坩埚下降法生长Bi12SiO20晶体中的散射颗粒研究

doi:10.15541/jim20250521

无机材料学报 ›› 2026, Vol. 41 ›› Issue (10): 1453-1458.DOI: 10.15541/jim20250521

坩埚下降法生长Bi₁₂SiO₂₀晶体中的散射颗粒研究

俞延强¹^,²(), 熊巍²(), 陈良², 周尧², 李颖¹(), 袁晖²

¹ 上海理工大学材料与化学学院, 上海 200093
² 中国科学院上海硅酸盐研究所, 功能晶体与器件全国重点实验室, 上海 200050

收稿日期:2025-12-31 修回日期:2026-01-29 出版日期:2026-10-20 网络出版日期:2026-04-03
通讯作者: 熊巍, 副研究员. E-mail: xiongwei@mail.sic.ac.cn;
李颖, 副教授. E-mail: liying@usst.edu.cn
作者简介:俞延强(1997-), 男, 硕士研究生. E-mail: yuyanqiang2023@163.com
基金资助:
国家自然科学基金(12375187);国家自然科学基金(52573302)

Scattering Particles in Bi₁₂SiO₂₀ Crystals Grown by the Vertical Bridgman Method

YU Yanqiang¹^,²(), XIONG Wei²(), CHEN Liang², ZHOU Yao², LI Ying¹(), YUAN Hui²

¹ School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China
² State Key Laboratory of Functional Crystals and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2025-12-31 Revised:2026-01-29 Published:2026-10-20 Online:2026-04-03
Contact: XIONG Wei, associate professor. E-mail: xiongwei@mail.sic.ac.cn;
LI Ying, associate professor. E-mail: liying@usst.edu.cn
About author:YU Yanqiang (1997-), male, Master candidate. E-mail: yuyanqiang2023@163.com
Supported by:
National Natural Science Foundation of China(12375187);National Natural Science Foundation of China(52573302)

摘要/Abstract

摘要：

硅酸铋(Bi₁₂SiO₂₀, BSO)晶体是一种宽带隙、高电阻率的非铁电立方半绝缘体, 凭借其线性电光效应、光电导特性、压电性能及光折变效应, 在诸多光电子领域展现出广阔的应用前景。目前, 采用坩埚下降法生长的BSO晶体中易形成散射颗粒缺陷, 严重制约其实际应用。本研究以坩埚下降法生长的BSO晶体为研究对象, 采用偏光显微镜、扫描电子显微镜-能量色散X射线光谱及分光光度计等表征手段, 系统分析了BSO晶体中散射颗粒的形貌、尺寸、空间分布及化学组成, 并结合晶体生长热力学与动力学过程, 探讨了散射颗粒的形成机制。结果表明, BSO晶体中的散射颗粒主要成分为金属铂, 其来源于高温下BSO熔体对铂金坩埚的腐蚀反应; 该类颗粒以棒状-H状过渡的线状缺陷存在, H状缺陷在纵向轮廓上呈连续的波峰-波谷锯齿状精细结构; 其形成与晶体生长环境相关, 主要分布在晶片中心区域, 且散射颗粒取向与晶体[100]生长方向基本一致。基于散射颗粒的本质与形成路径。本研究提出严格控制原料比、降低熔体生长温度等优化生长工艺参数的解决方案, 为制备大尺寸、低铂金散射颗粒、高光学均匀性的BSO晶体提供了依据。

关键词: Bi₁₂SiO₂₀晶体, 坩埚下降法, 散射颗粒, 晶体生长

Abstract:

Bismuth silicon oxide (Bi₁₂SiO₂₀, BSO) crystal is a wide-bandgap, high-resistivity and non-ferroelectric cubic semi-insulator. Due to its linear electro-optic effect, photoconductive properties, piezoelectric performance, and photorefractive effect, it exhibits broad applications in various optoelectronic fields. However, the scattering particles generated from the Bridgman crystal growth have seriously limited its practical applications. This study focuses on the scattering particles in BSO crystals grown via the vertical Bridgman method. The morphology, size, spatial distribution, and chemical composition of the scattering particles by transmission polarizing microscopy (TPM), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) were systematically analyzed. Combining thermodynamic and kinetic processes of crystal growth, the formation mechanism of these scattering particles was also discussed. Results indicate that the scattering particles are primarily composed of metallic platinum (Pt), originating from corrosion of the platinum crucible by the high-temperature melt. These particles exist as linear defects exhibiting a rod-like to H-shaped transitional morphology, where the H-shaped defects display a continuous peak-valley zigzag fine structure along their longitudinal profile. Their formation correlates with the crystal growth environment, showing predominant distribution in the central region of the wafer, while the orientation of the scattering particles aligns closely with the [100] crystal growth direction. Based on this work, the optimized growth parameters are proposed, including strict control of the raw material stoichiometry and reduction of the melt temperature, to suppress the incorporation of platinum. This work provides a practical foundation for producing large-size BSO crystals with low platinum-scattering defect density and high optical homogeneity.

Key words: Bi₁₂SiO₂₀ crystal, vertical Bridgman method, scattering particle, crystal growth

中图分类号:

TQ174

俞延强, 熊巍, 陈良, 周尧, 李颖, 袁晖. 坩埚下降法生长Bi₁₂SiO₂₀晶体中的散射颗粒研究[J]. 无机材料学报, 2026, 41(10): 1453-1458.

YU Yanqiang, XIONG Wei, CHEN Liang, ZHOU Yao, LI Ying, YUAN Hui. Scattering Particles in Bi₁₂SiO₂₀ Crystals Grown by the Vertical Bridgman Method[J]. Journal of Inorganic Materials, 2026, 41(10): 1453-1458.

图/表 9

图1 强光下观测到的散射颗粒及透过测试区

Fig. 1 Scattering particles observed under intense light and transmission test areas

图2 图1中标记区域的透射光谱

Fig. 2 Transmission spectra of the labeled areas in Fig. 1 Colorful figure is available on website

图3 散射颗粒取向与晶体[100]生长方向夹角分布的高斯拟合曲线

Fig. 3 Gaussian fitting curve of the angle distribution between the scattering particle orientation and the crystal growth direction [100]

图4 BSO晶体中散射颗粒位置分布示意图

Fig. 4 Schematic diagram of the spatial position distribution of scattering particles in BSO crystal (a) Angle with the growth direction [100]; (b) Distribution in the x-y plane

图5 BSO晶体腐蚀前散射颗粒在TPM与SEM下的形貌特征

Fig. 5 TPM and SEM images of scattering particles in BSO crystal before corrosion (a, c) Scattering particles on the A-side of the crystal; (b, d) Scattering particles on the B-side of the crystal

图6 硝酸腐蚀2 h后BSO晶体中散射颗粒的SEM照片

Fig. 6 SEM images of scattering particles in BSO crystal after 2 h HNO3 etching (a) Scattering particles on the A-side of the crystal; (b) Scattering particles on the B-side of the crystal

图7 硝酸腐蚀6 h后BSO晶体中散射颗粒的SEM照片

Fig. 7 SEM images of scattering particles in BSO crystal after 6 h HNO3 etching (a) Transition between cylindrical and H-shaped particles; (b-d) H-shaped scattering particles in the BSO crystal

图8 BSO晶体中散射颗粒SEM照片(a, d)及EDS图谱(b, c, e, f)

Fig. 8 SEM images (a, d) and EDS spectra (b, c, e, f) of scattering particles in BSO crystal

表1 BSO晶体中散射颗粒SEM-EDS成分分析

Table 1 SEM-EDS component analysis of the scattering particles in BSO crystal

Spectrum	Pt/% (in atomic)	Bi/% (in atomic)	Si/% (in atomic)	O/% (in atomic)
1	85.39	-	-	14.61
3	-	48.12	3.09	48.79
18	92.54	-	-	7.46
19	-	43.56	3.26	53.19

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坩埚下降法生长Bi₁₂SiO₂₀晶体中的散射颗粒研究

Scattering Particles in Bi₁₂SiO₂₀ Crystals Grown by the Vertical Bridgman Method

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