Preparation and Dielectric Properties of CaCu

3
Ti
4
O
12
Ceramics with Different Additives
Juanjuan Wang, Lajun Feng, Ali Lei, Kang Zhao, and Aijun Yan
(Submitted May 3, 2012; in revised form March 10, 2014; published online June 6, 2014)
Li
2
CO
3
, MgCO
3
, BaCO
3
, and Bi
2
O
3
dopants were introduced into CaCu
3
Ti
4
O
12
(CCTO) ceramics in order
to improve the dielectric properties. The CCTO ceramics were prepared by conventional solid-state
reaction method. The phase structure, microstructure, and dielectric behavior were carefully investigated.
The pure structure without any impurity phases can be conrmed by the x-ray diffraction patterns.
Scanning Electron Microscopy (SEM) analysis illuminated that the grains of Ca
0.90
Li
0.20
Cu
3
Ti
4
O
12
ceramics were greater than that of pure CCTO. It was important for the properties of the CCTO ceramics
to study the additives in complex impedance spectroscopy. It was foundthat the Ca
0.90
Li
0.20
Cu
3
Ti
4
O
12
ceramics had the higher permittivity (>45000), the lower dielectric loss (<0.025) than those of CCTO at
1 kHz at room temperature and good temperature stability from 230 to 75 C.
Keywords CaCu
3
Ti
4
O
12
ceramics, dielectric properties, phase
structure
1. Introduction
As we know, high dielectric constant is desirable to
miniaturize capacitor required for integrated circuits (Ref 1,
2). The pseudo-perovskite type CaCu
3
Ti
4
O
12
(CCTO) has
attracted much attention, not only because of the numerous
potential technological applications of the materials with such
properties, but also because of the origin of the giant dielectric
constant (Ref 3-5). Such properties are essential for the
components involved in charge storage capacitors and memory
devices (Ref 6). It shows colossal dielectric constant (CDC) at
room temperature and is weakly temperature dependent in the
frequency range between dc and 10
6
Hz (Ref 7-10).
There are many methods to improve the electrical properties
of CCTO including substitution, doping, and two-phase
composites, such as Ca
1x
La
x/3
Cu
3
Ti
4
O
12
(Ref 11, 12),
Cr
2
O
3
-doped CCTO (Ref 13), BaTiO
3
-CCTO (Ref 14),
CaCu
3x
Sr
x
Ti
4
O
12
(Ref 15), and SrTiO
3
-CCTO. However,
the main problems for their application are its high dielectric
loss and large leakage current. In order to solve this problem,
there have been some studies concerning with the CCTO bulk
material by using the composite routes. Patterson et al. reported
that the 0.5 wt.% ZrO
2
-doped CCTO ceramic exhibited low
dielectric loss over the frequency range from 50 Hz to 30 KHz
(Ref 16). Sulaimana et al. also investigated that the dielectric
loss and the low frequency dispersion of CCTO ceramics were
both reduced by B
2
O
3
addition (Ref 17). All these studies
mentioned decreased dielectric loss by controlling the compo-
sition and structure of interfacial regions at grain boundaries. It
is very necessary to investigate the dopants on room temper-
ature dielectric properties of CCTO ceramics and their temper-
ature dependence for obtaining giant dielectric constant with
better temperature stability.
In this work, the pure and doped CCTO ceramics were
prepared by the solid-state reaction method. The phase
structure, microstructure, and dielectric properties of the pure
and doped CCTO ceramics were investigated. Li
2
CO
3
, MgCO
3
,
BaCO
3
, and Bi
2
O
3
dopants were chosen primarily due to their
different preferential substitutions on Ca sites, which could
change the microstructure and the electrical properties of
CCTO. Temperature dependence of dielectric properties of the
pure and doped CCTO ceramics was also discussed.
2. Experimental
Ca
0.90
Li
0.2
Cu
3
Ti
4
O
12
(CCTO-1), Ca
0.90
R
0.10
Cu
3
Ti
4
O
12
(R = Mg and Ba) (CCTO-2 and CCTO-3), and Ca
0.90
Bi
0.1/3
Cu
3
Ti
4
O
12
(CCTO-4) powders were synthesized via the
conventional solid-state reaction method from high-purity
CaCO
3
, CuO, TiO
2
, BaCO
3
, MgCO
3
, Li
2
CO
3
, and Bi
2
O
3
.
The stoichiometry powders were mixed by ball milling in
ethanol for 16 h, then dried, and calcined at 900 C for 10 h.
The calcined powders were mixed with 5 wt.% polyvinyl
alcohol (PVA) solutionand then pressed into pellets with a
diameter of 15 mm in diameter and about 0.7 mm in thickness
under 100 MPa pressure. After burning off PVA at 500 C for
2 h, the samples were sintered at 1100 C for 24 h. Silver paste
was red at 800 C on both faces of the samples as the
electrodes. The electrical properties of all ceramics were
measured more than 24 h later.
The crystalline structure and microstructure of the sintered
specimens were characterized by x-ray diffraction (D/max-
2550/PC, Rigaku, Japan) and scanning electron microscopy
Juanjuan Wang, Lajun Feng, Ali Lei, and Kang Zhao, Shaanxi
Province Corrosion and Protection Key Laboratory, Advanced
Ceramic Material Laboratory, School of Materials Science and
Engineering, Xian University of Technology, Xian 710048 Shaanxi,
P.R. China; and Aijun Yan, Shaanxi Electric Power Research Institute,
Xian 710054 Shaanxi, P.R. China. Contact e-mail: juanwang@xaut.edu.cn.
JMEPEG (2014) 23:31333140 ASM International
DOI: 10.1007/s11665-014-1024-6 1059-9495/$19.00
Journal of Materials Engineering and Performance Volume 23(9) September 20143133
(SEM, Quanta 200, Philips, Netherlands), respectively. An
energy dispersive x-ray spectroscopy (EDS) and x-ray Photo-
electron Spectroscopy (XPS) were used to analyze the chemical
compositions. The electrical properties of the sintered samples
were measured by Agilent 4294A impedance analyzer in the
frequency range from 40 Hz to 110 MHz.
3. Results and Discussion
3.1 XRD of the CCTO Powder
Figure 1 shows the x-ray diffraction patterns of the CCTO
powder with different additives calcined at 900 C. As can be
seen on the plots, all diffraction peaks were matched with known
peaks of the pseudo-cubic-structured CCTObased on the Powder
Diffraction File data (PDF #75-2188). With increasing reaction
temperature, Li
2
CO
3
, MgCO
3
, and BaCO
3
form oxides (Li
2
O,
MgO, BaO) at rst and then diffuse into the crystal structure of the
pseudo-cubic-structured CCTO ceramics with no traces from
other impurity phases, demonstrating that a solid solution has
been formed. The curves of CCTO-1, CCTO-2, CCTO-3, and
CCTO-4 ceramics are almost identical with that of pure CCTO.
That is to say, lithium-, magnesium-, barium-, and bismuth-
related phases are not observed in the XRD patterns for doped
samples. In order to further determine the presented phase in
Fig. 1 and composition of the materials, the EDS and XPS
analyses are applied, and the results are shown in Fig. 1. The
results indicate that the element mole ratios of the grain surface of
CCTO, CCTO-2, and CCTO-3 are Ca:Cu:Ti = 1:3.03:4.06,
1:0.08:3.00:4.06, and 1:0.09:3.05:4.02, which are nearly stoi-
chiometric for CaCu
3
Ti
4
O
12
(CCTO), Ca
0.90
Mg
0.10
Cu
3
Ti
4
O
12
(CCTO-2), and Ca
0.90
Ba
.10
Cu
3
Ti
4
O
12
(CCTO-3), respectively.
Though Li element cannot be detected by EDS and XPS, the
result displays that the element mole ratio of the grain surface of
CCTO-1 is Ca:Cu:Ti = 0.91:3.07:4.00, which is close also to
stoichiometric of Ca, Cu, and Ti elements of Ca
0.90
Li
0.20
Cu
3
Ti
4
O
12
(CCTO-2). It is observed in EDS that the element mole
ratio of CCTO-4 is Ca:Cu:Ti = 0.98:3.08:4.00. Moreover, it is
also noted that the element mole ratio of CCTO-4 is Ca:Bi:
Cu:Ti=0.99:0.02:3.07:4.00. They are nearly stoichiometric for
Ca
0.90
Bi
0.10/3
Cu
3
Ti
4
O
12
(CCTO-4), respectively. The results are
good agreement with the XRD analysis obtained in Fig. 1.
It could be inferred that the lithium, magnesium, barium,
and bismuth atoms have entered the lattice and almost taken
place of some calcium atom, which indicate that the lithium,
magnesium, barium, and bismuth atoms almost did not
inuence the crystalline structure. Through the solid-state
reaction method, the reaction of the three starting materials,
CaCO
3
, CuO, and TiO
2
can produce CaCu
3
Ti
4
O
12
(Ref 16).
The chemical reaction involved is
CaCO
3
3CuO 4TiO
2
! CaCu
3
Ti
4
O
12
CO
3
Eq 1
Substituting, doping and two-phase composites are the main
methods employed to decrease dielectric loss of the ceramics.
In the case of CCTO, a doping process using Li
+
, Mg
2+
, Ba
2+
,
and Bi
3+
ions can substitute the Ca
2+
site in order to improve
the dielectric properties of CCTO. The chemical composition of
Li
2
CO
3
, MgCO
3
, BaCO
3
, and Bi
2
O
3
-doped CCTO is
1 xCaCO
3
3CuO 4TiO
2
xLi
2
CO
3
!Ca
1x
Li
2x
Cu
3
Ti
4
O
12
Eq 2
1 xCaCO
3
3CuO 4TiO
2
xMgCO
3
!Ca
1x
Mg
x
Cu
3
Ti
4
O
12
Eq 3
1 xCaCO
3
3CuO 4TiO
2
xBaCO
3
!Ca
1x
Ba
x
Cu
3
Ti
4
O
12
Eq 4
1 xCaCO
3
3CuO 4TiO
2
xBi
2
O
3
!Ca
1x
Bi
x=3
Cu
3
Ti
4
O
12
Eq 5
Addition of dopants can also improve densication and
increase lattice diffusivity of ions during the process. This
reason may be that ionic radius of R is close to ( r
Ba
2
1:43 A

), or smaller than ( r
Bi
3 1:03 A

, r
Mg
2 0:57 A

,
r
Li
0:76 A

) that of Ca
2+
( r
Ca
2 = 1.34 A

); furthermore, Li
+
,
Mg
2+
, Ba
2+
, and Bi
3+
enter into a cubic perovskite structure
lattice, forming a continuous solid solution (Fig. 2).
3.2 Microstructure and Electrical Property of the CCTO
Ceramics
Figure 3 displays SEM images of surface microstructure for
the samples with different additives. It can be found that from
Fig. 3(a) and (b), the grain of undoped and 10 mol.% Li-doped
CCTO demonstrated a rather big but uniform size and a clear
grain boundary. Moreover, the grain size of CCTO-1 ceramics
is greater and more uniform than pure CCTO. Obviously, they
show the microstructure distributed uniformly with the grain
size, abnormal grow grains, and the clear grain boundaries.
Fritsh et al. (Ref 18) reported that the huge grains observed for
the pure CCTO, which contain CuO are also probably related to
the appearance of a liquid phase that wets the grain during
sintering. Small amounts of CuO are believed to be responsible
for the abnormal grain growth of pure CCTO ceramics (Ref
19). The density of grainboundaries induced by the improved
grain size in the Li-doped CCTO ceramics is smaller than that
in the pure CCTO ceramic. It should be pointed out that Li
2
CO
3
with low melting temperature plays also an important role in
Fig. 1 X-ray diffraction patterns of the CCTO powder with different
additives calcined at 900 C
3134Volume 23(9) September 2014 Journal of Materials Engineering and Performance
liquid phase sintering. So, the Li-doped CCTO ceramics with
highly enhanced surface morphology were obtained (Ref 20).
Therefore, the grain size of CCTO-1 ceramics is greater and
more uniform than pure CCTO. Grain sizes of undoped and Li-
doped CCTO ranged from 30 to 400 lm. The key factor for the
abnormal grain growth is the presence of an intergranular liquid
phase during the sintering process (Ref 15). The literature has
also determined that the liquid phase of 5 and 10 mol% Nb-
doped CCTO at 1040 C promotes abnormal grain growth and
provides an enhanced diffusion path for abnormal grain growth
(Ref 16). However, MgCO
3
-, BaCO
3
-, and Bi
2
O
3
-doped CCTO
(with 10 mol.%) produced ne grains (Fig. 3c-e). Furthermore,
the grain size of CCTO-4 and CCTO-5 ceramics is smaller, and
the abnormally large grains gradually disappear. The presence
of Mg
2+
, Ba
2+
, and Bi
3
may decrease the abnormal grain
growth phenomena. We found that the abnormal grain growth
can be reduced by the addition of MgCO
3
, BaCO
3
, and Bi
2
O
3
.
As noted by Moulson and Herbert (Ref 14), donor dopants such
as Mg
2+
, Ba
2+
, and Bi
3+
have potential to reduce oxygen
vacancies which will lowerthe diffusion of oxygen ions through
the crystal lattice. The other reason can be thought that dopants
of small radius ionic ( r
Li
0:76 A

) can advance the growth

of grain size. The change of microstructure signicantly alters
the dielectric properties. According to the simple series-layer
Fig. 2 EDS and XPS analyses of the CCTO powder with different additives
Journal of Materials Engineering and Performance Volume 23(9) September 20143135
model for the BLC, the dielectric constant of the ceramic
specimens can be simply expressed as
e
r
e
b
d=t; Eq 6
where d (see the SEM image in the inset of Fig. 3) is the
grain size, t (about a few nanometers) is the boundary-layer
thickness, and e
b
is the dielectric constant of the boundary
layer and is roughly 10-50 estimated from measured e. From
this point of view, the dielectric constant e of the bulk ceram-
ics increases with increasing d (Li-doped CCTO ceramics)
(Ref 20). Therefore, abnormal grain growth must be con-
trolled in order to obtain a large and reproducible dielectric
constant. Figure 4 shows such a increase in the dielectric con-
stant with the Li addition.
On the other hand, the Li content has a remarkable effect on
the dielectric constant of the CCTO specimens, as shown in
Fig. 4. In the grain interiors, the carrier concentration rises with
increasing Li concentration, and more charges accumulate at
the two sides of the boundary layers, which are responsible for
the higher dielectric constant of the specimens. Figure 4 shows
Fig. 3 SEM images of surface microstructure for the samples with different additives
3136Volume 23(9) September 2014 Journal of Materials Engineering and Performance
the frequency vs. permittivity (e
r
) and frequency vs. dielectric
loss (tan d) of the samples with different additives at room
temperature. The dielectric behaviors of the samples are similar
to the reported results. Especially, they all have a Debye-like
relaxation with a steep decrease in e
r
at the frequency where tan
d displays a relaxation peak, and e
r
isindependent of the
frequency and temperature over a wide range. Figure 4(a)
reveals that the permittivity of the samples decreases gradually
with difference of ion from Li
+
, Mg
2+
, Ba
2+
to Bi
3+
. The
dielectric permittivity for the CCTO-1 ceramics is slightly
higher than that of the pure CCTO ceramics. The e
r
of CCTO-2
ceramics and pure CCTO ceramics is more than 4.7 910
4
in
the frequency range of 40-4.0 910
5
Hz. Furthermore, the e
r
of
CCTO-1 ceramics is bigger than that of the pure CCTO
ceramics at the same frequency, but CCTO-2, CCTO-3, and
CCTO-4 ceramics are not. Figure 4(b) shows the frequency
dependence of tan d of the samples at room temperature. It
exhibits that the dielectric losses of CCTO-1, CCTO-2, CCTO-
3, and CCTO-4 ceramics gradually increase in the frequency
range of 1.6 910
6
-5.6 910
7
Hz and reduce after that. CCTO-1
ceramics are of the biggest tan d but the same as pure CCTO
ceramics. It is well known that the electrical properties of
CCTO-based ceramics depend strongly on additives (nature
and amount of dopant concentrations). The different elements
play different role: two types of dopants (acceptor and donor).
Donor dopant is dened as dopant elements with a higher ionic
charge than ions they replace, causing cation vacancies (Ref
21). Cation vacancies tend to be separated by oxygen ions so
that there is a considerable energy barrier to be overcome
before the ion and its vacancy can be interchanged. The oxygen
ions, however, form a continuous lattice structure, and the
oxygen vacancies have oxygen ion neighbors which they can
easily exchange, increasingconductivity. Donor-cation vacancy
combinations can be assumed to have a stable orientation so
that their initially random state is unaffected by spontaneous
polarization or applied elds. Acceptor-oxygen vacancy com-
binations are likely to be less stable, and thermally activated
reorientation may take place in the presence of local or applied
elds. The dipoles, once oriented in a common direction, will
provide a eld, stabilizing the domain structure (Ref 22). These
may result from the change of the properties of the ceramics.
3.3 Complex Impedance Analysis
In order to interpret the origin of giant dielectric properties
for CCTO, several possible mechanisms have been reported.
Specially, Sinclair and colleagues have used impedance
spectroscopy (IS) to establish the electrical microstructure of
CCTO ceramics and have shown them to be electrically
inhomogeneous, containing semiconducting grains with insu-
lating grain boundaries. The complex impedance spectroscopy
is a powerful tool in separating out the grain and the grain
boundary effects. Hence, the impedance spectroscopy is
measured for the samples with different additives.
Figure 5 shows complex impedance spectroscopy for the
samples with different additives around room temperature. It
can been seen in Fig. 5, the complex impedance plots for all
ceramics show a large semicircular arc and a small semicircular
arc within the measuring frequency range of 40 Hz-110MHz at
room temperature, which indicate that all samples are electri-
cally heterogeneous. As we know, all impedance data can be
modeled on an equivalent circuit based on two parallel (resistor,
R, and capacitor, C) elements connected in series. For such a
circuit, each RC element ideally gives rise to semicircular arc in
complex impedance plane Z*. For one parallel RC element,
Z(x), Z(x), and Z(x) can beexpressed as
Z x
R
1 ixCR

R
1 xCR
2
i
xR
2
C
1 xCR
2
Z
0
x iZ
00
x Eq 7
Z
0
x
R
1 xCR
2
Eq 8
and
Fig. 4 The frequency vs. permittivity (e
r
) and frequency vs. dielectric loss (tan d) of the samples with different additives at room temperature
Fig. 5 Complex impedance spectroscopy for the samples with dif-
ferent additives around room temperature
Journal of Materials Engineering and Performance Volume 23(9) September 20143137
Z
00
x
xR
2
C
1 xCR
2
Eq 9
Equivalent circuit models have been previously suggested to
explain the experimental results of dielectric and electric
properties for CCTO ceramics, which one element corre-
sponds to semiconducting grains (R
g
C
g
), and the other corre-
sponds to insulating grain boundaries (R
gb
C
gb
).
For two parallel RC elements connected in series, Z(x),
Z(x), and Z(x) can be expressed as
Z x
R
g
1 ixC
g
R
g

R
gb
1 ixC
gb
R
gb
Eq 10
so
Z
0
x
R
g
1 xC
g
R
g

2

R
gb
1 xC
gb
R
gb

2
Eq 11
and
Z
00
x
xR
2
g
C
g
1 xC
g
R
g

2

xR
2
gb
C
gb
1 xC
gb
R
gb

2
; Eq 12
where R and C are the resistance and capacitance, respec-
tively, the subscripts g and gb refer to the grains and grain
boundaries, respectively, and x is the angular frequency.
Based on Eq 12, the response peaks of the grains and grain
boundaries are located at 1/(2pR
g
C
g
) and 1/(2pR
gb
C
gb
),
respectively, and the peak value is proportional to associated
resistance. In general, the peak frequency for grain boundaries
is much lower than that for grains due to their large resistance
and capacitance compared with those of grains (Ref 23).
Therefore, in the impedance spectra, we attribute the higher
frequency response, which corresponds to the small arc in
Fig. 4, to the grains, and the lower one to the grain bound-
aries.
The data for CCTO with different additives show two clear
semicircular arcs in the complex impedance spectroscopy,
corresponding to the two parallel RC elements in series,
indicating that higher permittivity is due to the internal barrier
layer capacitance (IBLC) model (Ref 3). The nonzero intercept
is attributed to the grain resistance R
g
of 10.17, 6.80, 9.25, and
6.64 Xcm when the additives are Li
2
CO
3
, MgCO
3
, BaCO
3
,
and Bi
2
O
3
, respectively. Generally, as shown in Fig. 4, the
grain resistance R
g
is much smaller than the boundary
resistance R
gb
. This result is consistent with the IBLC modelas
a basis to display the effect of different additives on the
electrical properties of the CCTO ceramics.
3.4 Temperature Stability
Figure 6 shows temperature dependence of dielectric prop-
erties of the specimens with different additives at 1 kHz in the
range of 50 to 150 C. Figure 6(a) shows that dielectric
Fig. 6 Temperature dependence of dielectric properties of the specimens with different additives at 1 kHz in the range of 50 to 150 C
Fig. 7 The dielectric properties of Ca
0.90
Li
0.20
Cu
3
Ti
4
O
12
ceramics with different frequencies in the range of 100 to 200 C
3138Volume 23(9) September 2014 Journal of Materials Engineering and Performance
constant for all ceramics is gradually increasing with temper-
ature increasing at 1 kHz. As is shown in Fig. 6(a), CCTO-1
ceramics show higher permittivity (9.5 910
4
) at 1 kHz. And
CCTO-1 ceramics display lower dielectric loss at the range of
50 to 150 C in Fig. 6(b). All the ceramics have good
temperature stability from 50 to 150 C. The results of Fig. 6
show that the CCTO-1 ceramics have higher permittivity with
good temperature stability.
To sum up, the results indicate that Ca
0.90
Li
0.20
Cu
3
Ti
4
O
12
(CCTO-1) ceramics have good dielectric properties and good
temperature stability at 1 kHz. Dielectric constant for Ca
0.90-
Li
0.20
Cu
3
Ti
4
O
12
ceramics is more than that of CCTO and
dielectric loss is below that of CCTO at 1 kHz in the range of
50 to 150 C. In general, Li
+
ion mainly replaces Ca
2+
ions in
the A sites of ACu
3
Ti
4
O
12
structure from the charge point of
view. Acceptor ions such as Li
+
on Ca
2+
sites give rise to
oxygen vacancies. The oxygen ions are usually less mobile than
cation; thus, a dopant favoring anincrease in the oxygen
vacancy may promote densication. Acceptor ions have the
effect of shifting the minimum conduction band to lower
oxygen pressures, so that the concentration of electrons in the
conduction band is reduced and positive holes in the valence
band become the majority carriers at oxygen pressures. The
oxygen vacancies and space charges (electrons) are produced in
the grain boundaries, resulting in higher conductivity. Thereby,
they also increase the properties of the ceramics (Ref 24).
Figure 7 indicates the dielectric properties of Ca
0.90
Li
0.20-
Cu
3
Ti
4
O
12
ceramics with different frequencies in the range of
100 to 200 C. Figure 7(a) reveals that the bigger dielectric
constant can be acquired at the frequency of 1 Hz for
Ca
0.90
Li
0.20
Cu
3
Ti
4
O
12
ceramics in the range of 100 to
200 C. Interestingly, dielectric relaxations are clearly observed
in Fig. 7(a). The relaxation shows step-like increase in with
increasing temperature, which shifts to higher temperatures
with increasing frequency. The behavior of relaxations indi-
cates that the dielectric relaxations are the frequency
(<10 kHz), it is presumed that it could beassociated with
surface layers interfacial polarization, and the similar result was
reported (Ref 6, 23). From Fig. 7(b), we can nd that there is
lower dielectric loss in the range of 30 to 75 C for
Ca
0.90
Li
0.20
Cu
3
Ti
4
O
12
ceramics at 1 Hz. So, the best service
condition for Ca
0.90
Li
0.20
Cu
3
Ti
4
O
12
ceramics is 30 to 75 C,
1 Hz.
4. Conclusions
Ca
0.90
Li
0.2
Cu
3
Ti
4
O
12
(CCTO-1), Ca
0.90
R
0.10
Cu
3
Ti
4
O
12
(R =
Mg and Ba) (CCTO-2 and CCTO-3), and Ca
0.90
Bi
0.1/3
Cu
3
Ti
4
O
12
(CCTO-4) giant dielectric ceramics were prepared by the
conventional solid-state reaction method. The x-ray diffraction
patterns show that all samples obtained a pure phase, and there
is no second phase. Scanning Electron Microscopy analysis
shows that the grains of Ca
0.90
Li
0.2
Cu
3
Ti
4
O
12
ceramics are
greater than that of pure CCTO, and then the grains of Ca
0.90
R
0.10
Cu
3
Ti
4
O
12
(R = Mg and Ba) and Ca
0.90
Bi
0.1/3
Cu
3
Ti
4
O
12
ceramics gradually decrease in the order of Li
2
CO
3
, MgCO
3
,
BaCO
3
, and Bi
2
O
3
. The dielectric losses of the Ca
0.90
R
0.10
Cu
3
Ti
4
O
12
(R = Mg and Ba) and Ca
0.90
Bi
0.1/3
Cu
3
Ti
4
O
12
ceramics rst increase and then decreased. In conclusions, the
permittivity and the dielectric loss for the Ca
0.90
Li
0.2
Cu
3
Ti
4
O
12
specimens are higher and lower than that of pure CCTO at
1 kHz at room temperature, respectively. As shown in complex
impedance spectroscopy, it is important for the electrical
properties of the CCTO ceramics to study the additives.
Dielectric constant for Ca
0.90
Li
0.2
Cu
3
Ti
4
O
12
ceramics is more
than 45000, and dielectric loss for it is below 0.025 at 1 kHz in
the range of 30 to 75 C. These results indicate that the
Ca
0.90
Li
0.2
Cu
3
Ti
4
O
12
ceramics can exhibit lower dielectric loss
and good temperature stability.
Acknowledgment
This work was supported by the National Nature Science
Foundation of China (NSFC, 51174160) and the Natural Science
Foundation of Shaanxi Province in China (101-221206).
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