Materials and Design 92 (2016) 494498

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Improved dielectric properties of (Y + Mg) co-doped CaCu3Ti4O12

ceramics by controlling geometric and intrinsic properties of
grain boundaries
Jakkree Boonlakhorn a, Bundit Putasaeng b, Pinit Kidkhunthod c, Prasit Thongbai d,
a

Materials Science and Nanotechnology Program, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand
National Metal and Materials Technology Center, National Science and Technology Development Agency, Thailand Science Park, Pathumthani 12120, Thailand
c
Synchrotron Light Research Institute (Public Organization), 111 University Avenue, Muang District, Nakhon Ratchasima 30000, Thailand
d
Integrated Nanotechnology Research Center (INRC), Department of Physics, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand
b

a r t i c l e

i n f o

Article history:
Received 1 August 2015
Received in revised form 3 December 2015
Accepted 11 December 2015
Available online 12 December 2015
Keywords:
Dielectric permittivity
Impedance spectroscopy
Loss tangent
CaCu3Ti4O12
Co-doping

a b s t r a c t
Signicantly improved dielectric properties of CaCu3Ti4O12 ceramics were accomplished by co-doping with Y3+
and Mg2+ to simultaneously control the geometric and intrinsic properties of grain boundaries (GB), respectively.
Substitution of these dopants strongly suppressed grain growth while enhancing the resistivity of an individual
GB, respectively. The resulting small grained microstructure with very high GB density and greatly increased resistivity resulted in a strong increase in the total resistance of GBs. This caused a large decrease in the loss tangent
(tan ~ 0.013). Furthermore, nonlinear currentvoltage properties were also improved.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Since colossal dielectric permittivity () of CaCu3Ti4O12 (CCTO) was
rst reported by Subramanian et al. [1], investigations to reduce the dielectric loss tangent (tan) of CCTO have been extensively done [28]. Although CCTO can exhibit very high ~ 104, its tan is still larger than the
acceptable standard value for capacitor applications. This is one of the
most serious problems inhibiting the use of CCTO. Clearly, CCTO polycrystalline ceramics are electrically heterogeneous, consisting of insulating
grain boundaries (GBs) and n-type semiconducting grains [9]. This is
called an internal barrier layer capacitor (IBLC) structure. Such microstructure is widely accepted to be the primary cause of a material's high
dielectric response. This also resulted in the formation of double Schottky
barriers at the GBs [9,10], producing the nonlinear currentvoltage (or
nonlinear current densityelectric eld, JE) behavior of CCTO [6,7,9].
Generally, low-frequency tan is closely correlated to conductivity
(dc) caused by long-range motion of charge carriers [6]. According to
the IBLC structure, low-frequency tan can be reduced by increasing
the total resistance of the bulk ceramics. This can be achieved by increasing the resistance of the insulating GBs (Rgb) because the grain resistance (Rg) of CCTO is much lower than that of the GB [11,12]. Many
strategies for reducing tan have been proposed that are based on
Corresponding author.
E-mail address: pthongbai@kku.ac.th (P. Thongbai).

http://dx.doi.org/10.1016/j.matdes.2015.12.042
0264-1275/ 2015 Elsevier Ltd. All rights reserved.

the enhancement of GB resistance or internal interface resistance [24,

7,8,13,14]. These can be divided into two primary groups based
on whether they improve geometric or intrinsic properties of GBs
[7]. The former can be achieved by controlling the microstructure
to obtain a small grained microstructure with a large number of insulating GB layers [4,7,13,14]. The latter is accomplished by modifying
the intrinsic properties of the GBs, i.e., by increasing in the resistivity
of individual GBs [3,8,15]. Decreasing tan and dc can be accomplished by improving either the geometric or intrinsic properties of
the GBs.
Usually, substitution of Ln3+ ions (e.g., La3+, Gd3+, and Y3+) into
Ca2+ sites of CCTO can effectively suppress the grain growth rate, achieving a small grained microstructure [13,14,16,17]. In this case, tan was decreased by means of improving the geometric factors at the GBs. On the
other hand, substitution of Mg2+ into Cu2+ sites caused an increase in
the mean grain size or decreased GB density, but can also reduce the
low-frequency tan [15]. This indicated that a largely enhanced resistivity
of each GB layer in Mg-doped CCTO ceramics was achieved. It is expected
that co-doping CCTO with Ln3+ and Mg2+ may inuence the geometric
and intrinsic properties of the GBs.
In this work, a novel strategy for simultaneously tuning a ceramic
microstructure and intrinsic electrical properties of GBs was explored
to achieve a high-performance CCTO with a very low tan. A high
~ 8634 and very low tan ~ 0.013 at 1 kHz were accomplished by
this method using Y3+ and Mg2+ co-doping ions.

J. Boonlakhorn et al. / Materials and Design 92 (2016) 494498

495

electrodes, surfaces of the sintered ceramics were polished and then

coated with Au for 8 min at 25 mA using a Polaron SC500 sputter coating
unit. The dielectric properties were measured using a precision impedance analyzer (Agilent 4294A) over the frequency range of 102107 Hz
with an oscillation voltage of 0.5 V. The measurement was performed
over a temperature range from 70 to 220 C. JE characteristics
were measured at room temperature using a high voltage measurement
unit (Keithley Model 247). Eb was dened as the electric eld breakdown strength at which J = 1 mA/cm2. The nonlinear coefcient ()
was calculated in the range of 110 mA.cm2.
3. Results and discussion

Fig. 1. XRD patterns of (a) CCTO, (b) Mg05, (c) Y05, and (d) Y-Mg05 samples.

2. Experimental details
CaCu3Ti4O12 (CCTO), Ca0.925Y0.05Cu3Ti4O12 (Y05), CaCu2.95Mg0.05
Ti4O12 (Mg05), and Ca0.925Y0.05Cu2.95Mg0.05Ti4O12 (Y-Mg05) were prepared using a modied solgel method. Ca(C2H3CO2)2H2O (99 + %,
Sigma-Aldrich), Cu(CH3COO)2H2O (99.0%, Sigma-Aldrich), C16H28O6Ti
(75 wt.% in isopropanol, SigmaAldrich), Mg(C4H6O4)4H2O (99.999%,
SigmaAldrich), Y(CH3CO2)3xH2O (99.9%, Sigma-Aldrich), ethylene glycol, citric acid, ethanol, and de-ionized water were used as starting raw
materials. Details of the preparation method are given elsewhere [6].
Dried precursors were heated at 900 C for 10 h. The powders obtained
were pressed by uniaxial compression at 200 MPa into disks 9.5 mm in diameter and ~1.2 mm in thickness. The compacted powders were sintered
in air at 1070 C for 6 h using heating and cooling rates 5 C/min.
X-ray diffraction (XRD; Philips PW3040 with Cu K radiation, =
0.15406 nm) was used to characterize the phase formation in the
sintered ceramics. Microstructures of the sintered ceramics were characterized using scanning electron microscopy (SEM) and energydispersive X-ray spectrometry (EDS) (SEC, SNE-4500M). To prepare

As shown in Fig. 1, a single phase of CaCu3Ti4O12 (JCPDS 75-2188)

can be observed in all the XRD patterns. No impurity phase was detected by this technique. The diffraction peaks in all the XRD patterns were
perfectly indexed to the bcc structure within the space group Im3. Lattice parameter (a) values of the CCTO, Y05, Mg05, and Y-Mg05 samples
were of 7.391, 7.391, 7.393, and 7.395 , respectively. Changes in a may
not be associated with the concentration of Mg2+ due to the similarity
of the ionic radii of the dopants and host ions. This slight variation
might be attributed to the effect of lattice distortion induced by the variations in this mixed-valent structure [15].
As shown in Fig. 2, the microstructures of the Y05 and Mg05 samples
were very dissimilar. The former and latter exhibited strongly reduced
and largely enhanced grain growth rates, respectively. The mean grain
sizes of the CCTO, Y05, and Mg05 samples were approximately
26.26 9.53, 2.52 1.07, and 45.65 17.16 m, respectively. Their relative densities were about 92.8, 89.25, and 94.4%, respectively. The increase in the mean grain size in the Mg05 sample was similar to that
observed in CaCu2.85Mg0.15Ti4O12 prepared using a solid state reaction
method [15]. Its grain size increased by a factor of 1.66 compared to
the un-doped CCTO. By doping Y3 + into Mg-doped CCTO, the grain
size was greatly reduced to 3.73 1.08 m with a relative density of
~ 89.1%. However, a small number of large grains were also observed
in the Y-Mg05 sample. The decrease in the mean grain size due to
substitution of Y3+ into the ceramic arises from the solute drag effect
[14,18].

Fig. 2. SEM images of the surface morphologies of (a) CCTO, (b) Mg05, (c) Y05, and (d) Y-Mg05 samples.

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J. Boonlakhorn et al. / Materials and Design 92 (2016) 494498

Segregation of Mg2 + ions and Y3 + doping ions as well as the

existence of major elements in the microstructure of Y-Mg05 sample
was characterized by using an SEM-EDS technique. As shown in
Fig. 3(a) and (b), a mall EDS peak corresponding to Mg is likely observed
in both of the large and small grains. Moreover, EDS results revealed
that Mg2+ ions segregated at both GBs region and within the grains. Unfortunately, Y3+ ions cannot be observed. All possible EDS peaks of the
major elements for Ca, Cu, Ti, and O were also detected.
A microstructure with high GB density and enhanced resistivity at
individual GB layer can only be accomplished if the macroscopic total
resistance of the GBs of the co-doped Y-Mg05 sample is signicantly
larger than that of the single-doped Y05 sample. To clarify this, an impedance spectroscopy analysis was carried out. The total resistances of
grains (Rg) and GBs (Rgb) of CCTO ceramics can generally be determined
from a nonzero intercept on the Z-axis in the high frequency range and
the diameter of a large semicircular arc in the low frequency range, respectively [1012]. As shown in Fig. 4(a) and inset (1), Rgb values at
80 C of the CCTO, Y05, Mg05, and Y-Mg05 samples were of
~1.71 104, 4.79 105, 2.01 105, and 1.28 106 cm, respectively.
Rgb of CCTO ceramics was largely increased by doping with a singledopant, either Y3 + or Mg2 +. From SEM images, increases in Rgb in

these two cases were primarily associated with geometric and intrinsic
parameters of the GBs, respectively. Rgb of the Mg05 sample was significantly increased by an order of magnitude compared to that of the
CCTO sample even though the GB density was decreased. This clearly indicates a great increase in resistivity of individual GB layers of the Mg05
sample. Alternatively, largely enhanced Rgb of the Y05 sample was dominated by the geometric parameter due to the increase in GB density.
Notably, Rgb of the Y-Mg05 sample was larger than that of the Y05 sample, while the geometric properties of these two samples were not signicantly different. The intrinsic factor of the GB of the Y-Mg05
sample was more dominant than that of the Y05 sample, which was improved by addition of Mg2+. Thus, in this current study, the desirable
ceramic microstructure was successfully achieved in the co-doped YMg05 sample. It is notable that the both single and co-doping ions
have a slight effect on the electrical properties of the grains, as shown
in the inset (2) of Fig. 4(a).
CCTO can exhibit nonlinear JE properties, which can be attributed
to the creation of an electrostatic potential barrier at the GBs [9]. Generally, both the intrinsic and geometric parameters of the GBs inuence
the nonlinear properties [7]. As shown in Fig. 4(b), the effect of single
and co-doping ions on the nonlinear properties is very consistent with

Fig. 3. EDS spectra of the Y-Mg05 sample detected at (a) small grain and (b) large grain regions; yellow circles in the SEM images are marked as the testing EDS points. (For interpretation
of the references to color in this gure legend, the reader is referred to the web version of this article.)

J. Boonlakhorn et al. / Materials and Design 92 (2016) 494498

Fig. 4. (a) Impedance complex plane (Z) plot at 80 C for all the samples; insets (1) and
(2) show expanded views close to the origin of Z* plot at 80 and 70 C, respectively.
(b) JE curves at room temperature for all the samples.

the results obtained from the impedance spectroscopy analysis, even

though these two measurements were conducted under different applied electric eld levels. Eb values of the CCTO, Y05, Mg05, and YMg05 samples were ~233.2, 2190.2, 811.3, and 3659.9 V/cm, respectively, whereas values were 3.32, 3.70, 4.85, and 6.60, respectively. These
results clearly conrm that both the intrinsic and geometric parameters
of the GBs of CCTO ceramics were simultaneously enhanced by codoping with Y3+ and Mg2+.
As demonstrated in Fig. 5(a) and its inset, and tan of CCTO ceramics were decreased by both single and co-doping. However, the
values at 1 kHz and 20 C of the CCTO, Y05, Mg05, and Y-Mg05 samples
were still quite large, 66,423, 5726, 18,156, and 8634, respectively. tan
values were about 0.108, 0.065, 0.045, and 0.013, respectively. As shown
in Fig. 2, dense ceramic microstructure was achieved in the CCTO and
Mg05 samples, while residual pores were observed on the surface of
the Y05 sample. Thus, the large difference in values of the CCTO and
Y05 samples is likely due to the effects of the GB response and porosity.
Interestingly, the slightly better microstructure of the sintered Y-Mg05
sample can signicantly enhance the dielectric properties compared to
that of the Y05 sample. This result is similar to that reported in literature
[19]. This indicates that the intrinsic properties of the GBs (e.g., the resistivity and capacitance of the GB) can be enhanced by Mg2+ doping ions.
Interestingly, the tan value of the Y-Mg05 sample was the lowest
among the samples presented. It was less than 0.05 over the frequency
range of 102105 Hz. Furthermore, at 20 C of the Y-Mg05 sample was
independent of frequency over the range from 102 to 106 Hz. It is notable that the temperature stability of at 1 kHz of the Y-Mg05 sample
was better than for other samples, as shown in Fig. 5(b). For the CCTO,

497

Fig. 5. (a) Frequency dependence of at 20 C for all the samples; inset shows tan as a
function of frequency at 20 C. (b) at 1 kHz as a function of temperature.

Y05, and Mg05 samples, at 1 kHz largely increased as temperature

higher than 100 C. This result is similar to those observed in literature
[14,17,2022]. Excellent dielectric properties of CCTO with a very low
tan and a high that was independent of frequency and temperature
were successfully achieved by simultaneously tuning the geometric and
intrinsic properties of the GBs by co-doping with Y3 + and Mg2 +,
respectively.
A high tan value over a low-frequency range is generally induced by
DC conduction (dc). Fig. 4(a) clearly shows that Rg Rgb. Thus, the
relationship between tan and dc (=1/Rgb) can be estimated by following equation [6]:
tan

1
;
0 0s C 0 Rgb

where s is the low-frequency dielectric permittivity. Co is the

empty cell capacitance. Clearly, the low-frequency tan value of the YMg05 sample was very much reduced by greatly increasing Rgb, which
was accomplished by simultaneously improving both the intrinsic and
geometric properties of the GBs.
4. Conclusions
A desirable CCTO microstructure of with a high GB density, greatly
enhanced Rgb with improved overall dielectric properties was obtained
by co-doping with Y3+ and Mg2+ into Ca2+ and Cu2+ sites, respectively. Signicantly enhanced dielectric properties were achieved as a result

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J. Boonlakhorn et al. / Materials and Design 92 (2016) 494498

of simultaneously controlling the geometric and intrinsic properties of

the GBs. Excellent dielectric properties were successfully achieved in
a (Y and Mg) co-doped CCTO ceramic. was high (~ 8634) and
tan was very low (~ 0.013) with good stability over a wide range of
temperatures and frequencies.
Acknowledgments
This work was nancially supported by the Thailand Research Fund
(TRF) and Khon Kaen University, Thailand (grant number RSA5880012).
J. Boonlakhorn would like to thank the Faculty of Science, Khon Kaen
University for his Master of Science Degree scholarship.
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