缺陷偶极子热稳定性对Fe掺杂PZT陶瓷机电性能影响研究

doi:10.15541/jim20240244

无机材料学报 ›› 2025, Vol. 40 ›› Issue (5): 545-551.DOI: 10.15541/jim20240244 CSTR: 32189.14.10.15541/jim20240244

缺陷偶极子热稳定性对Fe掺杂PZT陶瓷机电性能影响研究

孙雨萱¹^,²(), 王政¹, 时雪¹, 史颖¹^,², 杜文通¹^,², 满振勇¹, 郑嘹赢¹, 李国荣¹()

1.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
2.中国科学院大学材料科学与光电子工程中心, 北京 100049

收稿日期:2024-05-14 修回日期:2024-09-24 出版日期:2025-05-20 网络出版日期:2024-11-29
通讯作者: 李国荣, 研究员. E-mail: grli@mail.sic.ac.cn
作者简介:孙雨萱(1999-), 女, 硕士研究生. E-mail: sunyuxuan21@mails.ucas.ac.cn

Defect Dipole Thermal-stability to the Electro-mechanical Properties of Fe Doped PZT Ceramics

SUN Yuxuan¹^,²(), WANG Zheng¹, SHI Xue¹, SHI Ying¹^,², DU Wentong¹^,², MAN Zhenyong¹, ZHENG Liaoying¹, LI Guorong¹()

1. Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-05-14 Revised:2024-09-24 Published:2025-05-20 Online:2024-11-29
Contact: LI Guorong, professor. E-mail: grli@mail.sic.ac.cn
About author:SUN Yuxuan (1999-), female, Master candidate. E-mail: sunyuxuan21@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(U2241242);National Key R&D Program of China(2023YFB3812000);National Key R&D Program of China(2021YFA0716502)

摘要/Abstract

摘要：

在PbZr_yTi_1-_yO₃(PZT)基压电陶瓷的Ti⁴⁺位点掺杂受主离子是一种众所周知的增加机械品质因数(Q_m)的方法, 受主离子与氧空位结合形成缺陷偶极子, 阻碍畴在外电场下的转动。但通常而言, 氧空位随温度升高而迁移, 缺陷偶极子因此而解耦, Q_m降低。本研究发现掺杂0.40%(摩尔百分数)Fe₂O₃的Pb_0.95Sr_0.05(Zr_0.53Ti_0.47)O₃ (PSZT)陶瓷的Q_m随着温度升高而异常增大(在室温下陶瓷的Q_m、压电系数(d₃₃)和居里温度(T_C)分别为507、292 pC/N和345 ℃), 最大Q_m在120~160 ℃可达824, 比在室温下高62.52%, 而动态压电常数(d₃₁)仅降低了3.85%。X射线衍射(XRD)和压电力显微镜结果表明, 随着温度升高, 陶瓷内部晶面间距增加, 电畴细化。热激励去极化电流结果表明, 缺陷偶极子在240 ℃以下保持稳定, 细畴附近的氧空位逐渐聚集, 并与温度稳定性良好的缺陷偶极子结合, 增加了对畴的钉扎作用, 导致Q_m增加。本研究为压电陶瓷高温下高Q_m的应用提供了一种可能性。

关键词: 缺陷偶极子, 温度特性, 氧空位, 机电性能, 机械品质因数, 硬化掺杂

Abstract:

The accepted doping ion in Ti⁴⁺-site of PbZr_yTi_1-_yO₃ (PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor (Q_m), since the acceptor coupled by oxygen vacancy becomes defect dipole, which prevents the domain rotation. In this field, a serious problem is that generally, Q_m decreases as the temperature (T) increases, since the oxygen vacancies are decoupled from the defect dipoles. In this work, Q_m of Pb_0.95Sr_0.05(Zr_0.53Ti_0.47)O₃ (PSZT) ceramics doped by 0.40% Fe₂O₃ (in mole) abnormally increases as T increases, of which the Q_m and piezoelectric coefficient (d₃₃) at room temperature and Curie temperature (T_C) are 507, 292 pC/N, and 345 ℃, respectively. The maximum Q_m of 824 was achieved in the range of 120-160 ℃, which is 62.52% higher than that at room temperature, while the dynamic piezoelectric constant (d₃₁) was just slightly decreased by 3.85%. X-ray diffraction (XRD) and piezoresponse force microscopy results show that the interplanar spacing and the fine domains form as temperature increases, and the thermally stimulated depolarization current shows that the defect dipoles are stable even the temperature up to 240 ℃. It can be deduced that the aggregation of oxygen vacancies near the fine domains and defect dipole can be stable up to 240 ℃, which pins domain rotation, resulting in the enhanced Q_m with the increasing temperature. These results give a potential path to design high Q_m at high temperature.

Key words: defect dipole, temperature characteristic, oxygen vacancy, electro-mechanical property, mechanical quality factor, hardening doping

中图分类号:

TQ174

孙雨萱, 王政, 时雪, 史颖, 杜文通, 满振勇, 郑嘹赢, 李国荣. 缺陷偶极子热稳定性对Fe掺杂PZT陶瓷机电性能影响研究[J]. 无机材料学报, 2025, 40(5): 545-551.

SUN Yuxuan, WANG Zheng, SHI Xue, SHI Ying, DU Wentong, MAN Zhenyong, ZHENG Liaoying, LI Guorong. Defect Dipole Thermal-stability to the Electro-mechanical Properties of Fe Doped PZT Ceramics[J]. Journal of Inorganic Materials, 2025, 40(5): 545-551.

图/表 10

Fig. 1 Lattice, density and SEM image of PSZT-xFe ceramics (a) Lattice parameters of the T phase; (b) SEM image of PSZT-0.40Fe ceramics with inset showing the grain size distribution; (c) Relative density and average grain size

Fig. 2 Dielectric properties, P-E loops and I-E loops of PSZTs (a) ε and tanδ versus temperatures at 100 kHz of PSZT-xFe ceramics; (b) ε and tanδ versus temperatures at frequencies of 1, 10 and 100 kHz for PSZT-0.40Fe ceramic with inset showing tanδ versus temperatures in the range of 20-250 ℃; (c) P-E loops of PSZT-xFe ceramics; (d) I-E loops of PSZT-xFe ceramics. Colorful figures are available on website

Table 1 Electro-mechanical properties of PSZT-xFe ceramics

x	T_C/℃	T_θ/℃	C/(×10⁴)	E_C/(kV·cm^-1)	P_r/(μC·cm^-2)	d₃₃/(pC·N^-1)	Q_m	k_p	σ	ε(1 kHz)
0.36	343	336	7.0	31.3	1.95	300	409	0.67	0.31	1361
0.38	343	335	8.4	32.8	2.76	295	415	0.66	0.31	1253
0.40	345	333	11.3	34.5	1.65	292	507	0.64	0.32	1098
0.42	343	332	10.6	34.2	2.11	294	499	0.65	0.31	1109

Fig. 3 Electro-mechanical properties of PSZT-0.40Fe ceramic in the range of 20-240 ℃ (a) Impedance of 120-160 kHz; (b) Phase angle of 120-160 kHz; (c) Calculated Qm; (d) Calculated d31. Colorful figures are available on website

Fig. 4 Morphology and longitudinal piezoelectric response images of PSZT-0.40Fe ceramics in the same region (a) Morphology at room temperature; (b-f) Longitudinal piezoelectric response image in the range of 40-240 ℃. Colorful figures are available on website

Fig. 5 XRD patterns of PSZT-0.40Fe ceramics in the range of 20-240 ℃ (a) XRD patterns; (b) Color map. Colorful figures are available on website

Fig. 6 TSDC curve of poled PSZT-0.40Fe ceramic

Fig. S1 XRD patterns of PSZT-xFe ceramics (a) 2θ=17.5°-67.5°; (b) 2θ=42.7°-45.8°

Fig. S2 Rietveld refinement results of PSZT-xFe ceramics XRD patterns (a) x=0.36; (b) x=0.38; (c) x=0.40; (d) x=0.42

Fig. S3 SEM images of PSZT-xFe ceramics with insets showing corresponding grain size distribution (a) x=0.36; (b) x=0.38; (c) x=0.40; (d) x=0.42

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缺陷偶极子热稳定性对Fe掺杂PZT陶瓷机电性能影响研究

Defect Dipole Thermal-stability to the Electro-mechanical Properties of Fe Doped PZT Ceramics

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