric field is
applied to such a system, migration of charge carriers
occurs readily through the grain but is impeded when
 they reach the grain boundaries, so the loss of
CaCu3Ti3.5O11 is much larger because of its larger
quasi-DC conductivity. Therefore, it can be illuminated
that the barrier height and its grain boundary insulating
state are altered when Ti stoichiometry is changed.
CONCLUSIONS
In conclusion, CaCu3Ti4+xO12+2x ceramics with x = -0.5,0
and 0.5 have been prepared by a solid-state sintering
method. Phase composition analyses finds that CuO and
TiO2 phases are present for x = -0.5 and 0.5 respectly.
Then the I-V and dielectric characteristic indicates the
excess-TiO2 in CaCu3Ti4+xO12+2x ceramics can improve
the varistor voltage and non-linear coefficient but obtain
relatively low dielectric constant, then the excess-CuO
will result in the reversed reaction that the varistor
voltage and non-linear coefficient decrease as 29.7V/mm
and 2.33 for x = -0.5 that oppose to 128.8V/mm and 6.33
for x = 0.5. The experimental data shows the dielectric
loss is decreasing as x increases when the frequency is
less than 10kHz and all of this CaCu3Ti4+xO12+2x ceramics
exhibit high dielectric constant. Here the IBLC mode can
be effectively used to explain the difference when x is
altered. It is suggested that x = 0.5 for CaCu3Ti4+xO12+2x
is beneficial for its integrative electric and dielectric
properties, and it can further be pointed out that
moderately excessed TiO2 is beneficial for CaCu3Ti4O12’s
varistor property.
Bulletin 43 (2008) 284–291
[7] Ji-dan Chec, Zi-yu Liu. Dielectric physics.
Machinery Industry Press, Pekin ,1982
[8] Sung-Yoon Chung etc. Initial cation stoichiometry
and current-voltage behavior in Sc-doped calcium copper
titanate. APPLIED PHYSICS LETTERS 89, 191907
(2006)
[9] Yuan-Hua Lin, Jingnan Cai etc. High dielectric and
nonlinear electrical behaviors in TiO2-rich CaCu3Ti4O12
ceramics. APPLIED PHYSICS LETTERS 88, 172902
(2006)
[10] Jianjun Liu, Yucheng Sui etc. CaCu3Ti4O12:
Low-Temperature Synthesis by Pyrolysis of an Organic
Solution. Chem. Mater. 2006, 18, 3878-3882
[11] B. Shri Prakash, K.B.R. Varma. Effect of sintering
conditions on the dielectric properties of CaCu3Ti4O12
and La2/3Cu3Ti4O12 ceramics: A comparative study.
Physica B 382 (2006) 312–319
[12] D. C. Sinclair and A. R. West. Impedance and
modulus spectroscopy of semiconducting BaTiO3
showing positive temperature coefficient of resistance. J.
Appl. Phys. 66, 3850 (1989).

ACKNOWLEDGEMENTS

This work was supported by the National Natural

Science Foundation（Grant No.50747047）and Program
for New Century Excellent Talents in University (Grant
No.NCET-07-0607).

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