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Effect of tantalum substitutions on

microstructures and dielectric properties of
calcium copper titanate (CaCu3Ti4O12) ceramic

Article in Materials Science and Engineering B · August 2012

Impact Factor: 2.17 · DOI: 10.1016/j.mseb.2012.06.002

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Contents lists available at SciVerse ScienceDirect

Materials Science and Engineering B

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

1 Short communication

2 Effect of tantalum substitutions on microstructures and dielectric properties of

3 calcium copper titanate (CaCu3 Ti4 O12 ) ceramic
4 Q1 Alok Kumar Rai a , Nitish Kumar Singh a , Susant Kumar Acharya b , Laxman Singh c , K.D. Mandal c,∗
a
5 Department of Materials Science and Engineering, Chonnam National University, 300 Yongbong-dong, Bukgu, Gwangju 500-757, Republic of Korea
b
6 Department of Semiconductor Science and Technology, Basic Research Laboratory (BRL), Semiconductor Physics Research Center (SPRC),
7 Chonbuk National University, Jeonju 561–756, Republic of Korea
c
8 Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi 221005, UP, India
9

10 a r t i c l e i n f o a b s t r a c t
11
12 Article history: Tantalum (Ta5+ ) doped CaCu3 Ti4−x Tax O12 (x = 0.05 and 0.10) ceramics were prepared by semi-wet route
13 Received 17 February 2012 using solid Ta2 O5 powder and metal nitrate solutions. Powder X-ray diffraction confirmed the major phase
14 Received in revised form 4 June 2012 formation of cubic CaCu3 Ti4 O12 ceramic in the doped samples sintered at 900 ◦ C for 6 h. Microstructure has
15 Accepted 10 June 2012
been studied using field-emission scanning electron microscopy. The grain size is in the range of 150 nm
Available online xxx
to 1 ␮m for both compositions. Dielectric constant of the samples increases with increasing tantalum
16
concentrations.
17 Keywords:
© 2012 Published by Elsevier B.V.
18 Ceramic
19 Sol–gel preparation
20 Sintering
21 X-ray diffraction
22 Dielectric property

23 1. Introduction the second one involves the reduction of Cu2+ ions to Cu1+ ions 44

at high temperature [12,13]. In addition, some other explanations 45

24 High dielectric constant materials are immensely useful for for the observed permittivity response have been also reported, 46

25 miniaturization of electronic devices which is a recent goal of such as bimodal grain size model [14], internal domain [15], elec- 47

26 our technological process. In this situation, a new dielectric mate- trode polarization effect [15], Cu-stoichiometry effect [16], and so 48

27 rial, calcium copper titanate (CaCu3 Ti4 O12 or CCTO) has attracted on. However, no mechanism is complete enough to explain the 49

28 a lot of interest in the past few years. It was reported that the similar dielectric response in both CCTO ceramics and single crys- 50

29 dielectric constant (ε) of CCTO ceramic is more than 104 and tals within low and high temperature range. Although this ceramic 51

30 that of single crystal CCTO is close to 105 and it remains rea- has extremely high permittivity, but one serious drawback pos- 52

31 sonably invariant over a wide temperature range from 100–600 K sessing high dielectric loss and low varistor voltage which hinders 53

32 [1–3]. Moreover, CCTO also has high potential for use in many its commercial applications [9]. Much work based on ion substitu- 54

33 electronic applications such as capacitors, memory devices, gas tion at Cu or Ti ion site in CCTO ceramics has been carried out in 55

34 sensors, humidity sensors, and varistors [1,4–8]. But the reason order to improve the dielectric properties and extend the under- 56

35 is still unclear what mechanism is responsible for the anoma- standing of the origin of giant dielectric response in CCTO ceramics 57

36 lous dielectric behavior. Among the published works, a plausible [17–21]. Most of the substitutions in CCTO ceramics offered the 58

37 mechanism accepted that the existence of semi-conductive grain significant effects on the values of dielectric permittivity, loss tan- 59

38 and insulating grain boundaries in bulk CCTO ceramics resulted gent and electrical conductivity of grain boundaries. In addition to 60

39 an internal barrier layer capacitance (IBLC) effect and this mech- their giant dielectric properties, CCTO ceramics also exhibited the 61

40 anism was supported by impedance spectroscopy analysis [3,7,9]. nonlinear current–voltage (I–V) relationship [8,22–27]. This behav- 62

41 This IBLC effect is strongly related to CCTO’s dielectric behavior ior was also observed in other related-perovskite oxides such as 63

42 [8,10,11]. Two theories were also proposed to explain CCTO semi Na1/2 La1/2 Cu3 Ti4 O12 ceramics [28]. The cause of this behavior is 64

43 conducting grains: the first one is related to the oxygen loss and the existence of intrinsic potential barriers at the grain bound- 65

aries, i.e. the Schottky barrier [8,29]. The nonlinear I–V behavior 66

of CCTO ceramics is strongly related to the electrical properties of 67

∗ Corresponding author. Tel.: +91 542 6702868; fax: +91 542 2368428. grain boundaries and the overall dielectric response. Shao et al. also 68

E-mail address: kdmandal.apc@itbhu.ac.in (K.D. Mandal). reported that the stoichiometry played a crucial role in obtaining 69

0921-5107/$ – see front matter © 2012 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.mseb.2012.06.002

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70 the high dielectric permittivity when donor-type dopant (Nb5+ ) and citric acid (99.5%, Merck, India) were used as raw materials. 100

71 was added [16,30]. Recent literatures reported the doping of CCTO Measured amount of titanium butoxide was dissolved in acetic acid 101

72 ceramics using supervalent metal cations such as Nb5+ and Ta5+ by stirring for half an hour at room temperature. A second solu- 102

73 which can modify their nonlinear I–V relationship and the total tion consisting of calculated calcium acetate, copper acetate, acetic 103

74 macroscopic electrical resistivity of grain boundaries (Rgb ) [31,32]. acid and ethanol was prepared by stirring for 30 min at 120 ◦ C and 104

75 The breakdown voltage obtained from I–V curves and Rgb decreased both solutions were mixed together. Appropriate amount of solid 105

76 with increasing concentration of dopants. Unfortunately, a very tantalum oxide powder was added to the mixed solutions with stoi- 106

77 few results are reported about the influence of supervalent metal chiometric composition of CaCu3 (Ti4−x Tax )O12 (x = 0.05 and 0.10). 107

78 cations doping on the nonlinear I–V relationship, dielectric prop- Citric acid (equivalent to metal ions) was then added to this solu- 108

79 erties and resulting electrical responses at grain boundaries, as tion. The solution was heated to 80 ◦ C with constant stirring to 109

80 well as the microstructure of CCTO ceramics [31–33]. Moreover, evaporate the water, resulting in a highly viscous blue gel. It was 110

81 the mentioned literatures reported the conventional solid-state then dried in an oven at 100–120 ◦ C overnight to get a dry gel. The 111

82 synthesis of supervalent metal ion doped CCTO ceramics which dried CCTTO gel was calcined in air at 800 ◦ C for 6 h. The calcined 112

83 requires repeated calcination and sintering at high temperature powder was pressed into cylindrical pellets using a hydraulic press. 113

84 (≥1000 ◦ C) in comparison to chemical routes such as sol–gel and The pressed samples were sintered at 900 ◦ C for 6 h in air. Heat- 114

85 co-precipitation methods. ing as well as cooling rates were maintained at 5 ◦ C/min during 115

86 In the present work, we are reporting a systematic study calcination and sintering. 116

87 of Ta2 O5 doped CaCu3 Ti4−x Tax O12 (CCTTO) at higher concentra- The phase composition of the samples was revealed by using the 117

88 tions level (0.05 and 0.10 mol%) by semi-wet route at relatively X-ray diffraction analysis (Rigaku D/MAX–111A system) with Cu K␣ 118

89 lower temperature. This semi-wet route employs citrate–nitrate radiation ( = 1.5406 Å) and 2 range from 30◦ to 80◦ . Images of the 119

90 gel chemical method using Ta2 O5 solid powder. These samples are microstructure were studied using freshly fractured surface of the 120

91 characterized by powder X-ray diffraction (XRD), field-emission sintered sample by field-emission scanning electron microscope 121

92 scanning electron microscopy (FE-SEM) and energy dispersive X- (FE-SEM, S-4700 Hitachi). Energy dispersive X-ray spectroscopy 122

93 ray spectroscopy (EDX) techniques. The dielectric properties have (EDX) analysis was also performed on the grains. 123

94 also been discussed. Dielectric measurements were made using a pellet which both 124

surfaces were polished and coated with silver paint. An impedance 125

95 2. Experimental analyzer (Novocontrol Alpha-A High Performance Frequency Ana- 126

lyzer) was used to measure the dielectric constant (ε ), dielectric 127

96 Calcium acetate monohydrate [Ca(C2 H3 O2 )2 ·H2 O)] (99.99%,

97 Sigma–Aldrich), copper acetate monohydrate [Cu(C2 H3 O2 )2 ·H2 O]
98 (99.99%, Sigma–Aldrich), titanium butoxide [(C16 H36 O4 )Ti] (97%,
99 Sigma–Aldrich), tantalum oxide [Ta2 O5 ] (99.99%, Sigma–Aldrich)

Fig. 1. X-ray powder diffraction patterns of CaCu3 Ti4−x Tax O12 ceramics (a) x = 0.05 Fig. 2. FE-SEM micrographs of fractured surface of CaCu3 Ti4−x Tax O12 ceramics (a)
and (b) 0.10 sintered at 900 ◦ C for 6 h. 0.05 and (b) 0.10. (c) EDX spectra of CaCu3 Ti4−x Tax O12 ceramic (x = 0.10).

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128 loss (tan ı), impedance and modulus in the temperature and fre- size in the range of 150 nm to 1 ␮m and presence of agglomer- 156

129 quency range of 300–500 K and 102 –106 Hz respectively. ation. Disparity in grain size increases with increasing tantalum 157

doping. Grain size of these samples synthesized by this method is 158

relatively smaller than that formed by the ceramic method [38]. 159
130 3. Results and discussion
Fig. 2(c) shows the representative EDX spectrum of the whole 160

region containing both large as well as small grains of CCTTO 161

131 Fig. 1(a and b) shows the powder X-ray diffraction patterns of
(x = 0.10) ceramic. Ca, Cu, Ti, Ta and O are found to be 3.26, 39.93, 162
132 CCTTO samples doped with different concentrations of Ta2 O5 (0.05
24.65, 2.67 and 29.49 wt%, respectively, which confirmed the tan- 163
133 and 0.10 mol%) after sintering at 900 ◦ C for 6 h. Comparing these
talum doping. 164
134 patterns with those of the standard powder XRD pattern of CCTO
Variation of dielectric constant (ε ) with temperature at a few 165
135 (JCPDS Card No. 75-1149), the presence of CCTO was confirmed, in
selected frequencies between 100 Hz and 1 MHz of CCTTO for dif- 166
136 both the samples, as a major phase. Beside main perovskite CCTO
ferent compositions (x = 0.05 and 0.10) is shown in Fig. 3(a and 167
137 phase, the diffraction peaks show that a small amount of CuO and
b). It can be seen from Fig. 3 that values of dielectric constant 168
138 TiO2 secondary phase exist in the CCTTO ceramics. As expected,
ε ) for CCTTO samples is smaller than that reported for undoped 169
139 the pure CCTO phase is obtained only when the ratio of calcium,
CCTO ceramics [1]. This may be due to lower sintering temperature 170
140 copper and titanium are very close to the stoichiometric ones. It is
(900 ◦ C) and no segregation of impurity phase such as CuO at grain 171
141 also reported that the Ti content mostly controls the phase com-
boundaries [39–41]. Dielectric constant (ε ) increases with increas- 172
142 position (single or multiphased material) of the CCTO powder [34].
ing the tantalum concentrations. It is clearly seen that the dielectric 173
143 The authors believed that the secondary phases comes from one or
constant remains nearly constant up to 500 K at higher frequen- 174
144 more of the following reasons; (1) solubility of Ta5+ is less than
cies such as 100 kHz and 1 MHz. At lower frequency (100 Hz), 175
145 0.05 mol%, (2) charge neutrality is not maintained by electronic
the dielectric constant of CCTTO ceramics increases rapidly up to 176
146 compensation, (3) ion diffusing displacement is shortened in the
500 K and shows a broad anomaly around ∼465 K where dielectric 177
147 sol–gel process and at last, and (4) TiO2 is observed if more than
constant increases sharply. The author believes that this anomaly 178
148 four Ti per 12 oxygens are present in the powder [33,35–37]. It
will be also appear at higher temperature and higher frequencies 179
149 can be also observed that TiO2 peaks increases with increasing the
from 1 kHz to 1 MHz, which is beyond our temperature range of 180
150 tantalum concentrations.
measurement. These features has been observed and explained 181
151 Fig. 2(a and b) shows microstructure of the fractured surfaces
as a ferroelectric relaxor behavior [42] associated with the slow- 182
152 of the CCTTO ceramics (x = 0.05 and 0.10) sintered at 900 ◦ C for 6 h.
ing down of dipolar fluctuations within the polar nanoclusters 183
153 It is clearly seen that microstructure of CCTTO ceramics changes
[43]. 184
154 significantly with increase in concentration of tantalum. FE-SEM
155 image shows faceted grain-packed morphology with varying grain

Fig. 3. Temperature dependence of dielectric constants for CaCu3 Ti4−x Tax O12 Fig. 4. Temperature dependence of dielectric loss for CaCu3 Ti4−x Tax O12 ceramics (a)
ceramics (a) 0.05 and (b) 0.10 measured at various frequencies. 0.05 and (b) 0.10 measured at various frequencies.

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Fig. 5. Frequency dependence of dielectric constants for CaCu3 Ti4−x Tax O12 ceramics
(a) 0.05 and (b) 0.10 measured at various temperatures.
Fig. 6. Frequency dependence of dielectric loss for CaCu3 Ti4−x Tax O12 ceramics (a)
0.05 and (b) 0.10 measured at various temperatures.

185 Fig. 4(a and b) shows the variation of loss tangent (tan ı) val-
186 ues at different selected frequencies for both the compositions of Impedance and modulus analysis separates the contributions 214

187 CCTTO ceramics (x = 0.05 and 0.10) as a function of temperature. It of the grains, grain boundaries and electrode specimen interface to 215

188 is clearly observed that the dielectric loss for the sample x = 0.10 is the total observed resistance and capacitance of the sample, respec- 216

189 lower than that of sample x = 0.05 over the entire temperature range tively [45]. Typical complex plane impedance plot obtained for both 217

190 of measurement. This is higher than that for undoped CCTO [1]. CCTTO (0.05 and 0.10) ceramics at 400 K is shown in Fig. 7(a and b) 218

191 There is an increase of dielectric loss with increase in temperature. respectively. Similar plots are observed at other temperatures also. 219

192 This is due to increase in conductivity with increase in temperature. One arc is clearly observed in these plots at 400 K which is corre- 220

193 Fig. 5(a and b) shows the variation of dielectric constant vs log sponding to the grain boundaries because it has larger resistance 221

194 frequency at a few selected temperatures for CCTTO ceramics. As (for sample x = 0.10, Rgb = 6.48 × 107  and Rg = 2.31 × 104 ) [46]. 222

195 can be seen from the figure, the dielectric behaviors for both the As can be seen from Fig. 7, the resistance of grain boundaries of 223

196 CCTTO compositions are almost similar in the entire frequency CCTTO sample increases with increasing the dopant concentration 224

197 range and decreases with increase in frequency. In addition, the from 0.05 to 0.10. This may be one reason for higher dielectric con- 225

198 dielectric constant for the composition (x = 0.10) is higher than the stant of sample x = 0.10 as compared to x = 0.05, because increase 226

199 other composition (x = 0.05) over the entire measured frequency in grain boundaries resistance increase the capacitance of grain 227

200 range. Both the CCTTO compositions displayed a broad anomaly boundaries and hence the dielectric constant. 228

201 nearly 1 kHz frequency at 500 K temperature. This anomaly will Fig. 8(a and b) shows the modulus plot for both the CCTTO sam- 229

202 also appear in both the samples at higher frequency with increasing ples (x = 0.05 and 0.10) at different selected temperatures. Two arcs 230

203 temperatures which is beyond our temperature range of measure- are clearly observed over the entire measured frequency range in 231

204 ment. both the samples. In fact, the first arc is the contribution of grain 232

205 Fig. 6(a and b) shows the variation of loss tangent (tan ı) vs boundaries whereas the second arc is the contribution of grains 233

206 log frequency at a few selected temperatures for the doped CCTTO [46]. It is also observed that with increasing temperature, the capac- 234

207 ceramics. The frequency dependence of tan ı shown in figure indi- itance of grains (Cg ) as well as grain boundaries (Cgb ) decreases. 235

208 cates that tan ı decreases rapidly over the entire frequency range. As a representative, the calculated capacitance of grains and grain 236

209 This may be due to the presence of small interfacial polarization boundaries of CCTTO sample (x = 0.10) are 19.35 × 10−12 F and 237

210 in these materials [44]. At lower temperature, tan ı is almost fre- 44.8 × 10−12 F at 350 K whereas 18.9 × 10−12 F and 42.47 × 10−12 F 238

211 quency independent up to 1 MHz. More importantly, the dielectric are calculated at 400 K respectively. As can be seen from figure, the 239

212 loss of the CCTTO ceramic with x = 0.10 composition is lower than capacitance of grains and grain boundaries increase with increasing 240

213 that of x = 0.05 composition. the dopant concentrations. 241

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Fig. 9. Frequency dependence of imaginary part of electric modulus at different

Fig. 7. The Cole–Cole plot of impedance spectra at 400 K for CaCu3 Ti4−x Tax O12
temperature for CaCu3 Ti4−x Tax O12 ceramics (a) 0.05 and (b) 0.10.
ceramics (a) 0.05 and (b) 0.10.

Fig. 9(a and b) shows the variation of imaginary part of electrical 242

modulus (M ) with log frequency at various selected temperatures 243

for both the CCTTO ceramics (x = 0.05 and 0.10). It is observed that 244

the height of the peak increases with increasing temperature which 245

indicates the capacitance of grains and grain boundaries decreases 246

with increasing temperature. The resistance of the grains and grain 247

boundaries can be calculated from the peak frequency using the 248

formula ωRC = 1 which has the same value as calculated by the 249

impedance and modulus plots. Therefore, the results from modulus 250

spectroscopy support the conclusions drawn from the impedance 251

and modulus plots. 252

4. Conclusion 253

CaCu3 Ti4−x Tax O12 (CCTTO) (x = 0.05 and 0.10) samples were syn- 254

thesized by semi-wet route. Solutions of metal nitrate and solid 255

Ta2 O5 powder were used for preparation of CCTTO samples. XRD 256

analysis confirmed the major phase formation of CCTO in the pre- 257

pared CCTTO samples with the presence of CuO and TiO2 secondary 258

phases at 900 ◦ C/6 h. FE-SEM image shows faceted grain-packed 259

morphology with the grain size in the range of 150 nm to 1 ␮m 260

and presence of agglomeration. Impedance and modulus plots con- 261

firmed that resistance and capacitance of the samples increases 262

with increasing the dopant concentrations. This may be the rea- 263

son for increase of dielectric constant with increasing the tantalum 264

concentrations. 265

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