尖晶石型CuAl2O4掺杂对CaCu3Ti4O12陶瓷介电性能的影响

doi:10.15541/jim20150118

摘要/Abstract

摘要：

研究了尖晶石型CuAl₂O₄掺杂对CaCu₃Ti₄O₁₂陶瓷显微结构、介电性能以及松弛特征和缺陷结构的影响。在频率为10^-1~10⁷ Hz、温度为153~453 K的条件下测量了样品的介电性能。研究表明, 适量添加CuAl₂O₄, 使样品晶粒尺寸减小并趋于均匀, 击穿场强从CaCu₃Ti₄O₁₂陶瓷样品的3.0 kV/cm提高到13.0 kV/cm, 低频介电损耗减小。介电松弛中的高频松弛过程起源于晶粒本征缺陷的电子松弛过程, 其活化能~0.10 eV基本不变; 随着CuAl₂O₄含量增加, 与界面相关的松弛活化能从0.50 eV减小到0.22 eV, 可能与CuAl₂O₄在样品中引入杂质及更复杂的界面有关; 电导活化能从0.66 eV增至0.86 eV, 归因于CuAl₂O₄第二相抑制了晶界处的载流子跳跃, 提高了Schottky势垒高度。CuAl₂O₄掺杂量大于100mol%, 过量CuAl₂O₄会导致样品晶界势垒崩塌, 样品失去非欧姆特性和巨介电性能。

关键词: CaCu3Ti4O12, 介电性能, 压敏特性

Abstract:

The influences of CuAl₂O₄ doping on the microstructure and dielectric relaxation of CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. The dielectric properties were measured in the frequency from 10^-1 Hz to 10⁷ Hz under the temperature from 153 to 453 K. It was found that reduced CCTO grains as well as improved microstructure were achieved by addition of 30mol%-50mol% CuAl₂O₄. When sintered at 1100℃ for 4 h, enhanced electric breakdown field of 13 kV/cm was obtained with 50mol% CuAl₂O₄ addition, while its dielectric loss at low frequency was greatly suppressed. Three energy levels of dielectric relaxation processes were found. It is suggested that energy level 1 eV of ~0.10 eV, corresponding to high frequency relaxation and barely varied with CuAl₂O₄ addition, is attributed to the intrinsic electronic relaxation. Energy level 2 decreased from 0.50 eV to 0.22 eV with increased additional CuAl₂O₄, possibly resulted from multi impurities and boundaries. The energy level of conduction process rose from 0.66 eV to 0.86 eV with increased CuAl₂O₄ addition, which can be attributed to the block effect of more grain boundaries. In addition, the excessive content CuAl₂O₄ resulted in collapse of grain boundary barrier, leading to the vanish of non-ohmic properties and high dielectric constant.

Key words: CaCu3Ti4O12, dielectric properties, varistor properties

中图分类号:

TM281

李建英, 侯林林, 贾然, 高璐, 武康宁, 李盛涛. 尖晶石型CuAl₂O₄掺杂对CaCu₃Ti₄O₁₂陶瓷介电性能的影响[J]. 无机材料学报, 2015, 30(10): 1056-1062.

LI Jian-Ying, HOU Lin-Lin, JIA Ran, GAO Lu, WU Kang-Ning, LI Sheng-Tao. Influences of CuAl₂O₄ Doping on the Dielectric Properties of CaCu₃Ti₄O₁₂ Ceramics[J]. Journal of Inorganic Materials, 2015, 30(10): 1056-1062.

图/表 9

图1 1100 ℃烧结4 h的CCTO-xCuAl2O4(x=0、30mol%、50mol%、200mol%)陶瓷样品和CuAl2O4样品的XRD图谱(a), x=200mol%样品的BSEM照片(b)

Fig. 1 XRD patterns of CCTO-xCuAl2O4 (x=0, 30mol%, 50mol%, 200mol%) composite ceramics and CuAl2O4 samples sintered at 1100℃ for 4 h (a) and BSEM image of sample with 200mol% CuAl2O4 (b)

表1 图1(b)中测试点的EDS能谱结果

Table 1 EDS results for the marked points in Fig. 1(b)

Element /at%	A	B
O	10.54	13.53
Al	2.84	27.91
Ca	10.68	6.55
Ti	38.93	10.90
Cu	37.01	41.11

图2 不同组分和烧结条件下CCTO-xCuAl2O4陶瓷的SEM照片

Fig. 2 SEM image of CCTO ceramics CCTO ceramics sintered at 1100℃ for 4 h (a) and 10 h (b); CCTO- 50mol% CuAl2O4 ceramics sintered at 1100 ℃ for 4 h (c) and 10 h (d)

图3 CCTO-xCuAl2O4复相陶瓷和CuAl2O4样品的非线性系数(α)、击穿场强(Eb)和J-E特性

Fig. 3 α, Eb and J-E characteristics of the samples at room temperature (a) Dependence ofα and Eb on CuAl2O4 addition; (b) J-E characteristics of the samples sintered at 1100 ℃ for 4 h with different CuAl2O4 additions

图4 1100℃烧结4 h CCTO-xCuAl2O4复相陶瓷样品在室温下复阻抗谱图

Fig. 4 Impedance spectra of CCTO-xCuAl2O4 composite ceramics sintered at 1100 ℃ for 4 h at room temperature. (a) x=50mol%; (b) x=0, 100mol%

表2 室温下1100 ℃烧结4 h样品的晶粒晶界等效电阻值

Table 2 Resistivity for both bulk and grain boundary of the samples sintered at 1100℃ for 4 h at room temperature

Doping ratio	R_gb/MΩ	R_g/Ω
0	37	47
15mol%	274	140
30mol%	426	190
50mol%	2008	203
100mol%	520	264
200mol%	0.23	-

图5 1100 ℃烧结4 h CCTO-xCuAl2O4样品在室温下 (a) ε′ 和(b) tanδ随频率的变化关系

Fig. 5 Variation in dielectric constant (a) and dielectric loss tanδ (b) for the samples sintered at 1100 ℃ for 4 h with CuAl2O4 addition

图6 1100℃烧结4 h CCTO-50mol%CuAl2O4样品的复模量虚部M ''与频率的关系

Fig. 6 Frequency and temperature dependence of electric modulus for CCTO-50mol% CuAl2O4 composite ceramics sintered at 1100 ℃ for 4 h (a) 153-273 K, (b) 333-433 K. the inset in (b) shows the energy levels of defect relaxation calculated by Arrhenius law

表3 1100 ℃烧结4 h CCTO-xCuAl2O4 (x=0、50mol%、200mol%)样品的松弛活化能和击穿场强Eb

Table 3 Energy levels and breakdown field Eb of CCTO-xCuAl2O4 (x=0, 50mol%, 200mol%) ceramics sintered at 1100 ℃ for 4 h

Sample	Peak1/eV	Peak2/eV	Peak3/eV	E_b/(kV·cm^-1)
x=0	0.11	0.51	0.66	3.0
x=50mol%	0.15	0.40	0.86	13.0
x=200mol%	0.15	0.22	—	1.0

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尖晶石型CuAl₂O₄掺杂对CaCu₃Ti₄O₁₂陶瓷介电性能的影响

Influences of CuAl₂O₄ Doping on the Dielectric Properties of CaCu₃Ti₄O₁₂ Ceramics

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