J Mater Sci: Mater Electron (2011) 22:345350
DOI 10.1007/s10854-010-0140-9
Effects of Nd-substitution on microstructures and dielectric
characteristics of CaCu3Ti4O12 ceramics
Ying Wang Lei Ni Xiang Ming Chen
Received: 13 April 2010 / Accepted: 18 May 2010 / Published online: 30 May 2010
Springer Science+Business Media, LLC 2010
Abstract Ca1-3x/2NdxCu3Ti4O12 (x = 0, 0.1, 0.2) ceram-
ics were prepared by a solid state reaction process,
and single-phased structures were obtained for all the
compositions. The dielectric characteristics of pure and
Nd-substituted CaCu3Ti4O12 ceramics were investigated
together with the microstructures. The mixed-valent struc-
tures of Cu?/Cu2? and Ti3?/Ti4? in the present ceramics
were confirmed by X-ray photoelectron analysis. The dielec-
tric relaxation in the low temperature range was examined in
detail and the variation of dielectric constant and dielec-
tric loss was attributed to the modification mixed-valent
structures.
1 Introduction
Recently, the perovskite-like CaCu3Ti4O12 has attracted
much scientific attention because of its extraordinary
dielectric properties. It indicates an enormously large
dielectric constant of *104 and keeps almost temperature-
independent from 100 to 400 K [1, 2]. CaCu3Ti4O12 shows
great potential in applications for the miniaturization of
Y. Wang  L. Ni  X. M. Chen (&)
Laboratory of Dielectric Materials, Department of Materials
Science and Engineering, Zhejiang University,
310027 Hangzhou, China
e-mail: xmchen59@zju.edu.cn
Present Address:
L. Ni
School of Materials Science and Engineering,
Changan University, 710061 Xian, China
microelectronic devices such as capacitors and memories
due to these unique characteristics.
So far, intensive investigations have been focused on the
origin of giant dielectric response in CaCu3Ti4O12 and the
modifications of its dielectric characteristics [117]. Vari-
ous explanations for the observed permittivity response
have been reported, such as local dipole moments associ-
ated with off-center displacement of Ti ions [2], relaxorlike
dynamical slowing of dipolar fluctuations in nanosize
domains [3], nanoscale disorder of Cu and Ca atomic
substitution [4], electrode depletion effects [5], structural
model of planar defects [6] and grain boundary (internal)
barrier layer capacitance (IBLC) mechanisms [7]. How-
ever, no mechanism is complete enough to explain the
similar dielectric response in both CaCu3Ti4O12 ceramics
and single crystals within low and high temperature range,
but some micro-scale inhomogeneities maybe considered
for further understanding. Besides, partial substitutions at
different sites in CaCu3Ti4O12 were attempted to improve
its dielectric properties. Reduced dielectric loss or
enhanced giant dielectric constant has been obtained in
partially substituted ceramics such as Ca0.8La0.2Cu3Ti4O12
[8], CaCu2.9La0.067Ti4O12 [9], CaCu2.7Zn0.3Ti4O12 [10],
CaCu2.7Mg0.3Ti4O12 [11], CaCu3Ti3.94Al0.06O11.97 [12] and
CaCu3Ti3.8Nb0.2O12.1 [13].
In the present work, the substitution of Nd for Ca in
CaCu3Ti4O12 ceramics is performed, and the effects of
Nd-substitution on the microstructures and dielectric
characteristics are discussed.
2 Experiment
Ca1-3x/2NdxCu3Ti4O12 (x = 0, 0.1, 0.2) ceramics were
prepared by a solid state reaction process using the starting
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materials of CaCO3 (99.99%), CuO (99%), TiO2 (99.5%),
and Nd2O3 (99.9%). The raw powders were mixed by ball
milling with zirconia media in ethanol for 24 h. The
powders were calcined at 950 C in air for 3 h and then
shaped to form cylindrical compacts of 12 mm in diameter
and 23 mm in height under a uniaxial pressure of 98 MPa.
Finally, the compacts were sintered at 1,100 C in air for
3 h to yield the dense ceramics.
The crystal phase was confirmed by powder X-ray dif-
fraction using Cu Ka radiation (2550/PC, Rigaku, Tokyo,
Japan). The microstructures were evaluated by scanning
electron microscopy (SEM, S-4800, Hitachi, Tokyo, Japan).
The element valences were examined by X-ray photoemis-
sion spectroscopy with Mg Ka radiation (hm = 1,253.6 eV)
Fig. 1 XRD patterns of Ca1-3x/2NdxCu3Ti4O12 (x = 0, 0.1, 0.2)
ceramics
Fig. 2 SEM images of
Ca1-3x/2NdxCu3Ti4O12 ceramics
with various compositions
a x = 0, b x = 0.1, c x = 0.2
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J Mater Sci: Mater Electron (2011) 22:345350
(XPS, RBD upgraded PHI-5000C ESCA system (Perkin
Elmer), USA). The experimental curves were fitted with a
program (XPSPEAK4.1) made use of a combination of
GaussianLorentzian lines. The dielectric characteristics of
the present ceramics were evaluated with a broadband
dielectric spectrometer (Turkey Concept 50, Novocontrol
Technologies, Germany) in a broader range of temperature
(128573 K) and frequency (1 Hz10 MHz), and silver
paste was adopted as the electrodes.
3 Results and discussions
XRD patterns of Ca1-3x/2NdxCu3Ti4O12 (x = 0, 0.1, 0.2)
ceramics are shown in Fig. 1. All the diffraction patterns
can be assigned to a cubic cell (space group Im3) and no
secondary phase is detected. Microstructures of the present
ceramics with various compositions are shown in Fig. 2.
Grain size decreases from *5 to *2 lm with increasing
Nd content. Some small pores are observed in CaCu3-
Ti4O12 ceramics because the density is a little lower than
the other two samples. The decreased grain size in the
present ceramics is due to that the grain growth is inhibited
by the solute atoms of Nd in CaCu3Ti4O12 lattices which
reduce the diffusion coefficient.
Figure 3 shows the frequency dependence of dielectric
constant and dielectric loss in Ca1-3x/2NdxCu3Ti4O12 (x =
0, 0.1, 0.2) ceramics at 298 and 128 K, respectively. At room
temperature, two significant dielectric relaxations are
observed in the low and high frequency ranges, while at
128 K, however, the low-frequency dielectric relaxation
J Mater Sci: Mater Electron (2011) 22:345350
Fig. 3 Frequency dependence
of dielectric constant and
dielectric loss of Ca1-3x/
2NdxCu3Ti4O12 ceramics with
various compositions at 298 K
(a, b) and 128 K (c, d)
almost disappears and the high-frequency dielectric relaxa-
tion still remains with the relaxation peak shifting towards
the low frequency side. With increasing Nd content, the
dielectric constant decreases at 298 K while the magnitude
of dielectric plateau for x = 0 is a little lower than that for
x = 0.1 at 128 K. The high-frequency dielectric loss is sig-
nificantly decreased but the low-frequency dielectric loss is
increased at 298 K, while the low-frequency dielectric loss is
significantly decreased at 128 K with increasing x. It should
be noted here that the low-frequency dielectric relaxation is
just active at higher temperatures, and the high frequency
dielectric relaxation is active both at the higher and lower
temperatures. The low-frequency dielectric relaxation
should be the results of interface polarization originating
from inhomogeneous microstructures or grain boundaries,
while the high-frequency dielectric relaxation should be due
to some more intrinsic mechanism such as the mixed-valent
structures of Cu?/Cu2? and Ti3?/Ti4? [14]. The details will
be discussed later.
Temperature dependence of real and imaginary parts of
permittivity in Ca1-3x/2NdxCu3Ti4O12 (x = 0, 0.1, 0.2)
ceramics is shown in Fig. 4. All ceramics present giant
dielectric constant in a wide temperature range and two
dielectric relaxations in low and high temperature ranges.
As frequency increases from 1 kHz to 1 MHz, the
dielectric relaxation peaks move towards the high tem-
perature side. Furthermore, the low temperature relaxation
in e00 T curves (Fig. 5) are examined. The variation of
critical temperature with frequency obeys the Arrhenius
law
f f0 expEa =kT 1 temperature range should be ascribed to more intrinsic
347
where f0 is pre-exponential term, Ea is activation energy
and k is Boltzmann constant. The fitting parameters Ea and
f0 are 93 meV, 1.1 9 108 Hz for x = 0, 86 meV,
2.6 9 107 Hz for x = 0.1, and 90 meV, 2.2 9 108 Hz for
x = 0.2, respectively. According to Eq. (1), f0 represents
the responding frequency at infinite high temperature. Nd-
substitution leads to a slight variation of activation energy
but considerable change of f0. It reveals that the dipoles
related to this heat-activated relaxation originate from the
same physical mechanism. Increasing Nd-content will
change the effective mass of the corresponding dipoles,
resulting in the change of responding frequency f0.
Effects of composition upon temperature dependence of
dielectric characteristics are shown in Fig. 6. The dielectric
constant plateau for CaCu3Ti4O12 ceramics is not obvious
because of the overly influence of the relaxation peak in
high temperature range. As a result, dielectric constant of
CaCu3Ti4O12 ceramics is elevated and is higher than other
compositions above 250 K. However, dielectric constant of
x = 0 sample is slightly lower than that of x = 0.1 sample
below 250 K. When x increases to 0.2, lower dielectric
constant and dielectric loss are obtained. Besides, com-
paring with CaCu3Ti4O12 ceramics, Ca0.85Nd0.1Cu3Ti4O12
ceramics exhibit improved dielectric characteristics. The
magnitude of dielectric constant plateau is as high as
*2.2 9 104 and the lowest tand value reaches 0.06 in the
temperature range of 150350 K.
The grain size decreases with increasing x, however, the
dielectric constant at low temperature range is not
decreasing monotonously. Thus the relaxation in the low
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Fig. 4 Temperature
dependence of real and
imaginary parts of permittivity
of Ca1-3x/2NdxCu3Ti4O12
ceramics with various
compositions: a x = 0,
b x = 0.1, and c x = 0.2
(1, 4, 10, 40, 100, 400 kHz
and 1 MHz)

mechanisms such as electron hopping between Ti3?/Ti4?
and Cu?/Cu2? [14]. During the process of sintering, at
elevated temperatures in air, oxygen vacancy is formed:
OO ! 1=2O2 VO 2e0 . Meanwhile, the existence of
Cu? and Ti3? is compensated by the formation of oxygen
vacancies. Considering the different electronic configura-
tion of Ti and Cu, hopping process exhibits alternative
forms: The Ti3? and Ti4? form Ti3?OTi4? bonds and
the Ti-3d electrons in Ti3? ions can hop to Ti4? under
electric field [15], Cu1? at the Cu2? site may form dipoles
0
with the VO presenting 2Cu Cu2
 VO and may change
orientation due to hopping of electrons among Cu1? and
Cu2? [16].
The variation of mixed-valent structures of Cu?/Cu2?
and Ti3?/Ti4? in Ca1-3x/2NdxCu3Ti4O12 ceramics with x
can be determined by XPS analysis. As shown in Fig. 7,
both the 2p3/2 peaks for Cu and Ti can be split into two
peaks by GaussianLorentzian curve fitting. Quantitative
analysis is carried out and the binding energy for each
different valent ion is within the range of binding energies
in NIST XPS database. The results show that Cu?/Cu2?
and Ti3?/Ti4? ratios in Ca1-3x/2NdxCu3Ti4O12 (x = 0, 0.1,

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J Mater Sci: Mater Electron (2011) 22:345350 349

Fig. 5 Frequency dependence of the peak temperature of imaginary

dielectric constant for low-temperature dielectric relaxation in Ca1-3x/
2NdxCu3Ti4O12 (x = 0, 0.1, 0.2) ceramics. The symbols are the
experimental data and the lines are the Arrhenius fittings

0.2) ceramics are 0.70, 0.65, 0.63 and 0.71, 0.71, 0.59,
respectively. That is, the mixed-valent structures of Cu?/
Cu2? and Ti3?/Ti4? are suppressed by Nd-substitution. It
should be mentioned here that the CaCu3Ti4O12 ceramics
are relatively less dense, and the effect of corresponding
dipoles will be weakened in a certain extent. Therefore, the
dielectric constant of CaCu3Ti4O12 ceramics is slightly
lower than that of Ca0.1Nd0.85Cu3Ti4O12 ceramics in spite
of the higher amount of Cu? content. As x increases from
0.1 to 0.2, magnitude of dielectric constant and dielectric
loss in the low temperature range decrease together with
the suppressed mixed-valent structures. Moreover, Nd
substituting Ca results in the formation of A-site vacancies,
but its direct effect on dielectric constant may be excluded
[17]. It is reasonable to ascribe the variation of dielectric
constant and dielectric loss to the modification of mixed-
valent structures.
Fig. 6 Effects of composition upon temperature dependence of a
dielectric constant and b dielectric loss of Ca1-3x/2NdxCu3Ti4O12
ceramics at 10 kHz
4 Conclusion
The solid solutions with cubic structure are obtained in
Ca1-3x/2NdxCu3Ti4O12 ceramics. Both dielectric constant
and dielectric loss changes with increasing x, as the results
of the modified mixed-valent structures of Cu?/Cu2? and
Ti3?/Ti4?. The present results provide the general way to
modify the dielectric characteristics by tailoring the mixed-
valent structure.

Fig. 7 XPS spectra of a Cu and

b Ti regions in Ca1-3x/
?
2NdxCu3Ti4O12 ceramics (Cu /
2? 3? 4?
Cu and Ti /Ti ratios in
Ca1-3x/2NdxCu3Ti4O12 (x = 0,
0.1, 0.2) ceramics are 0.70, 0.65,
0.63 and 0.71, 0.71, 0.59,
respectively)

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Acknowledgments The present work was financially supported by
National Science Foundation of China under grant numbers
50832005.
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