Bi₁₂GeO₂₀晶体是一种多功能光电材料, 在可见光范围内具有高速光折变响应, 以及良好的压电、声光、磁光, 旋光和电光等性能。目前, 提拉法生长Bi₁₂GeO₂₀晶体, 存在生长成本高、晶锭形状不规则、生长产率低、晶体光学质量差和有效晶体截面小等问题。本研究率先采用改进的坩埚下降法, 在铂金坩埚和空气气氛中生长大尺寸Bi₁₂GeO₂₀晶体。通过各种分析测试方法研究生长获得的Bi₁₂GeO₂₀晶体中宏观缺陷的形态、分布和成分构成, 探讨了晶体生长过程中主要宏观缺陷的形成过程和成因。坩埚下降法生长的Bi₁₂GeO₂₀晶体存在两种主要宏观缺陷：枝蔓状和管状包裹体。其中, 枝蔓状包裹体与铂金溶蚀后的析晶相关, 而管状包裹体与铂金析出、接种界面不稳定性和温度波动有关。本研究提出了消除坩埚下降法生长晶体中宏观缺陷的技术途径, 通过降低生长控制温度、缩短高温熔体保持时间和优选籽晶等措施, 可重复地生长光学质量良好、55 mm× 55 mm× 80 mm的大尺寸Bi₁₂GeO₂₀晶体, 显著提升晶体的光学透过性能。

As a multifunctional opto-electro material, Bi₁₂GeO₂₀ crystal shows high-speed photorefractive response in visible range, excellent piezoelectric, acousto-optic, magneto-optic, optical rotation, and electro-optic properties, etc. Presently, Czochralski (Cz) method, which is commonly used to grow Bi₁₂GeO₂₀ crystals, has several bottle-necks, such as high growth cost, irregular crystal boule shapes, low growth yield, poor optical quality in large crystals, and small effective crystal cross-sectional area. In this study, large Bi₁₂GeO₂₀ crystals were firstly grown by using modified vertical Bridgman method in platinum crucibles and air atmosphere. Morphology, distribution, and constitutes of main macroscopic defects in as-grown Bi₁₂GeO₂₀ crystals were investigated, and the formation process and causes of the main macroscopic defects during the crystal growth were studied. Dendrite and tubular inclusions are two types of main macroscopic defects existed in as-grown Bi₁₂GeO₂₀ crystals. The formation of dendrite inclusions is closely related to the platinum corrosion, while the formation of tubular inclusions is associated with precipitation of platinum, a mismatch in the stacking of growth units due to instability of the seeding interface, and instability temperature field. Technical approaches to eliminate or reduce these two types of macroscopic defects during the growth using vertical Bridgman method were proposed. High optical quality, large Bi₁₂GeO₂₀ crystals with sizes up to 55 mm×55 mm×80 mm and significantly improved optical transmittance were grown reproducibly by reducing control temperature, decreasing period of melt preserved at high temperature, and selecting seed crystals with better quality.