(Nb, Al)共掺BaTiO3陶瓷的巨介电及介电弛豫现象

doi:10.15541/jim20160280

摘要/Abstract

摘要：

(Nb, Al)共掺的BaTiO₃陶瓷(BaTi_0.98(Nb_0.5Al_0.5)_0.02O₃)表现出巨介电现象, 介电常数可以达到3×10⁵, 介电损耗为0.2。在10^-1~10⁷ Hz范围内, 观察到三种介电弛豫现象, 并分别对其进行了分析。低频段(10^-1~10 Hz)和中频段(10³~10⁵ Hz)属于非德拜弛豫, 分别是由于Maxwell-Wagner电极界面极化和晶界层电容器效应引起的; 相反, 高频段(10⁵~10⁷ Hz)属于德拜弛豫, 通过阿伦尼乌斯公式的拟合, 得到其激活能E = 15 meV和频率因子 f₀= 7×10⁶ Hz。较小的激活能和频率因子表明其弛豫过程可能来源于复杂缺陷团簇中的电子的局域运动, 被称为钉扎电子-缺陷偶极子效应。本研究显示钉扎电子-缺陷偶极子效应可以作为设计新型巨介电钙钛矿材料的依据。

关键词: (Nb, Al)共掺, 钙钛矿, 巨介电常数, 钉扎电子-缺陷偶极子

Abstract:

Nb and Al co-doped BaTiO₃ ceramics, BaTi_0.98(Nb_0.5Al_0.5)_0.02O₃, have a colossal permittivity (ε_r≈3×10⁵, tanδ≈0.2) at room-temperature. Three distinct relaxation processes are observed in the frequency range from 10^-1 to 10⁷ Hz. The low-frequency relaxation between 10^-1 and 10 Hz and the intermediate-frequency relaxation between 10³ and 10⁵ Hz are non-Debye relaxations, which are attributed to Maxwell-Wagner interfacial polarization, electrode interfacial polarization, and barrier layer capacitor. While the high-frequency process between 10⁵ and 10⁷ Hz is a typical Debye-type relaxation with an activation energy of E≈15 meV and a frequency factor of f₀≈7×10⁶ Hz. The small activation energy and relatively small frequency factor in the BaTi_0.98(Nb_0.5Al_0.5)_0.02O₃ ceramics indicate that this relaxation process may derive from local motion of electrons in the complex defect clusters, which results from co-doping and can be named as electron-pinned defect-dipoles. This study suggests that the electron-pinned defect-dipoles mechanism can be used to design colossal permittivity in perovskites, like BaTiO₃.

Key words: (Nb, Al) co-doped, perovskites, colossal permittivity, electron-pinned defect-dipoles

中图分类号:

TQ174

黄栋, 吴颖, 苗纪远, 刘志甫, 李永祥. (Nb, Al)共掺BaTiO₃陶瓷的巨介电及介电弛豫现象[J]. 无机材料学报, 2017, 32(2): 219-224.

HUANG Dong, WU Ying, MIAO Ji-Yuan, LIU Zhi-Fu, LI Yong-Xiang. Colossal Permittivity and Dielectric Relaxations of (Nb, Al)Co-doped BaTiO₃ Ceramics[J]. Journal of Inorganic Materials, 2017, 32(2): 219-224.

图/表 6

Fig. 1 shows the temperature dependence of dielectric spectra of BTNA and pure BaTiO3 ceramics. Comparing to BaTiO3, the permittivity of BTNA is significantly improved. Colossal permittivity, εr >105, is observed for BTNA ceramic sample between 150 K and 450 K. Meanwhile, the temperature stability of BTNA is also enhanced. There is no permittivity peak related to the phase transition which is observed in the BaTiO3 sample. The permittivity shows a relatively flat platform at the temperature range from 280 K to 370 K. The considerable improvement of permittivity and its temperature stability in BTNA demonstrates that its CP doesn’t originate from ferroelectricity. No impurity phase is found in XRD pattern and the shift of the diffraction peaks implies that Nb and Al have been introduced into the lattice of the BaTiO3 crystal grains. The microstructural and elemental investigation also show the uniform distribution of dopants. And the BTNA ceramic is single tetragonal phase, the same as BaTiO3[11]. Hence, the CP should not be from other phases.

Fig. 1 Temperature dependence of permittivity and dielectric loss for BaTiO3 ceramic sintered at 1623 K/6 h and BTNA ceramic sintered at 1593 K/6 h in temperature range from 123 K to 459 K

Fig. 2 Comparison of the dependent permittivity and dielectric loss of BTNA, CaCu3Ti4O12[12], (Li, Ti) co-doped NiO[14], (Nb, In) co-doped TiO2[8] and spark plasma sintered BaTiO3[13] in the frequency range from 10 Hz to 107 Hz

Fig. 3 Frequency dependence of the dielectric loss of BTNA ceramic in the frequency range from 10 Hz to 107 Hz measured from 143 K to 383 K. The inset shows the M’’ spectroscopic plots for the BTNA at low frequency range (0.04 Hz to 10 Hz)

Fig. 4 The dependence of dielectric loss peak frequency on testing temperature from 143 K to 383 K

Fig. 5 Core level XPS (open circles) and corresponding fitting results (solids lines) of BTNA sample

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(Nb, Al)共掺BaTiO₃陶瓷的巨介电及介电弛豫现象

Colossal Permittivity and Dielectric Relaxations of (Nb, Al)Co-doped BaTiO₃ Ceramics

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