压电材料中缺陷偶极子特性的研究进展

doi:10.3724/SP.J.1077.2013.12127

无机材料学报 ›› 2013, Vol. 28 ›› Issue (2): 123-130.DOI: 10.3724/SP.J.1077.2013.12127 CSTR: 32189.14.SP.J.1077.2013.12127

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压电材料中缺陷偶极子特性的研究进展

杜刚, 梁瑞虹, 李涛, 卢晓蓉, 王根水, 董显林

(中国科学院上海硅酸盐研究所, 中国科学院无机功能材料与器件重点实验室, 上海200050)

收稿日期:2012-03-01 修回日期:2012-05-23 出版日期:2013-02-10 网络出版日期:2013-01-23
作者简介:杜刚(1987–), 男, 博士研究生. E-mail: dugang0623@163.com
基金资助:
国家高技术研究发展计划(863计划)(2009AA03Z108);上海市科学技术发展基金(9595810900);中国科学院上海硅酸盐研究所创新基金(Y03ZC3130G)

Recent Progress on Defect Dipoles Characteristics in Piezoelectric Materials

DU Gang, LIANG Rui-Hong, LI Tao, LU Xiao-Rong, WANG Gen-Shui, DONG Xian-Lin

(Key Laboratory of Inorganic Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China)

Received:2012-03-01 Revised:2012-05-23 Published:2013-02-10 Online:2013-01-23
About author:DU Gang. E-mail: dugang0623@163.com
Supported by:
National High Technology Research and Development Program of China (2009AA03Z108);Shanghai Foundation for Development of Science and Technology, China (9595810900);Technology Innovation Foundation of Shanghai Institute of Ceramics, Chinese Academy of Sciences, China (Y03ZC3130G)

摘要/Abstract

摘要：

压电材料通过受主掺杂或烧结挥发等可以形成缺陷偶极子, 缺陷偶极子对材料的性能有显著的影响。本文综述了压电材料中缺陷偶极子的产生及其在外场下的响应机理, 同时, 从缺陷偶极子运动的角度分析了压电材料中老化、电滞回线异常及电致形状记忆效应等现象的起源, 简要分析了偶极子弛豫现象, 并对未来发展高可靠性压电驱动器的研究作了展望。

关键词: 压电材料, 缺陷偶极子, 束腰电滞回线, 对称一致性原理, 综述

Abstract:

Defect dipoles which have pronounced effects on properties of piezoelectric materials can be introduced either by partially modifying with acceptor impurities or volatizing of cation elements in perovskite lattice during sintering. The formation mechanism of defect dipoles and responses under external fields were reviewed in the present paper. Besides, the main physic mechanisms of ferroelectric aging, hysteresis loop abnormalities and electro- shape-memory effects in piezoelectric materials were discussed in detail from the defect dipoles viewpoints. Based on a defect mediated reversible domain switching mechanism, large recoverable electro-strain, as well as constricted hysteresis loops were obtained in unpoled aged ferroelectric crystals and/or ceramics, which indicated that aging was not always a detrimental effect, and may be promising for future novel applications. Furthermore, the defect dipole relaxation process was briefly described and the development trends of the high reliability piezoelectric actuators were proposed.

Key words: piezoelectric materials, defect dipoles, constricted hysteresis loops, symmetry-conforming principle, review

中图分类号:

TM282

杜刚, 梁瑞虹, 李涛, 卢晓蓉, 王根水, 董显林. 压电材料中缺陷偶极子特性的研究进展[J]. 无机材料学报, 2013, 28(2): 123-130.

DU Gang, LIANG Rui-Hong, LI Tao, LU Xiao-Rong, WANG Gen-Shui, DONG Xian-Lin. Recent Progress on Defect Dipoles Characteristics in Piezoelectric Materials[J]. Journal of Inorganic Materials, 2013, 28(2): 123-130.

图/表 10

图1 钙钛矿结构中氧空位的分布(a)顺电相和(b)铁电相

Fig. 1 The distribution of oxygen vacancies in perovskite structure

图2 (a)BaTi0.98Ca0.02O2.98陶瓷压电常数d33的老化曲线[30], (b)Ba(Ti1-xFex)O3陶瓷介电常数及损耗的老化曲线[29]

Fig. 2 (a) Aging of the piezoelectric coefficient for BaTi0.98Ca0.02O2.98 ceramic after poling[30]; (b) Aging of the dielectric constant and the dielectric loss for Ba(Ti1-xFex)O3 ceramics[29]

图3 含有缺陷偶极子的压电陶瓷极化老化后的(a)电滞回线, (b)极化反转电流-电场曲线, (c)电畴反转示意图(图中P是自发极化, Ei是内偏场)[18]

Fig. 3 Schematic representation of (a) asymmetric polarization hysteresis curve (b) I-E curve (c) domain switching of aged piezoelectric ceramics containing defect dipoles (P denotes spontaneous polarization, Ei denotes internal bias field) [18]

图4 (a)[001]取向PMNT62/38-0.2Fe单晶[7]和(b)PNZTM95/5陶瓷的束腰电滞回线[7,34]

Fig. 4 Constricted double hysteresis loops of (a) [001] oriented PMNT62/38-0.2Fe crystals[7] and (b) PNZTM95/5 ceramics[7,34]

图5 点缺陷的对称一致性原理: (a)顺电相和(b)铁电相

Fig. 5 Symmetry-conforming property of point defects in (a) Cubic phase and (b) ferroelectric tetragonal phase

图6 缺陷偶极子导致的可逆畴变过程

Fig. 6 Defect dipoles related reversible domain switching process

图7 电致形状记忆效应机理示意图: (a)老化后的多畴四方铁电相, (b)施加电场后的单畴结构, (c)可逆畴变产生的双电滞回线, (d)大的可回复电致应变[37]

Fig. 7 Mechanism of large electro-shape-memory by reversible domain switching in aged ferroelectrics (a) multidomain tetragonal ferroelectrics after aging (b) single-domain state by electric field E (c) double hysteresis loop (P-E curve) during reversible domain switching (d) huge electrostrain (ε-E curve) during reversible domain switching[37]

图8 老化的[001]取向BaTiO3单晶及PZN-PT单晶、PZT陶瓷的电致形变的对比示意图[13]

Fig. 8 Large electric-field-induced strain in an aged [001]- oriented BaTiO3 single crystal in comparison with the piezoelectric effect of PZT ceramics and PZN-PT single crystals[13]

图9 (a) Mn掺杂Ba0.95Sr0.05TiO3陶瓷的电致形状记忆效应与BaTiO3 及PZT的线性压电效应对比, (b) Mn掺杂的 KNbO3基压电陶瓷老化前后的电致应变[11,14]

Fig. 9 (a) Comparison of the nonlinear recoverable electrostrain in Ba0.95Sr0.05TiO3-1Mn ceramics with linear piezoelectric strain of BaTiO3 and PZT ceramics and (b) bipolar electrostrain curves for the aged and fresh Mn-doped KNbO3 based piezoelectric ceramics[11,14]

图10 KNN-Cu陶瓷的电滞回线随(a)频率和(b)温度的变化[42]

Fig. 10 P-E loops of KNN-Cu ceramics measured at different (a) frequencies and (b) temperatures[42]

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压电材料中缺陷偶极子特性的研究进展

Recent Progress on Defect Dipoles Characteristics in Piezoelectric Materials

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