Bi4Ti3O12铋层状压电陶瓷的A/B位掺杂及其电学性能

doi:10.15541/jim20240480

无机材料学报 ›› 2025, Vol. 40 ›› Issue (6): 690-696.DOI: 10.15541/jim20240480

Bi₄Ti₃O₁₂铋层状压电陶瓷的A/B位掺杂及其电学性能

张家维¹^,²(), 陈宁¹, 程原², 王博², 朱建国¹(), 金城²()

1.四川大学材料科学与工程学院, 成都 610065
2.成都凯天电子股份有限公司, 成都 610083

收稿日期:2024-11-13 修回日期:2025-01-08 出版日期:2025-06-20 网络出版日期:2025-01-24
通讯作者: 朱建国, 教授. E-mail: nic0400@scu.edu.cn;
金城, 高级工程师. E-mail: jin_int@163.com
作者简介:张家维(1999-), 男, 硕士研究生. E-mail: 2451220096@qq.com
基金资助:
国家自然科学基金重点项目(51932010);四川省科技计划项目(2023YFG0042)

Electrical Properties of Bismuth Layered Piezoelectric Bi₄Ti₃O₁₂ Ceramics with A/B-site Doping

ZHANG Jiawei¹^,²(), CHEN Ning¹, CHENG Yuan², WANG Bo², ZHU Jianguo¹(), JIN Cheng²()

1. College of Material Science and Engineering, Sichuan University, Chengdu 610065, China
2. AVIC Chengdu CAIC Electronics Co., Ltd., Chengdu 610083, China

Received:2024-11-13 Revised:2025-01-08 Published:2025-06-20 Online:2025-01-24
Contact: ZHU Jianguo, professor. E-mail: nic0400@scu.edu.cn;
JIN Cheng, senior engineer. E-mail: jin_int@163.com
About author:ZHANG Jiawei (1999-), male, Master candidate. E-mail: 2451220096@qq.com
Supported by:
Key Program of National Natural Science Foundation of China(51932010);Sichuan Science and Technology Program(2023YFG0042)

摘要/Abstract

摘要： 近年来, 随着航天、航空和核能领域的快速发展, 对能够在450 ℃及以上温度正常工作的压电陶瓷材料的需求日益迫切。钛酸铋(Bi₄Ti₃O₁₂, BIT)是铋层状结构陶瓷中具有较高居里温度(T_C~650 ℃)的压电陶瓷, 能够在高温环境下工作。但是纯相BIT陶瓷压电常数(d₃₃)和高温电阻率较低, 阻碍了其在高温环境下的应用。本工作采用固相反应法制备了A位Ce离子和B位W、Ta、Sb离子共同掺杂的BIT基压电陶瓷(BCTWTaS-100x, x=0~0.04), 系统研究了Ce掺杂对BIT基陶瓷结构和电学性能的影响。引入Ce离子造成BIT陶瓷晶格畸变以及畴结构变化, 显著增强了陶瓷的压电性能(x=0.03时, BCTWTaS-3陶瓷d₃₃=37 pC/N)。随着离子掺杂浓度的增大, TiO₆八面体顶部氧原子的相对位移增大, BIT陶瓷的晶格畸变程度相应增加。BCTWTaS-3陶瓷具有较高的T_C(673 ℃)以及高温电阻率(500 ℃时电阻率保持在10⁶ Ω·cm数量级)。此外, 该陶瓷还表现出良好的d₃₃热稳定性, 在600 ℃退极化2 h后, d₃₃仍能保持其初始值的85%以上。结果表明, BCTWTaS-100x陶瓷在450 ℃以上高温环境中具有很大的应用潜力。

关键词: Bi₄Ti₃O₁₂, 高居里温度, 压电陶瓷, 晶格畸变

Abstract:

In recent years, there has been an urgent need for piezoelectric ceramic material capable of operating at temperatures of 450 ℃ and above, which serves as a piezoelectric sensing element in high-temperature piezoelectric vibration sensors. Bi₄Ti₃O₁₂ (BIT) is a piezoelectric ceramic with a high Curie temperature (T_C~650 ℃) within the family of bismuth-layered ferroelectric ceramics, making it a promising candidate for high-temperature applications. However, inherent low piezoelectric constant (d₃₃) and low high-temperature resistivity of pure phase BIT ceramics limit their application in such environments. This work used solid-phase reaction method to prepare BIT-based piezoelectric ceramics with substitutions at A-site by Ce ions and at B-site by W/Ta/Sb ions (BCTWTaS-100x, x=0-0.04). Effect of Ce doping on the structure and electrical properties of BIT-based ceramics was studied. Introduction of Ce ions induces lattice distortion and modifies domain structure of BIT-based ceramics, thereby enhancing their piezoelectric properties (with a d₃₃ of 37 pC/N at x=0.03). With doping concentration of ions increasing, relative displacement of oxygen atoms at apex of TiO₆ octahedra increases, resulting in increased lattice distortion within BIT-based ceramic. Furthermore, BCTWTaS-3 ceramics demonstrate a high T_C of 673 ℃ and high-temperature resistivity maintaining on the order of 10⁶ Ω·cm at 500 ℃. These ceramics also exhibit good thermal stability of d₃₃. Notably, after depolarization at 600 ℃ for 2 h, d₃₃ can still maintain over 85% of its initial value. These finds indicate that BCTWTaS-100x ceramics have great potential for application in high-temperature environments exceeding 450 ℃.

Key words: Bi₄Ti₃O₁₂, high Curie temperature, piezoelectric ceramic, lattice distortion

中图分类号:

TQ174

张家维, 陈宁, 程原, 王博, 朱建国, 金城. Bi₄Ti₃O₁₂铋层状压电陶瓷的A/B位掺杂及其电学性能[J]. 无机材料学报, 2025, 40(6): 690-696.

ZHANG Jiawei, CHEN Ning, CHENG Yuan, WANG Bo, ZHU Jianguo, JIN Cheng. Electrical Properties of Bismuth Layered Piezoelectric Bi₄Ti₃O₁₂ Ceramics with A/B-site Doping[J]. Journal of Inorganic Materials, 2025, 40(6): 690-696.

图/表 9

图1 BCTWTaS-100x陶瓷的(a) XRD图谱、(b) Raman图谱和(c~e)各声子振动模的Raman位移随x的变化

Fig. 1 (a) XRD patterns, (b) Raman spectra, and (c-e) Raman shifts of each mode as a function of x for BCTWTaS-100x ceramics

图2 BCTWTaS-100x陶瓷(a~e)抛光热蚀刻表面的SEM照片及(f)密度

Fig. 2 (a-e) SEM images of the polished thermally-etched surfaces of BCTWTaS-100x ceramics and (f) corresponding density

图3 (a, b) BCTWTaS-100x陶瓷O元素、Bi元素和(c) BCTWTaS-3陶瓷Ce元素的XPS精细谱

Fig. 3 High-resolution XPS spectra of (a, b) O, Bi for BCTWTaS-100x ceramics and (c) Ce for BCTWTaS-3 ceramic

图4 (a, b)BCTWTaS-0与(c, d)BCTWTaS-3陶瓷在4 μm×4 μm扫描区域内垂直扫描PFM的(a, c)振幅图与(b, d)相位图

Fig. 4 (a, c) Amplitude and (b, d) phase images of vertical PFM for (a, b) BCTWTaS-0 and (c, d) BCTWTaS-3 ceramics with a scanning region of 4 μm×4 μm

图5 (a~e)BCTWTaS-100x陶瓷的P-E回线和I-E曲线，以及(f) Pr和Ec随组分的变化

Fig. 5 (a-e) P-E hysteresis loops and I-E curves of BCTWTaS-100x ceramics, and (f) composition dependence of Pr and Ec

图6 BCTWTaS-100x陶瓷的(a) d33随组分的变化曲线和(b) d33、(c) εr和(d) tanδ(100 kHz)随温度的变化曲线

Fig. 6 (a) Composition dependence of d33 and (b-d) temperature dependence of (b) d33, (c) εr and (d) tanδ (100 kHz) for BCTWTaS-100x ceramics Colorful figures are available on website

图S1 BCTWTaS-100x陶瓷在不同温度下的复阻抗图谱

Fig. S1 Complex impedance spectra of BCTWTaS-100x ceramics at different temperatures

图S2 (a-e) BCTWTaS-100x陶瓷的M''/M''max在不同温度下随频率的变化; (g) BCTWTaS-x陶瓷的直流电阻率与温度的关系; (h) BCTWTaS-x陶瓷在200~600 ℃范围内的直流电阻率与温度之间的Arrhenius关系; (i) 通过拟合低温区和高温区的实验数据计算得到的活化能

Fig. S2 (a-e) M''/M''max as a function of frequency of BCTWTaS-100x ceramics at different temperatures; (g) Temperature dependence of DC resistivity of BCTWTaS-100x ceramics; (h) Arrhenius relationship between DC resistivity and temperature of BCTWTaS-100x ceramics in the range of 200-600 ℃; (i) Activation energy calculated by fitting the experimental data from low-temperature region and high-temperature region

图S3 (a)纳米压痕示意图和(b~f) BCTWTaS-x陶瓷的载荷-深度曲线

Fig. S3 9(a) Schematic diagram of nanoindentation and (b-f) load-depth curves for the BCTWTaS-x ceramics

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Bi₄Ti₃O₁₂铋层状压电陶瓷的A/B位掺杂及其电学性能

Electrical Properties of Bismuth Layered Piezoelectric Bi₄Ti₃O₁₂ Ceramics with A/B-site Doping

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