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Enhanced Dielectric and Non-Ohmic Properties in Cacu Ti O / Catio Nanocomposites Prepared by A Chemical Combustion Method
Enhanced Dielectric and Non-Ohmic Properties in Cacu Ti O / Catio Nanocomposites Prepared by A Chemical Combustion Method
DOI 10.1007/s10854-016-5358-8
Received: 18 May 2016 / Accepted: 11 July 2016 / Published online: 14 July 2016
Ó Springer Science+Business Media New York 2016
Abstract CaCu3Ti4O12 and CaTiO3 nanoparticles with though the origin of the giant dielectric response in CCTO
sizes of about 30–90 nm were simultaneously prepared is still unclear today. According to several elegant works
using a chemical combustion method employing glycine as [2, 17], CCTO is obviously electrically heterogeneous,
fuel. CaCu3Ti4O12 and CaTiO3 phases without impurity consisting of n-type semiconducting grains and insulating
were successfully achieved using a relatively low calcina- grain boundaries (GBs). Thus, the dielectric properties can
tion temperature of 800 °C. Dense microstructure was be improved by tuning the electrical properties of GBs and/
obtained after sintering for 2 h. The sintered CaCu3Ti4O12/ or other internal interfaces. The dielectric loss tangent
CaTiO3 nanocomposites exhibited a low loss tangent of (tand) at 1 kHz of CCTO ceramics is still too high ([0.05)
0.05 and high dielectric permittivity of 1.01 9 104 at [1, 5, 10, 11, 18], which is the serious problem preventing
1 kHz with good temperature stability over the range of the use of CCTO in capacitor applications.
-60 to 100 °C. The nonlinear current–voltage properties Generally, reduction in DC conductivity (rdc) to
were also investigated. The dielectric response and non- decrease tand of CCTO has been carried out by increasing
linear electrical properties can be well described to be the resistances of GBs (Rgb) or other internal interfaces
associated with the electrical responses of internal inter- [19]. Enhancement of Rgb can be performed by several
faces, i.e., CaCu3Ti4O12–CaTiO3 and CaCu3Ti4O12– ways such as doping CCTO with suitable metal ions to
CaCu3Ti4O12 interfaces. intrinsically improve electrical properties of GBs [18, 20],
filling oxygen vacancies at GBs [21], or altering Ca2? and
Cu2? molar ratios to produce CCTO/CaTiO3 (CTO) com-
1 Introduction posites [3, 7, 22, 23]. However, reduced tand of CCTO by
using these methods rarely results in materials that fulfill
Recently, CaCu3Ti4O12 (CCTO) ceramics have been all of the requirements of capacitor applications, i.e., high
extensively investigated because of the fascinating physics e0 , low tand, and good temperature stability of e0 . For
underlying the origin of an ultra-high dielectric permittivity example, a strong decrease in tand (*0.02 at 1 kHz)
(e0 ) in CCTO without any detectable phase transition over a observed in Ca2Cu2Ti4O12 (consisting of 33.3 mol% of
wide temperature range [1–16]. CCTO is promising for a CCTO and 66.7 mol% of CTO) caused a large decrease in
new generation of multilayer ceramic capacitors even e0 (*1.8 9 103) [3].
To investigate CCTO-based ceramics for use applica-
tions in electronic devices, selection of the synthesis
& Prasit Thongbai method is one of the most important decisions, which
pthongbai@kku.ac.th largely determines the sintered bulk properties of CCTO
1 ceramics. Generally, CCTO-based ceramics are prepared
Materials Science and Nanotechnology Program, Faculty of
Science, Khon Kaen University, Khon Kaen 40002, Thailand by the solid state reaction (SSR) method [1–3, 7, 17, 18].
2 However, the SSR method requires high temperatures
Integrated Nanotechnology Research Center (INRC),
Department of Physics, Faculty of Science, Khon Kaen (1000–1050 °C) and long reaction times (12–14 h) to
University, Khon Kaen 40002, Thailand eliminate all possible impurity phases [3, 18]. On the other
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12086 J Mater Sci: Mater Electron (2016) 27:12085–12090
hand, syntheses of ceramic powder from chemical solu- (C2S5), C1S10 (C2S10), and C1S15 (C2S15) samples,
tions offer the possibility of closer stoichiometric control respectively.
compared to the SSR method. Low-temperature chemical Scanning electron microscopy (SEM) (LEO 1450VP,
reactions with short reaction times are usually sufficient UK) with an energy dispersive X-ray spectrometry (EDS)
used to produce a pure phase [4]. The combustion method and X-ray diffraction (XRD) (Philips PW3040, the
is one of the most interesting routes to produce nanocrys- Netherlands) techniques were used to characterize the
talline ceramics. Organic compounds like glycine, urea, surface morphologies and phase compositions of the sin-
citric acid, and EDTA have been widely used as fuels for tered CCTO/CTO composite ceramics, respectively. Par-
gel combustion [24]. The combustion method using glycine ticle size and shape of the composite powders were
as a fuel is one of the most attractive methods. This method revealed using transmission electron microscopy (TEM)
was firstly reported by Chick et al. [25] which can be used (FEI Tecnai G2, Eindhoven, the Netherlands). Surfaces of
effectively to prepare homogeneous nanoparticles of cera- the sintered ceramics were polished and sputtered with Au
mic powders by a self-ignited combustion process. at a current of 25 mA for 8 min using a Polaron SC500
According to our previous work, a pure CCTO phase can sputter coating unit. Keysight E4990A and Agilent 4294A
be prepared by this method using a low sintering temper- Precision Impedance Analyzer were used to test the
ature and short reaction time [26]. The dielectric properties dielectric properties. The measurement was carried out
of CCTO ceramics can be improved by using nanocrys- over the frequency range from 102 to 107 Hz using an
talline CCTO powder to form the bulk ceramics. To the oscillation voltage of 0.5 V under the temperature range
best our knowledge, preparation of CCTO/CTO compos- from -70 to 220 °C with step increases of 10 °C. Each
ites using wet chemical routes was rarely reported [22, 23]. temperature step was held with an accuracy of ±1 °C.
Furthermore, syntheses of CCTO/CTO composites using a Current density–electric field (J–E) characteristics were
combustion method and their dielectric properties have measured at various temperatures using a high voltage
never been reported. measurement unit (Keithley Model 247). Eb was defined as
Therefore, in this work, the glycine combustion method the electric field breakdown strength at which J = 1 mA/
was used to synthesize nanocrystalline CCTO and CTO cm2. The nonlinear coefficient (a) was calculated using the
powders by using one-step process from the nominal following formula:
chemical formula of Ca2Cu2Ti4O12. Dense ceramic logðJ2 =J1 Þ
microstructure of CCTO/CTO nanocomposites was a¼ ; ð1Þ
logðE2 =E1 Þ
achieved by sintering under a short reaction time for 2 h.
The e0 values of the sintered CCTO/CTO ceramics were where E1 and E2 are the applied electric fields, at which
significantly enhanced by factors of 4–5 compared to those J1 = 1 and J2 = 10 mA cm-2, respectively.
ceramics prepared by SSR method, while tand was still too
low.
2 Experiment
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J Mater Sci: Mater Electron (2016) 27:12085–12090 12087
Intensity (a.u.)
75-2188) and CTO (JCPDS 82-0231). A small amount of C2S10
CuO phase is still in the C1 powder. This result is similar to C2S5
that reported in the literature for Ca2Cu2Ti4O12 ceramics
C2S2
prepared by SSR method and polymer pyrolysis method C1S15
[3, 7, 23]. From the nominal formula of Ca2Cu2Ti4O12, two
C1S10
phases of *66.7 mol% of CTO and *33.3 mol% of
C1S5
CCTO can be formed. This is because the ionic radius of
C1S2
Cu2? much smaller than that of Ca2?. Thus, the excess
Ca2? ions cannot occupy on Cu2? lattice sites for a planar 20 30 40 50 60 70 80
square of CuO4 to form Ca(CaCu2)Ti4O12 structure. Lattice 2θ (degree)
parameters (a) of the CCTO phase in the C1 and C2
composite powders were calculated and found to be 7.3955 Fig. 3 XRD patterns of the sintered ceramic composites using C1
and C2 powders and sintered under different conditions
and 7.3956 Å, respectively. These values are comparable
to 7.391 Å for a single CCTO phase [1]. Morphologies of
the C1 and C2 powders are shown in Fig. 2. The TEM grains were clearly proved to be the CCTO and CTO
images revealed that particle size increases with increasing phases, respectively. As illustrated in Fig. 5, it is clear
calcination temperature. The particles sizes of the C1 and shown that the rough surface grain (detected on point-2) is
C2 powders are of about 30–80 and 60–90 nm, CTO phase because only EDS peaks of Ca, Ti, and O are
respectively. detected. All of Ca, Cu, Ti, and O peaks are detected in the
Figure 3 shows the XRD patterns of the sintered com- smooth surface grain (detected on point-1), indicating to be
posite ceramics using the C1 and C2 powders as green the CCTO phase. This result is similar to that reported in
bodies. As clearly seen, the CCTO and CTO phases are literature [7, 27].
detected in all the XRD patterns. A values of the C1S2 Figure 6 demonstrates the dielectric properties as a
(C2S2), C1S5 (C2S5), C1S10 (C2S10), and C1S15 function of frequency for the CCTO/CTO composites at
(C2S15) samples were found to be 7.3913 (7.3924), 7.3866 20 °C. e0 of all the samples is nearly independent on fre-
(7.3904), 7.3901 (7.3904), and 7.3906 (7.3903) Å, quency in the range of 102–105 Hz. Interestingly, e0 values
respectively. Figure 4 demonstrates SEM images of the of all the CCTO/CTO samples are of about 104. These e0
C1S2 and C1S10 samples. Large and small grains are values of all the CCTO/CTO samples are much larger than
observed. According to previous works [7, 27], by using the e0 value of *1800 for the CCTO/CTO composite
the backscattered SEM images of CCTO/CTO composites prepared by SSR method and sintered at 1090 °C for 24 h,
coupled with EDS technique, smooth and rough surface as first reported by Kobayashi and Terasaki [3]. Moreover,
100 nm 100 nm
123
12088 J Mater Sci: Mater Electron (2016) 27:12085–12090
(a)
4
10
0.25
0.20
3
ε'
10
tanδ
0.15
0.10
0.05 o C1S2
20 C
0.00 2 C1S5
3 4 5 6
10 10 10 10 10
C1S10
20 μm Frequency (Hz)
10
2 C1S15
2 3 4 5 6 7
10 10 10 10 10 10
Frequency (Hz)
(b) Fig. 6 Frequency dependence of e0 at 20 °C for CCTO/CTO
composites fabricated by using C1 powder; inset shows tand as a
function of frequency
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J Mater Sci: Mater Electron (2016) 27:12085–12090 12089
10
5
(1538.7), and 1912.7 (2326.37) V/cm, respectively. a val-
ues are of about 6.08 (5.69), 5.31 (5.15), 7.35 (6.21), and
7.03 (7.12), respectively. It is important to note that the Eb
and a values of the CCTO/CTO composites in this current
10
4 study are lower than those of CCTO/CTO composites
2
prepared by SSR method [27, 28, 30]. According to the
10 C1S2
C1S5
microstructure analyses, large grains with sizes of about
ε'
1
C1S10
10 C1S15
10–40 lm were observed in the microstructure of CCTO/
tanδ
at 1 kHz
3 C1S2 10
0
CTO composites prepared by a glycine combustion
10
C1S5 -1 method, while fine grains with sizes of 2–3 lm were
10
C1S10
observed in the composites prepared by SSR method [30].
C1S15 10
-2
15 C2S10
2
0
5 1
10 10
2 3
10
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