Author’s Accepted Manuscript

Very high performance dielectric and non-ohmics

properties of CaCu3Ti4.2O12 ceramics for X8R
capacitors

Krissana Prompa, Ekaphan Swatsitang, Chatree

Saiyasombat, Thanin Putjuso
www.elsevier.com/locate/ceri

PII: S0272-8842(18)31027-7
DOI: https://doi.org/10.1016/j.ceramint.2018.04.156
Reference: CERI18073
To appear in: Ceramics International
Received date: 5 March 2018
Revised date: 14 April 2018
Accepted date: 16 April 2018
Cite this article as: Krissana Prompa, Ekaphan Swatsitang, Chatree Saiyasombat
and Thanin Putjuso, Very high performance dielectric and non-ohmics properties
of CaCu3Ti4.2O12 ceramics for X8R capacitors, Ceramics International,
https://doi.org/10.1016/j.ceramint.2018.04.156
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 1

Very high performance dielectric and non-ohmics properties

of CaCu3Ti4.2O12 ceramics for X8R capacitors

a a,b c d*
Krissana Prompa , Ekaphan Swatsitang , Chatree Saiyasombat , Thanin Putjuso

a
Integrated Nanotechnology Research Center (INRC) and Department of Physics, Faculty of Science,

Khon Kaen University, Khon Kaen, 40002 Thailand

b
Nanotec-KKU Center of Excellence on Advanced Nanomaterials for Energy Production and Storage,

Khon Kaen University, Khon Kaen, 40002 Thailand

c
Synchrotron Light Research Institute (Public Organization), 111 University Avenue, Muang District,

Nakhon Ratchasima 30000, Thailand

d
School of General Science, Faculty of Liberal Arts, Rajamangala University of Technology

Rattanakosin, Wang Klai Kangwon Campus, Hua Hin,

Prachaubkerekhan 77110, Thailand

*Corresponding author: Dr. Thanin Putjuso

Tel.: +66-3261-8500; Fax: +66-3261-8570
Email address: thanin.put@rmutr.ac.th
 2

ABSTRACT

CaCu3Ti4O12 (CCTO) and CaCu3Ti4.2O12 (Ti02) precursor powders were prepared by

the polymer pyrolysis solution method. Effect of sintering time/temperature on

microstructural, dielectric and non-linear properties of CCTO and Ti02 ceramic samples

obtained by sintering all precursor powders at various sintering conditions were investigated.

Interestingly, very low tanand high   7,221 with temperature coefficients ' <

±15% in a wide temperature range of −60 to 180 ºC were achieved in the Ti02 ceramic

sample sintered at 1025 ºC for 12 h (Ti02-2 sample). This suggested the potential use of Ti02-

2 sample for EIA X5R, X7R and X8R capacitors. Moreover, sintering could enhance the non-

linear characteristics of all ceramic samples with a non-linear coefficient () of ~ 29.04 and

the maximum breakdown field (Eb) of ~ 12221 V/cm-1 in Ti02-2 sample. Enhancement of

due to the sintering was suggested to originate from the promotion of oxygen vacancies and

the increase of grain size.

Keywords: CaCu3Ti4.2O12 ceramics; X8R capacitors; XANES; Dielectric properties; Non-

Ohmic properties.
 3

1 Introduction

Research on materials of high dielectric permittivity (' ~ 103 – 105) such as

CaCu3Ti4O12 (CCTO)-based [1-9], ACu3Ti4O12 (A = Na1/2Y1/2, Y2/3, Bi2/3) compounds and

other related materials [10-14] have been continuously and intensively investigated, since the

report on giant dielectric in CCTO by Subramanian et al. in 2000 [15]. This is owing to their

potent applications in various fields of technology such as multilayers ceramic capacitors

(MLCC), memory devices and high density energy storage devices. Besides the unusually

high dielectric permittivity over a wide range of frequency and temperature [15-17],

nonlinear J–E characteristics are also observed in these compounds [18-20]. Principally, the

explanation for high ' behavior and J–E characteristics of these CCTO-based compounds is

based on the internal barrier layer capacitor (IBLC) model, which directly correlates with the

insulating grain boundaries (GBs) and n‒ type semiconducting grains in these ceramic

compounds. Therefore, it is proposed that the overall dielectric performance of the materials

can be improved by the modification of internal interfaces at GBs. However, high dielectric

permittivity in CCTO-based [3, 16, 21, 22] and ACu3Ti4O12 [10, 12, 14] compounds is

usually accompanied by the increase of dielectric loss tangent (tan over a commercially

limitable value of 0.04 [23]. In addition to this, temperature stability of ' (') is one

inevitably important parameter to be considered for commercial electronic devices.

Specifically,  of the EIA code X5R, X7R and X8R capacitors are limited within ± 15% or

less over a temperature range of -55 85 ºC, -55 125 ºC and -55 150 ºC, respectively [24].

Usually, ' < ±15% in CCTO-based compounds is found to be in a temperature range of -

55 100 ºC [2, 3, 5, 16, 19], which is suitable for the X5R capacitor only. Therefore, it is still

a challengeable work that attract researchers to search for materials of high ' with low

tanvalue and ' < ±15% in a wider range of temperature. Recently, different approaches
 4

have been extensively employed to improve the dielectric properties of CCTO-based

compounds such as (1) by doping and co-doping of CCTO-based compounds with some

transition metals [2, 4, 5, 25-29], (2) compounds modification by molar ratio regulation of

some cations in ceramic samples for instance, variation of Ca2+/Cu2+ ratios had been studied

in CCTO/CaTiO3 ceramics [30-33] and another example was to adjust Ti molar concentration

in CCTO/TiO2 ceramics [34-37], (3) sintering conditions (time and temperature) adjustment,

which could significantly improve the density of GB layers [38-40]. Accordingly, a number

of research works [34-37, 41] have been emphasized on the improvement of dielectric and

nonlinear J-E properties of CCTO/TiO2 ceramics. For instance, Lin et al. [36] reported the

study on electrical properties and nonlinear characteristics of CaCu3Ti4+xO12+2x (x=0.0, 0.5,

1.0 and 1.5) ceramics sintered at 1100 C for 3h. They found that both ' and tanwere

significantly decreased due to the potential barrier of TiO2 created at the GBs. Moreover,

Ouyang et al. [37] reported that microstructural and ' properties of CCTO/ TiO2 ceramics

could be enhanced after sintering at 1075 C for 8h. However, the investigation on electrical

and nonlinear properties of CCTO/TiO2 samples with the fulfillment of all three parameters

i.e. high ', low tan δ, and excellent dielectric response ('<15%) within a definite

temperature range is rarely reported. Moreover, the effect of sintering conditions (sintering

time/temperature) on the microstructural, dielectric properties (' and tan), nonlinear J-E

properties and temperature stability of ' (') in a wide range of CCTO/TiO2 ceramics has

never been reported. In addition, the study on CCTO/TiO2 ceramics is currently attractive to

researchers due to a number of their advantage such as (1) the nominal CCTO/TiO2

composition can be prepared by a one-step process [34-37, 41], (2) CCTO/TiO2 ceramics

exhibit no piezoelectricity, which is helpful to reduce mechanical damage in ac operation and

(3) sintering temperature employed for the preparation of this material is lower than that of

BaTiO3 [34-37, 41]. Therefore, it is a challenge to simultaneously improve the performance

 5

of dielectric, nonlinear J-E characteristics and a wide temperature range of '<15% in

CCTO/TiO2 ceramics. 

In this work, CaCu3Ti4O12 (CCTO) and CaCu3Ti4.2O12 (TiO02) precursor powders were

prepared by a well establish polymer pyrolysis (PP) route [2, 4, 17, 27, 38, 42, 43]. Effect of

sintering conditions i.e. sintering time and sintering temperature (sintering time/temperature)

on dielectric and nonlinear (J ‒ E) properties with the condition of '<15% of CCTO and

TiO02 ceramic samples were analyzed and discussed based on the promotion of oxygen

vacancy at GB. Surprisingly, excellent performance of dielectric properties ('4469 ‒

8932, tan 0.008 ‒ 0.032) with '<15% in a wide temperature range of -60 ‒ 180 C were

achieved in CaCu3Ti4.2O12 ceramics. Moreover, nonlinear J-E properties of all CaCu3Ti4O12

and CaCu3Ti4.2O12 ceramics were significantly enhanced by the appropriate sintering

conditions. In order to clarify the effect of sintering conditions on the dielectric and non-

ohmics properties of ceramic samples, impedance measurements were performed.

2 Experimental details

2.1 Samples preparation

CaCu3Ti4O12 (CCTO) and CaCu3Ti4.2O12 (Ti02) precursor powders were prepared by

the polymer pyrolysis (PP) method. Cu(NO3)2.3H2O (99.5% Carlo Erba), Ca(NO3)2.4H2O

(99.99% Kanto), TiC16H28O6 (75 wt.% in isopropanol), (NH4)2S2O4 (99.95% Carlo Erba) and

acrylic acid were employed as starting materials. Details for the preparation of CCTO

precursor powders were described elsewhere [17]. To prepare Ti02 precursor powders [17],

stoichiometric amount of TiC16H28O6 (5 mL) was dissolved in 12 mL of an aqueous acid

solution at room temperature (RT). Then, 0.576 g of Ca(NO3)2.4H2O and 1.738 g of

Cu(NO3)2.3H2O were added in this solution with constant stirring at 150 ºC for 15 min.

Meanwhile, 4 ‒ 5 drops of an aqueous 5% (NH4)2S2O8 solution (4.02 mL) were added into

the solution with constant stirring, until blue viscous gels of Ti02 precursors were obtained.
 6

Dry gels of CCTO and TiO02 precursors were subsequently grounded to fine powders,

heated at 350 ˚C for 2h, ground to fine powders again and then calcined at 900 ˚C for 10h.

These calcined CCTO and Ti02 precursor powders were pressed at a pressure of 150 MPa

into pellets of 4.75 mm in radius and  1.2 mm in thickness. CCTO and Ti02 pellets were

sintered at three different sintering conditions of 1025 ˚C for 5 h (denoted as CCTO-1 and

Ti02-1), 1025 ˚C for 12 h (denoted as CCTO-2 and Ti02-2) and 1095 ˚C for 5 h (denoted as

CCTO-3 and Ti02-3). All sintered pellets of CCTO and Ti02 are named as ceramic samples.

2.2 Characterization

Phase composition of ceramic samples were investigated by X-ray diffraction (PW3040

Philips; Cu-Kα radiation; λ = 0.15406 nm). Field emission scanning electron microscopy

(FESEM) (FEI Helios Nano Lab G3 CX) coupled with element mapping was employed for

the microstructural study of ceramic samples and elemental distribution of Ca, Cu, Ti and O

elements in these samples. Mean grain size (MGS) of each ceramic sample was estimated

using a standard line intercept technique, randomly made for at least 100 grains in each

FESEM image. Prior to the dielectric measurements, both surfaces of each ceramic samples

were subsequently polished, cleaned and then coated with Au, using a Polaron SC500

sputtering unit. The ratio of Ti3+/Ti4+ ions of ceramic samples were studied by X-ray

absorption near edge structure (XANES) using the multiples X-ray techniques (BL1.1W

(KKU), electron energy of 4 ‒ 48 keV; bending magnet; beam current 100 mA; 107 ‒ 1010

photon/s) at the Synchrotron Light Research Institute (SLRI), Nakhon Ratchasima, Thailand.

The complete details for the characterization method and analysis, including normalized

XANES data analysis by using ATHENA software comprised in an IFEFFIT package are

given elsewhere [44, 45]. The percentage of Ti3+ ions in ceramic samples were calculated

using equation (1),

 7

 E of sample 
%of Ti3 for each sample  100  1  3 4  (1)
 E of Ti and Ti std. 

where E is the difference of energy edge value between each ceramic sample and the TiF3

(Ti3+) standard.

2.3 Dielectric and nonlinear (J ‒ E) measurements

The dielectric loss tangent (tan) and capacitance (C) of ceramic samples were

measured by using an impedance gain phase analyzer (Hewlett Packard Model 4294A) in a

wide temperature and frequency range of -50 – 210 ˚C and 100 Hz – 1MHz, respectively.

Nonlinear (J ‒ E curves) measurements were performed at RT by using a high voltage

measurement unit (Keithley Model 247). Nonlinear coefficient () was calculated by

equation (2) and breakdown electric field (Eb) was determined at a current density (J) = 1

mA/cm2.

log( J 2 / J1 )
 (2)
log( E2 / E1 )

where E1 and E2 are the electric field, corresponding to J1 = 1 mA/cm2 and J2 = 10 mA/cm2,

respectively.

3 Results and discussion

Phase composition and crystal structure of ceramic samples were studied. Rietveld

refinement fitting profiles for the XRD patterns of CCTO-1, CCTO-2, CCTO-3, Ti02-1,

Ti02-2 and Ti02-3 samples are shown in Fig. 1 (a) – (f), respectively. Clearly seen in Fig.1,

all fitting profiles confirm the main XRD peaks correspond to those of the standard

CaCu3Ti4O12 ceramic (ICSD card No.95714). In addition, a minor peak around 2  33

corresponds to the CaTiO3 peak (ICSD card No.37263), is observed in the XRD patterns of

CCTO-2 and CCTO-3 samples. Moreover, the secondary phase of a rutile TiO2 peak (ICSD

card No.26715) is detected in the XRD patterns of all Ti02 ceramic samples, which is
 8

possibly due to an excess of Ti content. From Rietveld refinement fitting profiles the

CaCu3Ti4O12:TiO2 ratios of Ti02-1, Ti02-2 and Ti02-3 samples were determined from the

main diffraction peaks of each sample and found be 98.6:1.4, 98.3:1.7 and 98.9:1.1,

respectively. It is notable that all the diffraction peaks of the XRD patterns can be perfectly

indexed based on the bcc structure of a space group Im3. Quality of the refinement for each

ceramic sample is quantified by a profile residual (Rp), an expected residual (Rexp), a

weighted profile residual (Rwp), and a goodness of fit (GOF) [46] as summarized in Table1.

The GOF values of all ceramic samples are found to be in a range of approximately 1.0 ‒

2.0. The percentages of R (Rexp, Rwp, and Rp) factors for all ceramics are in the appropriate

range of approximately 3 ‒ 7%. Details for R values analysis of powder diffraction data

using Rietveld refinement were discussed elsewhere [47, 48]. According to the Rietveld

refinement fitting profiles, lattice parameters (a) of CCTO-1, CCTO-2, CCTO-3, Ti02-1,

Ti02-2 and Ti02-3 samples are found to be 7.391(3), 7.392(1), 7.393(1), 7.390(4), 7.391(3)

and 7.392(1) Å, respectively. These values are consistent and comparable with a value of

7.391 Å reported in literatures [2, 15, 38]. It is obvious that lattice parameter (a) of these

ceramic samples is slightly increased with the increase of sintering time/temperature,

resulting in the expansion of a unit cell. This result is similar to that observed in the CCTO

ceramics previously reported [38]. The theoretical density (Dxrd) of CCTO-1, CCTO-2,

CCTO-3, Ti02-1, Ti02-2 and Ti02-3 samples determined by the Rietveld refinement method

are found to be 5.0518, 5.0497, 5.0485, 5.0535, 5.0519 and 5.0500 g.cm-3, respectively. It is

notable that, Dxrd of all ceramic samples decrease with increasing sintering time/temperature,

which could be ascribed by the evaporation of intergranular phase affected by the sintering

process.

To study the effect of sintering time/temperature on the grain growth of ceramic

samples, polished surface of CCTO and Ti02 ceramic samples were taken by FESEM as
 9

shown in Fig. 2 (a)-(c) and (d)-(f), respectively. As illustrated in Fig. 2, the microstructural

evolution of CCTO and Ti02 ceramic samples are significantly influenced by sintering

conditions. The mean grain sizes (MGSs) of CCTO-1, CCTO-2 and CCTO-3 samples are

determined and found to be ∼5.50 ± 0.41, ∼11.02 ± 2.26 and ∼52.15 ± 8.37 m,

respectively. While those of Ti02-1, Ti02-2 and Ti02-3 samples are ∼3.06 ± 0.36, ∼3.63 ±

0.40 and ∼47.47 ± 8.41 m, respectively. It is remarkable that for the same sintering

condition, the MGSs of Ti02 ceramic samples are smaller than those observed in CCTO

ceramic samples, which could result from the solute drag mechanism effect [8, 49].

Moreover, it is also found that the MGSs of CCTO-2 and CCTO-3 samples are

approximately 2 and 10 times higher than that of CCTO-1 sample. Whereas, that of Ti02-3

sample display approximately 13 and 15 times higher than those of Ti02-2 and Ti02-1

samples. It is obvious that both sintering time/temperature can affect the grain growth, but the

most effective parameter is the sintering temperature. To clearly seen the composition

contrast in all ceramic samples, backscattered FESEM images of these samples was

examined. As seen in the insets of Fig. 2 (a)-(c), only a lighter phase can be observed in

CCTO-1 sample, whereas both of lighter and darker phases (red circles) are observed in

CCTO-2 and CCTO-3 samples. Similarly, for Ti02 ceramic samples with these images

illustrated in the insets of Fig. 2 (d)-(e), lighter and darker phases (blue circles) of Ti02-2 and

Ti02-3 samples are observed, whereas only a lighter phase is detected in Ti02-1 sample.

Moreover, white lines phases are observed along the grain boundary (GB) regions in Ti02-3

sample, corresponding to the CuO impurity phase. Therefore, it can be concluded that

impurity phases such as CaTiO3 and CuO) are observed in CCTO ceramic samples with

increasing of both sintering time/temperature and it is more effective by sintering

temperature. For Ti02 ceramic samples, it is obvious that any impurity phase is almost

generated by increasing sintering temperature.

 10

To observe the dispersion of the major elements Ca, Cu, Ti, and O in ceramic

samples, element mappings of these samples were performed using FESEM. As seen in Fig.3

(a) – (f) are the backscattered FESEM mapping images of Ca, Cu, Ti and O in the CCTO-1,

CCTO-2, CCTO-3, Ti02-1, Ti02-2 and Ti02-3 samples, respectively. Clearly seen in Fig.3,

all mapping images of ceramic samples confirm the existence of Ca, Cu, Ti, and O elements

with their homogeneous dispersion in grains and GBs. As illustrated in Fig. 3 (b) and (c),

only the CaTiO3 impurity phase is detected in CCTO-2 sample and CaTiO3 phase with small

amount of CuO are observed along the GB regions in CCTO-3 sample. Clearly seen in Fig. 3

(c), only element mapping of Ca, Ti and O are observed in the green point (red circle), while

the element mapping of Cu and O are detected on the pink spot (blue circle). Moreover, the

observed CaTiO3 and CuO impurity phases are consistent with the darker phase and white

lines phase, obviously seen in the inset of Fig. 2 (c). Obviously seen in Fig.3 (d), impurity

phases of TiO2 and CuO are not observed in Ti02-1 sample and only TiO2 secondary phase is

detected in Ti02-2 sample as shown in Fig.3 (e). Moreover, CuO and TiO2 secondary phases

are observed along the GBs (white lines) and at the GBs (blue spots) for Ti02-3 sample as

shown in Fig. 3 (f). Clearly seen in Fig. 3 (f), only the element mapping of Cu and O are

observed at the white lines along GBs regions, whereas only Ti and O elements are detected

at GBs (blue spots). Thus, it is concluded that sintering time/temperature significantly

influence on the formation of CaTiO3 impurity phase in CCTO ceramics and effectively

response by the sintering temperature. Whereas, the formation of TiO2 and CuO impurity

phases in the Ti02 samples is influenced only by the sintering temperature.

Effect of sintering time/temperature on  of CCTO and Ti02 ceramic samples are

shown in Fig.4 (a) and (b), respectively. Fig. 4 (a) and inset display the frequency

dependence of  and tanat 30 ˚C of CCTO ceramic samples. It can be seen in Fig. 4 (a) that

 and tan values increase with increasing sintering time/temperature due to the increase of
 11

dc conductivity (σdc) at GBs [50], consistent with the result reported in literature [5]. At 30 ˚C

and 1 kHz,  values of CCTO-1, CCTO-2 and CCTO-3 samples are found to be 13000,

56984 and 208598, respectively. It is remarkable that  values of CCTO-2 and CCTO-3

samples are approximately 4 and 16 times larger than that of CCTO-1 sample. It is obvious

that sintering temperature is a more effective parameter than sintering time on the

improvement of  properties. This might be due to the larger grain size of CCTO-3 sample

compare with those of CCTO-1 and CCTO-2 samples. Concurrently, tan values at 30 ˚C and

1 kHz of CCTO-1, CCTO-2 and CCTO-3 samples are found to be 0.077, 0.556 and 0.342,

respectively. Remarkably, tan values of CCTO-2 and CCTO-3 samples are about 7 and 4

times higher than that of CCTO-1 sample. It is obvious that sintering temperature can greatly

influence on tan values more than sintering time. As shown in Fig. 4 (b),  and tanof

Ti02-1, Ti02-2 and Ti02-3 samples at 30 ˚C and 1 kHz are determined and found to be 4469,

7221, 89302 and 0.021, 0.008, 0.032, respectively. Generally, the specification of tanvalue

for commercial applications of high performance dielectric should below 0.05 [23]. Clearly

seen in the inset of Fig. 4 (b), tanvalue of Ti02-2 sample is lower than 0.05 (below the blue

dash line) in a wide frequency range (102 ‒ 105 Hz), which is wider than those of Ti02-1

sample (102 ‒ 3×104 Hz) and Ti02-3 sample (102 ‒ 5×103 Hz). Remarkably,  values of

Ti02-3 and Ti02-2 samples is approximately 1.6 and 20 times higher than that of Ti02-1

sample. Interestingly, at 30 ˚C and 1 kHz, tanvalue of Ti02-2 sample can be reduced by

approximately 2.6 times, while that of Ti02-3 sample slightly increases by approximately 1.5

times compare with that of Ti02-1 sample. This corresponds to the increasing  values of

Ti02-2 and Ti02-3 samples compare with that of Ti02-1 sample. It is obvious that both of

sintering time/temperature can significantly affect the increase of  values of CCTO and

Ti02 ceramic samples. In addition, tanvalues of CCTO and Ti02 ceramic samples are
 12

increased with increasing sintering time/temperature, exceptional for Ti02-2 sample. It is

obvious that Ti02-2 sample displays the lowest tan value of 0.008, which might result from

the high Rgb value, compare with other ceramic samples. This might originate from the excess

TiO2 phase in the microstructure of Ti02-2 sample, as obviously confirmed by the XRD

results. Generally, it was reported that the excess of TiO2 could influence on the Rg and Rgb,

especially for Rgb [36]. Thus, it can be concluded that Ti02-2 sample can demonstrate a very

high dielectric performance i.e. it performs a very low tan and a high  over a wide

frequency range. Very low tan and high  values of Ti02-2 sample are comparable with

those values reported in CCTO ceramics [2-4, 27]. Comparison of dielectric constant () and

dielectric loss tangent (tan) of Ti02 ceramic samples with those of other capacitor materials

are provided in Table 2.

In addition to high  and very low tan another important parameter considered for

perfect dielectric properties of commercial capacitor commercials is the temperature

coefficient of   of which the standard specification is defined to be less than ± 15% over

a wide range of temperature. For instance, the temperature range of EIA code X5R, X7R and

X8R capacitors with  < ±15% are -55 85 ˚C, -55 125 ˚C and -55 150 ˚C, respectively

[51]. As shown in Fig. 5 (a) and (b),  of all ceramic samples are evaluated at the frequency

 T   30

of 1 kHz and defined as    100  (%) [38], where  T and  30 are ' at a

 30

temperature of T and 30 ºC, respectively. As seen in Fig. 5(a),  of all CCTO samples

greatly increase with increasing temperature and the value is far beyond the standard

specification. In Fig. 5(b), the value of  < ±15% for Ti02-1, Ti02-2 and Ti02-3 samples are

found to be in a temperature range of -60 ˚C ‒ 130 ˚C, -60 ˚C ‒ 180 ˚C, and -60 ˚C ‒ 110

˚C, respectively. It is remarkable that, dielectric properties of Ti02-1, Ti02-2 and Ti02-3

samples are suitable for the EIA code X5R and X7R; X5R, X7R and X8R; and X5R
 13

capacitors, respectively. It is evident that giant  and very low tan with the excellent

temperature coefficient of Ti02 ceramic samples can be accomplished by a specific sintering

condition, which is difficult to achieve in others CCTO ceramic samples. In this study,  <

±15% of the Ti02-2 sample is valid and satisfy in a wider temperature range than those of

other CaCuTi4O12-based ceramics [2, 9, 25, 26, 29, 30]. Moreover, the validity of  < ±15%

in a wider temperature range of Ti02-2 sample is comparable with those reported in co-doped

TiO2 ceramics [52, 53]. Comparison of temperature stability ranges (T) of  < ±15% (at 1

kHz) and tan< 0.05 for Ti02 ceramic samples with those of other high temperature

capacitive materials are provided in Table 2.

Temperature dependence of  at 1 kHz for all CCTO and Ti02 ceramic samples are

shown in Fig. 5(c) and (d), respectively. It is observed in Fig. 5(c) that, at 1 kHz,  values of

all CCTO ceramic samples start to increase at a temperature higher than 60 ˚C. Temperature

dependence of  in our CCTO ceramic samples behave similar to those observed in other

CCTO ceramics reported in literatures [2, 3, 38]. As shown in Fig 5 (d), at 1 kHz,  of Ti02-2

sample are moderately temperature dependent in a temperature range of -60 ˚C − 210 ˚C,

whereas those of Ti02-1 and Ti02-3 samples are in a narrower temperature range of -60 ˚C ‒

140 ˚C. The insets of Fig. 5(c) and (d) display the temperature dependence of tanδ at 1 kHz

for all CCTO and Ti02 ceramic samples, respectively. In the insets of Fig.5 (c) and Fig.5 (d),

the red dashed lines represent tan= 0.05. As illustrated in the inset of Fig.5 (d), tan values

of Ti02-2 sample are under 0.05 in a temperature range -60 – 100 ºC, which is wider than

those of -60 – 70 ºC and -60 – 50 ºC for Ti02-1 and Ti02-3 samples, respectively. In addition,

tanvalues of all CCTO ceramic samples (inset of Fig. 5(c)) are above 0.05 through the

whole temperature range from -50 to 210 ºC. The large increase in tan δ at high temperature

of all CCTO ceramic samples is consistent with their great increase in . It is evident that

sintering time/temperature can significantly influence not only on the improvement of

 14

dielectric properties (high and very low tanδ values) of Ti02 ceramic samples, but also

simultaneously improve the temperature stability of  in a wider range than usual. These very

high performance dielectric as well as the condition of  < ±15% are difficult to achieve in

other giant dielectric materials, especially in CCTO ceramics with excess Ti [36, 37, 41]. It

can be concluded that very high performance dielectric properties (high and very low-

tanwith stability of  in wide temperature range) can be achieved in the nominal

CaCu3Ti4.2O12 ceramic sintered at 1025 ˚C for 12 h (Ti02-2), where the Ti02 precursor

powders are prepared by the polymer pyrolysis solution method.

Nonlinear characteristics (J−E curves) of Ti02 and CCTO ceramic samples are shown

in Fig. 6 and inset of Fig. 6, respectively. In these figures both types of all ceramic samples

display a nonlinear J−E curves. α and Eb values of Ti02 and CCTO ceramic samples can be

determined from these J−E curves. At RT, α values of CCTO-1, CCTO-2 and CCTO-3

samples are found to be 8.02, 2.40 and 2.91, while Eb values are 3994, 506 and 164 V.cm-1,

respectively. In case of Ti02-1, Ti02-2 and Ti02-3 samples, α and Eb values are found to be

55.06, 29.40 and 6.07; and 9313, 12221 and 870 V.cm-1, respectively. It can be seen that Eb

values of CCTO ceramic samples significantly decrease with increasing sintering

time/temperature, which is more effectively by sintering temperature. Accordingly, Eb value

of CCTO-3 sample is lower than those of CCTO-1 and CCTO-2 samples. In addition, it is

evident that Eb value of Ti02-2 sample is approximately 1.3 and 14 times higher than those of

Ti02-1 and Ti02-3 samples, respectively. Remarkably, the highest α value obtained in Ti02-

1sample is ~2.75 times greater than that of a general varistor material ZnO [54] and ~ 5  19

times higher than those values reported in literatures [2, 9, 20, 43, 49]. This suggests a potent

application of Ti02-1sample for varistor. In addition, the maximum Eb value observed in

Ti02-2 sample is closely correlated with the highest Rgb value, which might result in the
 15

lowest tan value. It is notable that enlargement of Eb value might be arising from a strongly

enhanced Rgb.

Effect of sintering time/temperature on grain (Rg) and grain boundary (Rgb) resistance

were performed through the Z* plots. Generally, large- and small- semicircular arcs at low-

and high-frequency ranges in the Z* plots correspond to Rgb and Rg, respectively [9]. In this

work, only large-semicircular arcs can be observed in all ceramic samples. In order to

estimate the Rgb values of all CCTO and Ti02 ceramic samples, Z* plot at high temperature

was performed. As seen in Fig. 7 (a) and inset (1) of Fig. 7(a), Rgb values at 150 ˚C of CCTO-

1, CCTO-2 and CCTO-3 samples were estimated from the large-semicircular arcs and found

to be 9032, 354 and 500.cm, respectively. It is obvious that Rgb values of CCTO ceramic

samples largely decrease with increasing sintering time from 5 h to 12 h as for CCTO-2

sample and this similar manner is also observed with increasing sintering temperature from

1025 C to 1095 C as for CCTO-3 sample. Clearly seen in Table 2 for the list of Rgb and Rg

values, Rgb values of CCTO-2 and CCTO-3 samples are approximately 25 and 18 times lower

than that of CCTO-1 sample. As shown in inset (2) of Fig. 7 (a), Rg values estimated from a

nonzero intercept on the Z axis at high frequencies [9] are found to be 42.6, 26.8 and

12.7.cm for CCTO-1, CCTO-2 and CCTO-3 samples, respectively. Obviously, Rg

decreases with increasing sintering time/temperature, indicating the increase of free charge

carriers concentration in grains. As seen in Fig. 7 (b) and inset (1) of Fig. 7 (b), Rgb values at

150 ˚C of Ti02-1, Ti02-2 and Ti02-3 samples are found to be 360000, 656000 and

3000.cm, respectively. As shown in inset (2) of Fig. 7 (b), Rg values of Ti02-1, Ti02-2 and

Ti02-3 samples are estimated and found to be 186, 40.8 and 11.4.cm, respectively. It is

notable that Rgb values of Ti02-2 and Ti02-3 samples are approximately 1.8 and 0.008 times

of Ti02-1 sample. It is obvious that sintering time can effectively improve Rgb values of Ti02

ceramic samples rather than sintering temperature. Notably, at the same sintering condition,
 16

Ti02 ceramic samples display Rgb values about 40, 1312 and 9 times higher than that of

CCTO ceramic samples. It is remarkable that the highest Rgb value of Ti02-2 sample is

correlate with the lowest tan and the highest Eb values of this sample. This result might

originate from the excess TiO2 phase in the microstructure of Ti02-2 sample.

To understand the electrical mechanism of grain boundaries for all ceramic samples, the

imaginary part (Z) of the complex impedance (Z*) were determined. Z* can be calculated by

using Eq. (3) as described in our previous work [17]. As seen in Fig. 8 (a), the maximum

peak position of Z (Zmax) decreases and shifts to a higher frequency region with increasing

temperature. Rgb of ceramic samples can be calculated using Rgb = 2Zmax [17]. Fig. 8 (b)

displays the relationship between grain boundary conductivity (gb) (gb =1/Rgb) and

temperature, according to the Arrhenius law,

 Egb
 gb  0 exp( ) (3)
kBT

where 0, kB and T are the pre-exponential term, Boltzmann constant and absolute

temperature, respectively. Egb is the activation energy for the conduction at GBs. Egb values

of CCTO-1, CCTO-2 and CCTO-3 samples were determined and found to be 0.568, 0.506

and 0.531 eV, respectively. For Ti02-1, Ti02-2 and Ti02-3 samples, Egb values are 0.605,

0.650 and 0.638 eV, respectively. As illustrated in the inset (2) of Fig. 8 (a), Egb values of

CCTO ceramic samples decrease with increasing sintering time from 5 h to 12 h as for

CCTO-2 sample and further increase with increasing sintering temperature from 1025 C to

1095 C as for CCTO-3 sample. This behavior is correlated with the enhancement of Rgb and

tan as clearly seen from the data listed in Table 2. As shown in the inset (1) of Fig. 8 (a), Egb

values of Ti02 ceramic samples significant increase with increasing sintering time as for

Ti02-2 sample, and slightly decrease with increasing sintering temperature as for Ti02-3

sample. Remarkably, the highest Egb value of Ti02-2 sample is correlated with the lowest
 17

tan and the maximum Rgb value. Notably, at the same sintering condition, Egb values of Ti02

ceramic samples are approximately 1.2 ‒ 1.3 times higher than those of CCTO ceramic

samples. These Egb values of Ti02 ceramic samples (Egb  0.605 – 0.650 eV) are comparable

with those values reported in other CCTO ceramics (Egb  0.46–0.75 eV) [22, 38, 39, 42],

Ln3+-doped CaCu3Ti4O12 ceramics (Egb  0.55–0.76 eV) [9, 43, 49] and co-doped CCTO

ceramics (Egb  0.61–0.81 eV) [25, 26, 28]

Other important parameter that effect dielectric properties is the correlation between

semiconducting grains and oxidation states of Ti ions in grains of CCTO and Ti02 ceramic

samples. Oxidation states of Ti ions can be determined by the XANES technique. Fig.9

displays the normalized Ti K-edge XANES spectra of CCTO and Ti02 ceramic samples

compare with those of the TiF3 (Ti3+) and TiO2 (Ti4+) standards. In Fig.9, the edge energies of

TiF3, TiO2, CCTO-1, CCTO-2, CCTO-3, Ti02-1, Ti02-2 and Ti02-3 spectra appear at

approximately 4977.43, 4979.76, 4979.60, 4979.45, 4979.52, 4979.48, 4979.43 and 4979.40

eV, respectively. It can be seen that, the edge energies of all CCTO and Ti02 ceramic

samples are close to that of TiO2 standard (4979.76 eV), indicating the oxidation state of 4+

for Ti ion. However, an infinitesimal change in the edge values of Ti K-edge XANES spectra

for CCTO and Ti02 ceramic samples due to the existence of Ti3+ ions were detected. Similar

results had been observed in our previous works [9, 38]. By using Eq. (1), Ti3+/Ti4+ (%) ratios

in CCTO and Ti02 ceramic samples are obtained and summarized in Table 2. It is also found

that Ti3+/Ti4+ (%) ratios for CCTO ceramic samples increase with increasing sintering

time/temperature. Notably, Ti3+/Ti4+ (%) ratios of CCTO-3 sample is smaller than that of

CCTO-2 sample. The increase of (%) Ti3+/Ti4+ (%) ratios are consistent with the increase of

oxygen vacancies inside grains, which can result in an increasing of ' in CCTO-2 and

CCTO-3 samples. Similarly, effect of sintering time/temperature on Ti3+/Ti4+ (%) ratios of

Ti02 ceramic samples were observed. Obviously seen in Fig. 9 and data listed in Table 2,
 18

Ti3+/Ti4+ (%) ratios for Ti02-3 and Ti02-2 samples are approximately 1.4 and 1.2 times

higher than that of Ti02-1 sample, consistent with the increase of ' values. It is suggested

that the increase of Ti3+/Ti4+ (%) ratios corresponds to the oxygen vacancies inside the grains.

In addition, semiconducting grain of n-type in all CCTO and Ti02 ceramic samples are

supposed to originate from the possible hopping of electron between Ti3+ ↔ Ti4+ sites in the

structure. Therefore, it is concluded that the promotion of oxygen vacancies is effectively

influenced by the sintering temperature rather than by the sintering time and vice versa for

the tan values.

4 Conclusion
A nominal CaCu3Ti4O12 (CCTO) and CaCu3Ti4.2O12 (Ti02) ceramic compounds were

prepared by sintering their precursor powders obtained by the polymer pyrolysis solution

method at three different conditions. Microstructure, dielectric properties, non-linear

properties and temperature stability of  were investigated according to the sintering

conditions. It was found that microstructural evolution of all ceramic samples was strongly

dependent on sintering temperature i.e. increasing sintering temperature could yield a larger

mean grain size (MGS) than that obtained by increasing sintering time. Sintering time and

sintering temperature could effectively influenced on  and tanvalues of all ceramic

samples i.e.  and tanvalues increased with increasing sintering time/temperature. Although

very high  values were achieved in all CCTO ceramic samples, their corresponding

tanvalues were also very high as well. On the other hand, Ti02 ceramic samples with

properly high  values and very low tanvalues had demonstrated themselves to be

appropriate materials for capacitor applications. This was suggested to originate from the

excess Ti ions in their structures that formed a secondary phase of TiO2 at GBs, which could

result in very high Rgb. In addition, the promotion of oxygen vacancies at GBs could also

affect dielectric properties. Interestingly, Ti02 ceramic sample showed  and tanvalues in
 19

the range of 4469 ‒ 89302 and 0.008 ‒ 0.032, respectively. Surprisingly, very low

tan0.008 and  7221 with temperature stability of  < ±15% in a wide range of -60 ‒

180 ºC were achieved in Ti02 ceramic sample sintered at 1025 ºC for 12 h (Ti02-2 sample).

Therefore, this Ti02-2 sample is suggested to be a promising material for EIA code X5R,

X7R and X8R capacitors. Non-linear coefficient () and breakdown field (Eb) of all ceramic

samples were significantly improved by the sintering conditions as well. In case of Ti02-2

sample,  and Eb values were found to be ~ 29.04 and ~ 12221 V/cm-1, respectively. As

shown by impedance spectroscopy, Rgb of Ti02 ceramic samples significantly increased with

increasing sintering conditions. The enhancement of dielectric and nonlinear properties in

Ti02 ceramic samples as a result of sintering process were suggested to originate from the

microstructure evolution of grain and the improvement of GBs intrinsic properties.

Acknowledgments

This work was financially supported by the National Research Council of Thailand

(NRCT) under Rajamangala University of Technology Rattanakosin (Grant No.A-59/2561).

It was also supported by the Thailand Research Fund through the Royal Golden Jubilee Ph.D.

Program (PHD/0207/2558). The Nanotec-KKU Center of Excellence on Advanced

Nanomaterials for Energy Production and Storage, Khon Kaen University are also grateful

for their co-financial support. Integrated Nanotechnology Research Center (INRC), Khon

Kaen University was acknowledged for co-financial support. The authors express their

appreciation to the Synchrotron Light Research Institute (SLRI), Nakhon Ratchasima,

Thailand is acknowledged for XANES measurements.

 20

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0.4(Ba0.8Ca0.2)TiO3–0.6Bi(Mg0.5Ti0.5)O3 lead-free ceramics, Journal of Materials Science:

Materials in Electronics, 27 (2016) 12128-12133.

[58] X. liu, L. Liu, F. Han, S. Liu, H. Xiang, L. Fang, Erratum to: Dielectric behavior of

La2O3-modified 0.4(Ba0.8Ca0.2)TiO3–0.6Bi(Mg0.5Ti0.5)O3 lead-free ceramics, Journal of

Materials Science: Materials in Electronics, 28 (2017) 12372-12372.

[59] S. Zheng, D. Shi, L. Liu, G. Li, Q. Wang, L. Fang, B. Elouadi, Oxygen vacancy-related

dielectric relaxation and electrical conductivity in La-doped Ba(Zr0.9Ti0.1)O3 ceramics,

Journal of Materials Science: Materials in Electronics, 25 (2014) 4058-4065.

 27

LIST OF TABLE CAPTIONS

Table 1 Lattice parameter (a), mean grain size (MGS) and structural data obtained from the

Rietveld refinement fitting profiles of XRD patterns of all ceramic samples.

Table 2 Comparison of dielectric constant (), dielectric loss tangent (tan), Rg and Rgb,

temperature range (T) of  < ±15% (at 1 kHz), temperature range (T) of tan< 0.05,

and Eb values at RT, and Ti3+/Ti4+ (%) ratios of all ceramic samples obtained in this work

with those reported in other capacitor materials.

Table 1 Lattice parameter (a), mean grain size (MGS) and structural data obtained from the

Rietveld refinement fitting profiles of XRD patterns of all ceramic samples.

Samples CCTO-1 CCTO-2 CCTO-3 Ti02-1 Ti02-2 Ti02-3

a (Å) 7.391(3) 7.392(1) 7.393(1) 7.390(4) 7.391(3) 7.392(1)

5.50 ± 11.02 ± 52.15 ± 3.06 ± 3.63 ± 47.40 ±
MGS (m)
0.41 2.26 8.37 0.36 0.40 8.41
Rexp (%) 5.131 4.109 5.828 4.060 4.099 4.162

Rp (%) 4.074 4.095 4.651 3.321 3.925 3.754

Rwp (%) 5.997 5.791 6.956 4.444 5.197 5.068

GOF 1.365 1.986 1.424 1.198 1.607 1.482

 28
Table 2 Comparison of dielectric constant (), dielectric loss tangent (tan), Rg and Rgb, temperature range (T) of  < ±15% (at 1 kHz),
temperature range (T) of tan< 0.05, and Eb values at RT, and Ti3+/Ti4+ (%) ratios of all ceramic samples obtained in this work with those
reported in other capacitor materials.
Sample Sintering  tan Rg Rgb T(˚C) of T (˚C) of  Eb (%)
conditions (RT) (RT) (.cm) (.cm)  < ±15% tan< 0.05 (V.cm-1) Ti3+/Ti4+
CCTO-1(CaCu3Ti4O12)a 1025 ˚C/5h 13000 0.077 42.6150 9032150 -40 ‒ 80 − 8.02 3994 7.37
CCTO-2(CaCu3Ti4O12)a 1025 ˚C/12h 56984 0.556 26.8150 354150 − − 2.40 506 15.34
CCTO-3(CaCu3Ti4O12)a 1095 ˚C/5h 208598 0.342 12.7150 500150 -20 ‒ 40 − 2.91 164 11.48
Ti02-1(CaCu3Ti4.2O12)a 1025 ˚C/5h 4469 0.021 186150 360000150 -60 ‒ 130 -60 ‒ 70 55.06 9313 13.65
Ti02-2(CaCu3Ti4.2O12)a 1025 ˚C/12h 7221 0.008 40.8150 656000150 -60 ‒ 180 -60 ‒ 100 29.40 12221 16.50
Ti02-3(CaCu3Ti4.2O12)a 1095 ˚C/5h 89302 0.032 11.8150 3000150 -60 ‒ 110 -60 ‒ 50 6.07 870 18.27
CCTO-Zn10(CaCu2.9Zn0.10Ti4O12) [2] 1070 ˚C/6h 6554 0.016 10520 163000090 -60 ‒ 155 − 5.62 1832 14.67
Ca0.97Pr0.02Cu3Ti4O12 [9] 1015 ˚C/10h 8469 0.016 4530 130200080 -70 ‒ 140 -70 ‒ 40 14.74 5640 8.4
SmZn10(Ca0.925Sm0.05Cu2.90Zn0.10Ti4O12)[26] 1070 ˚C/6h 5313 0.041 6920 8955000080 − − − 4601 6.41
YbMg05(Ca0.925Yb0.05Cu2.95Mg0.05Ti4O1)[29] 1070 ˚C/4h 10000 0.018 5020 83000080 -70 ‒ 110 -70 ‒ 60 − − −
Mg30(Ca2Cu2.7Mg0.3Ti4O12) [30] 1100 ˚C/6h 3550 0.014 − 1770000120 -60 ‒ 160 -60 ‒ 82 27.2 8859 −
10%ScNTO(Sc0.5Nb0.5)0.1Ti0.9O2 [53] 1300 ˚C/5h 6000 0.035 5020 >100000200 -60 ‒ 170 -30 ‒ 110 − − −
CaCu3Ti3.98Y0.02O12 [55] 1080 ˚C/12h 32000 0.80 1228RT 4647 RT − − − − −
BNT-0.03Yb((Bi0.5Na0.5)0.97Yb0.03TiO3) [56] 1200 ˚C/2h 1204 0.038* − − 147 ‒ 528b 154 ‒ 356c − − −
BB30La (0.4(Ba0.8Ca0.2)0.7La0.3TiO3- 1350 ˚C/4h 700 0.064* − − 30 ‒ 550b 93 ‒ 353c − − −
0.6Bi(Mg0.5Ti0.5)O3) [57, 58]
BLZT-3(Ba0.94La0.06(Zr0.9Ti0.1)0.985O3) [59] 1380 ˚C/4h 400577* 0.25577* − 650000577* − − − − −
a
in this work, 20 = at 20 ˚C, 30 = at 30 ˚C, 80 = at 80 ˚C, 90 = at 90 ˚C, 120 = at 120 ˚C, 150 = at 150 ˚C, 200 = at 200 ˚C, 577 = at 577 ˚C, b
 <±10% and c tan< 0.05
*
Estimated numerical values from figures in cited references
 29

LIST OF FIGURE CAPTIONS

Fig.1 Rietveld refinement fitting profiles of (a) CCTO-1, (b) CCTO-2, (c) CCTO-3, (d) Ti02-

1, (e) Ti02-2 and (f) Ti02-3 samples.

Fig. 2 FESEM images of (a) CCTO-1, (b) CCTO-2, (c) CCTO-3, (d) Ti02-1, (e) Ti02-2 and

(f) Ti02-3 samples with their corresponding insets display the backscattered FESEM images.

Fig. 3 Mapping of Ca, Cu, Ti and O elements for (a) CCTO-1, (b) CCTO-2, (c) CCTO-3, (d)

Ti02-1, (e) Ti02-2 and (f) Ti02-3 samples.

Fig. 4 (a) and (b) display frequency dependence of  at 30 ˚C for all CCTO and Ti02 ceramic

samples, respectively. Insets of (a) and (b) display frequency dependence of tan for these

ceramic samples.

Fig. 5 (a) and (b) display temperature coefficient of dielectric constant  at 1 kHz for all

CCTO and Ti02 ceramic samples, respectively. (c) and (d) with their insets display

temperature dependence of  (-60 − 210 ˚C) and tan(-60 − 180 ˚C) at 1 kHz for all CCTO

and Ti02 ceramic samples, respectively.

Fig.6 J-E curves at RT of Ti02-1, Ti02-2 and Ti02-3 samples with inset shows those of

CCTO-1, CCTO-2 and CCTO-3 samples.

Fig. 7 Impedance complex plane plots (Z*) at 150 C of (a) all CCTO and (b) all Ti02 ceramic

samples with their corresponding insets display the magnification of (1) the overlapping

region and (2) the expanded view of high frequency data close to the origin.

Fig.8 (a) Frequency dependence of Z at various temperatures ranging from 140 C ‒ 200 C

for Ti02-2 sample. (b) Arrhenius plots of ln (gb) versus 1000/T for all CCTO (solid symbol)

and Ti02 (open symbol) ceramic samples.

Fig. 9 Normalized Ti K-edge XANES spectra of CCTO-1, CCTO-2, CCTO-3, Ti02-1, Ti02-

2 and Ti02-3 samples with those of TiO2 and TiF3 standards.

 30

Fig. 1
yobs
(a) CCTO-1 yobs (d) Ti02-1
ycalc
ycalc
Intensity (a.u.)

yobs-ycalc
yobs-ycalc

Intensity (a.u.)
CCTO peaks
Bragg peaks TiO2 peaks

20 30 40 50 60 70 80 20 30 40 50 60 70 80
2 (Deg.) 2 (Deg.)
(b) CCTO-2 yobs (e) Ti02-2 yobs
ycalc ycalc
Intensity (a.u.)

yobs-ycalc yobs-ycalc
Intensity (a.u.)
Bragg peaks CCTO peaks
TiO2 peaks

20 30 40 50 60 70 80 20 30 40 50 60 70 80
2 (Deg.) 2 (Deg.)
(c) CCTO-3 yobs (f) Ti02-3 yobs
ycalc ycalc
Intensity (arb. unit)
Intensity (a.u.)

yobs-ycalc yobs-ycalc
Bragg peaks CCTO peaks
TiO2 peaks

20 30 40 50 60 70 80 20 30 40 50 60 70 80
2 (Deg.) 2 (Deg.)

Fig.1 Rietveld refinement fitting profiles of (a) CCTO-1, (b) CCTO-2, (c) CCTO-3, (d) Ti02-

1, (e) Ti02-2 and (f) Ti02-3 samples.

 31

Fig. 2

Fig. 2 FESEM images of (a) CCTO-1, (b) CCTO-2, (c) CCTO-3, (d) Ti02-1, (e) Ti02-2 and

(f) Ti02-3 samples with their corresponding insets display the backscattered FESEM images.
 32

Fig. 3

Fig. 3 Mapping of Ca, Cu, Ti and O elements for (a) CCTO-1, (b) CCTO-2, (c) CCTO-3, (d)

Ti02-1, (e) Ti02-2 and (f) Ti02-3 samples.

 33

Fig. 4

106
(a)
5
10

104
'

103 1.0
CCTO-1
0.8 CCTO-2 CCTO-1
tan

2 0.6 CCTO-3
10 0.4
o
@ 30 C CCTO-2
0.2 CCTO-3
101 0.0 2 3 4 5
10 10 10
Frequency(Hz)
10
@ 30 oC
100 2
10 103 104 105 106
Frequency (Hz)
(b)
105

104
'

103 0.10
Ti02-1 @ 30 C
o
0.08 Ti02-2
Ti02-1
102
tan

0.06 Ti02-3
0.04
Ti02-2
0.02 Ti02-3
101 0.00 2
@ 30 oC
3 4 5
10 10 10 10
Frequency(Hz)
100 2
10 103 104 105 106
Frequency (Hz)

Fig. 4 (a) and (b) display frequency dependence of  at 30 ˚C for all CCTO and Ti02 ceramic

samples, respectively. Insets of (a) and (b) display frequency dependence of tan for these

ceramic samples.
 34

Fig. 5
6
30 10
(a) (c)
CCTO-1
20 CCTO-2 10
5

10 CCTO-3
'(%)

'
10
101
0 3
@ 1kHz
10 100

tan
-10 10-1 CCTO-1
CCTO-1
10
2 CCTO- CCTO-2
X5R X7R X8R 10-2 CCTO-3
-20 @1 kHz CCTO-3
o 1 10-3-60 -30
@ 30 C, 1 kHz 10 0 30 60 90 120150180
-30 Temperature(oC)
-60 -30 0 30 60 90 120 150 180 210
o
Temperature( C) -60 -30 0 30 60 90 120 150 180 210
o
Temperature( C)
30
(b) (d) 5
Ti02-1 10
20 Ti02-2
4
Ti02-3 10
10
'(%)

'

3 101
0 10 Ti02-1
@ 1kHz
100 Ti02-
tan

Ti02-3 Ti02-1
-10 2 10-1
10 Ti02-2
X5R X7R X8R 10-2
-20 @1 kHz Ti02-3
o 1 10-3-60 -30 0 30 60 90 120150180
@ 30 C, 1 kHz 10
Temperature(oC)
-30
-60 -30 0 30 60 90 120o
150 180 210 -60 -30 0 30 60 90 120 150 180 210
Temperature( C) o
Temperature( C)

Fig. 5 (a) and (b) display temperature coefficient of dielectric constant  at 1 kHz for all

CCTO and Ti02 ceramic samples, respectively. (c) and (d) with their insets display

temperature dependence of  (-60 − 210 ˚C) and tan(-60 − 180 ˚C) at 1 kHz for all CCTO

and Ti02 ceramic samples, respectively.

 35

Fig. 6

25 20

J(mA.cm )
-2
15
CCTO-1
20 10
CCTO-2
CCTO-3
J(mA.cm )
-2

15 0
0 2000 4000 6000
-1
E(V.cm )

10
Ti02-1
Ti02-2
5 Ti02-3

0
0 3000 6000 9000 12000 15000
-1
E(V.cm )
Fig.6 J-E curves at RT of Ti02-1, Ti02-2 and Ti02-3 samples with inset shows those of

CCTO-1, CCTO-2 and CCTO-3 samples.

 36

Fig. 7

1.0 5 8
(a) (1) (2)

-Z"(102 .cm)
4

-Z"(10 .cm)
6
3 @ 150 oC
4 @ 150 oC
-Z"(104 .cm)
2
1 2
0 0
0 1 2 3 4 5 6 7 0 2 4 6 8 10 12
Z'(102.cm) Z'(10 .cm)
0.5

CCTO-1
CCTO-2
@ 150 oC CCTO-3
0.0
0.0 0.5 1.0 1.5
Z'(10 .cm) 4

8 4
4
(b) (1) (2)
-Z"(102 .cm)
-Z"(103 .cm)

3 3
@ 150 oC
@ 150 oC
-Z"(105 .cm)

2 2
6
1 1

0 0
0 1 2 3 4 5 0 1 2 3 4
Z'(103 .cm) Z'(102.cm)
4

2 Ti02-1
Ti02-2
@ 150 oC Ti02-3
0
0 3 6 9
Z'(10 .cm) 5

Fig. 7 Impedance complex plane plots (Z*) at 150 C of (a) all CCTO and (b) all Ti02 ceramic

samples with their corresponding insets display the magnification of (1) the overlapping

region and (2) the expanded view of high frequency data close to the origin.
 37

Fig. 8
o 0.66
(a) 5 140 C 0.64 (1)
0.62

Egb(eV)
0.60
Ti02-1 Ti02-2 Ti02-3
-Z"(105 .cm) 4 0.58
0.56
0.54

3 0.52 (2)
0.50
CCTO-1 CCTO-2 CCTO-3
Samples
2 Ti02-2 170 oC
140 oC 180 oC
1 150 oC 190 oC
160 oC 200 oC
0 200 oC
102 103 104 105 106
Frequency (Hz)

(b)
-6
Lngb(S.cm-1)

-9

-12

-15 Ti02-1 CCTO-1

Ti02-2 CCTO-2
GB Ti02-3 CCTO-3
-18
2.0 2.4 2.8 3.2
-1
1000/T(K )

Fig.8 (a) Frequency dependence of Z at various temperatures ranging from 140 C ‒ 200 C

for Ti02-2 sample. (b) Arrhenius plots of ln (gb) versus 1000/T for all CCTO (solid symbol)

and Ti02 (open symbol) ceramic samples.

 38

Fig. 9

1.5
Normalized x(E)

1.2

0.9
TiF3
0.6
TiO2
CCTO-1 Ti02-1
0.3
CCTO-2 Ti02-2
CCTO-3 Ti02-3
0.0
4960 4980 5000 5020 5040
Energy (eV)
Fig. 9 Normalized Ti K-edge XANES spectra of CCTO-1, CCTO-2, CCTO-3, Ti02-1, Ti02-

2 and Ti02-3 samples with those of TiO2 and TiF3 standards.