Aurivillius结构Bi2MoxW1-xO6铁电功能晶体的生长与性质表征

摘要/Abstract

摘要： 本文采用固相反应法探索了Aurivillius结构Bi₂Mo_xW_1-xO₆体系的合成条件以及能够形成固溶体的成分范围,探索了Bi₂Mo_xW_1-xO₆晶体的助熔剂法生长体系,并对晶体的结构、变温介电性质和电阻率进行了测定和分析。Bi₂Mo_xW_1-xO₆体系中Mo的占比x可以在0~1的范围内连续变化,采用固相反应法可以在500~870 ℃范围内的不同温度合成纯的Bi₂Mo_xW_1-xO₆铁电相。采用Li₂B₄O₇-Bi₂O₃(摩尔比2∶1)作为助熔剂生长得到了厘米级Bi₂WO₆单畴晶体,厚度不小于2 mm,最大尺寸则达到了约40 mm。在n(Bi₂O₃)∶n(MoO₃)∶n(WO₃)∶n(Li₂B₄O₇)=1∶1∶1∶1(摩尔比)体系中生长得到了厚度约1 mm的Bi₂Mo_0.15W_0.85O₆厘米量级单畴晶体,结构解析表明Bi₂Mo_0.15W_0.85O₆属于正交晶系,Aba2(No.41)空间群。变温介电性质测试表明,Bi₂Mo_0.15W_0.85O₆晶体的介电常数ε₃₃由Bi₂WO₆晶体的70提高到了102,介电弛豫现象发生的温度由Bi₂WO₆晶体的430 ℃降到了330 ℃附近。变温电阻率测试表明,Bi₂WO₆与Bi₂Mo_0.15W_0.85O₆晶体的电阻率均随温度升高而降低,在100 ℃以下,Bi₂WO₆的电阻率高于Bi₂Mo_0.15W_0.85O₆晶体,且随温度升高,二者电阻率的差距在逐渐缩小。

关键词: Bi₂Mo_xW_1-xO₆, Aurivillius结构, 助熔剂法, 晶体结构, 介电性质, 铁电晶体, 电阻率

Abstract: Synthesis conditions of Aurivillius structure Bi₂Mo_xW_1-xO₆ series and the composition range of solid solution were explored by solid phase reaction method, and the flux growth system of Bi₂Mo_xW_1-xO₆ crystal was explored. The structure, variable temperature dielectric property and resistivity of the crystal were measured and analyzed. Due to their large spontaneous polarization and high Curie temperatures, ferroelectric Aurivillius Bi₂Mo_xW_1-xO₆ have attracted tremendous research attention in petroleum mining industries, communication equipments, meidcal ultrsonic diagnostics, structural health monitoring, et al. In this study, the composition variation range of n(Mo)∶n(W) ratio in Bi₂Mo_xW_1-xO₆ solid solution were studied in detail through changing the sintering temperature and dewelling time. According to the synthetic results, the proportion(x) of Mo in the solid solution can be continuously tuned in the range of 0 to 1, and the pure ferroelectric phase of Bi₂Mo_xW_1-xO₆ can be synthesized under different temperatures in the range of 500 ℃ to 870 ℃. Growth of the Bi₂Mo_xW_1-xO₆ single crystals through the high temperature solution method were also explored systematically. By employing Li₂B₄O₇-Bi₂O₃ (molar ratio 2∶1) as a flux, centimeter-sized Bi₂WO₆ single domain crystals were grown with the thickness of about 2 mm and the maximum dimension reaching as large as 40 mm. Centimeter-sized single domain crystals of Bi₂Mo_0.15W_0.85O₆ with the thickness of about 1 mm were also grown in n(Bi₂O₃)∶n(MoO₃)∶n(WO₃)∶n(Li₂B₄O₇)=1∶1∶1∶1 (molar ratio) flux system. Structural refinement reveals that Bi₂Mo_0.15W_0.85O₆ crystallizes into the orthorhombic system, Aba2 (No.41) space group. Variable temperature dielectric measurements show that the dielectric constant ε₃₃ increases from 70 of Bi₂WO₆ crystal to 102, and the temperature at which the dielectric relaxation occurs decreases from 430 ℃ of Bi₂WO₆ crystal to around 330 ℃. The temperature varying resistivity shows that the resistivity of Bi₂WO₆ and Bi₂Mo_0.15W_0.85O₆ crystals both decrease with the increase of temperature. Below 100 ℃, the resistivity of Bi₂WO₆ is higher than that of Bi₂Mo_0.15W_0.85O₆ crystal, and with the increase of temperature, the difference of resistivity between the two crystals is gradually narrowing.

Key words: Bi₂Mo_xW_1-xO₆, Aurivillius structure, flux method, crystal structure, dielectric property, ferroelectric crystal, resistivity

中图分类号:

O782
O73

丁小南, 田相鑫, 赵鹏, 高泽亮, 刘敬权. Aurivillius结构Bi₂Mo_xW_1-xO₆铁电功能晶体的生长与性质表征[J]. 人工晶体学报, 2022, 51(11): 1858-1870.

DING Xiaonan, TIAN Xiangxin, ZHAO Peng, GAO Zeliang, LIU Jingquan. Growth and Property of Aurivillius Structure Bi₂Mo_xW_1-xO₆ Series Ferroelectric Functional Single Crystals[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(11): 1858-1870.

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Aurivillius结构Bi₂Mo_xW_1-xO₆铁电功能晶体的生长与性质表征

Growth and Property of Aurivillius Structure Bi₂Mo_xW_1-xO₆ Series Ferroelectric Functional Single Crystals

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