| Aurivillius结构Bi2MoxW1-xO6铁电功能晶体的生长与性质表征 |
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| 引用本文： | 丁小南,田相鑫,赵鹏,高泽亮,刘敬权.Aurivillius结构Bi2MoxW1-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. |
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| 作者姓名： | 丁小南 田相鑫 赵鹏 高泽亮 刘敬权 |
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| 作者单位： | 1.临沂大学材料科学与工程学院,临沂 276000; 2.中材人工晶体研究院有限公司,北京 100018; 3.山东大学晶体材料国家重点实验室,济南 250100 |
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| 基金项目： | 山东省自然科学基金(ZR2019BEM029) |
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| 摘 要： | 本文采用固相反应法探索了Aurivillius结构Bi2MoxW1-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Bi2MoxW1-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。Bi2MoxW1-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Bi2MoxW1-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Bi2Mo0.15W0.85O6厘米量级单畴晶体,结构解析表明Bi2Mo0.15W0.85O6属于正交晶系,Aba2(No.41)空间群。变温介电性质测试表明,Bi2Mo0.15W0.85O6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Bi2Mo0.15W0.85O6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Bi2Mo0.15W0.85O6晶体,且随温度升高,二者电阻率的差距在逐渐缩小。
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| 关 键 词： | Bi2MoxW1-xO6 Aurivillius结构 助熔剂法 晶体结构 介电性质 铁电晶体 电阻率 |
| 收稿时间： | 2022-07-11 |
Growth and Property of Aurivillius Structure Bi2MoxW1-xO6 Series Ferroelectric Functional Single Crystals |
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| DING Xiaonan,TIAN Xiangxin,ZHAO Peng,GAO Zeliang,LIU Jingquan.Growth and Property of Aurivillius Structure Bi2MoxW1-xO6 Series Ferroelectric Functional Single Crystals[J].Journal of Synthetic Crystals,2022,51(11):1858-1870. |
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| Authors: | DING Xiaonan TIAN Xiangxin ZHAO Peng GAO Zeliang LIU Jingquan |
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| Affiliation: | 1. School of Materials Science and Engineering, Linyi University, Linyi 276000, China; 2. Sinoma Synthetic Crystals Co., Ltd., Beijing 100018, China; 3. State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China |
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| Abstract: | Synthesis conditions of Aurivillius structure Bi2MoxW1-xO6 series and the composition range of solid solution were explored by solid phase reaction method, and the flux growth system of Bi2MoxW1-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 Bi2MoxW1-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 Bi2MoxW1-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 Bi2MoxW1-xO6 can be synthesized under different temperatures in the range of 500 ℃ to 870 ℃. Growth of the Bi2MoxW1-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 Bi2Mo0.15W0.85O6 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 Bi2Mo0.15W0.85O6 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 Bi2Mo0.15W0.85O6 crystals both decrease with the increase of temperature. Below 100 ℃, the resistivity of Bi2WO6 is higher than that of Bi2Mo0.15W0.85O6 crystal, and with the increase of temperature, the difference of resistivity between the two crystals is gradually narrowing. |
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| Keywords: | Bi2MoxW1-xO6 Aurivillius structure flux method crystal structure dielectric property ferroelectric crystal resistivity |
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