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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.
495
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
Fig. 2. SEM images of the surface morphologies of (a) CCTO, (b) Mg05, (c) Y05, and (d) Y-Mg05 samples.
496
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.)
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.
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.
1
;
0 0s C 0 Rgb
498
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