坩埚下降法生长大尺寸Bi12GeO20晶体的宏观缺陷

doi:10.15541/jim20220642

无机材料学报 ›› 2023, Vol. 38 ›› Issue (3): 280-287.DOI: 10.15541/jim20220642

坩埚下降法生长大尺寸Bi₁₂GeO₂₀晶体的宏观缺陷

齐雪君¹(), 张健¹, 陈雷¹, 王绍涵¹, 李翔¹, 杜勇¹, 陈俊锋¹^,²()

1.中国科学院上海硅酸盐研究所, 上海201899
2.上海交通大学 ISFA协同创新中心, 上海200240

收稿日期:2022-11-01 修回日期:2022-12-05 出版日期:2023-01-11 网络出版日期:2023-01-11
通讯作者: 陈俊锋, 研究员. E-mail: jfchen@mail.sic.ac.cn
作者简介:齐雪君(1969-), 女, 高级工程师. E-mail: qixuejun@mail.sic.ac.cn
基金资助:
中国科学院战略性先导科技专项(XDA25030600);国家自然科学基金(U1867211);上海市“科技创新行动计划”重点项目(20511107402)

Macroscopic Defects of Large Bi₁₂GeO₂₀ Crystals Grown Using Vertical Bridgman Method

QI Xuejun¹(), ZHANG Jian¹, CHEN Lei¹, WANG Shaohan¹, LI Xiang¹, DU Yong¹, CHEN Junfeng¹^,²()

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
2. Collaborative Innovation Center of IFSA, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2022-11-01 Revised:2022-12-05 Published:2023-01-11 Online:2023-01-11
Contact: CHEN Junfeng, professor. E-mail: jfchen@mail.sic.ac.cn
About author:QI Xuejun (1969-), female, senior engineer. E-mail: qixuejun@mail.sic.ac.cn
Supported by:
Strategic Priority Research Program of Chinese Academy of Sciences(XDA25030600);National Natural Science Foundation of China(U1867211);Science and Technology Commission of Shanghai Municipality, China(20511107402)

摘要/Abstract

摘要：

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。

关键词: Bi₁₂GeO₂₀晶体, 坩埚下降法, 宏观缺陷, 晶体生长

Abstract:

As a multifunctional opto-electro material, Bi₁₂GeO₂₀crystal 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.

Key words: Bi₁₂GeO₂₀ crystal, vertical Bridgman method, macroscopic defect, crystal growth

中图分类号:

TQ174

齐雪君, 张健, 陈雷, 王绍涵, 李翔, 杜勇, 陈俊锋. 坩埚下降法生长大尺寸Bi₁₂GeO₂₀晶体的宏观缺陷[J]. 无机材料学报, 2023, 38(3): 280-287.

QI Xuejun, ZHANG Jian, CHEN Lei, WANG Shaohan, LI Xiang, DU Yong, CHEN Junfeng. Macroscopic Defects of Large Bi₁₂GeO₂₀ Crystals Grown Using Vertical Bridgman Method[J]. Journal of Inorganic Materials, 2023, 38(3): 280-287.

图/表 10

图1 Bi12GeO20晶体的TG-DSC曲线(a)和XRD谱图(b)

Fig. 1 TG-DSC curves (a) and XRD patterns (b) of Bi12GeO20 crystal

图2 Bi12GeO20晶锭中的宏观缺陷

Fig. 2 Macroscopic defects in as-grown Bi12GeO20 crystal ingots (a) As-grown Bi12GeO20 crystal ingots; (b, c) Dendritic inclusions; (d) Tubular scattering defects under the illumination of 532 nm laser light; (e) Tubular inclusions in polished crystals

图3 Bi12GeO20晶体中枝蔓状包裹体的光学显微镜(100×)照片

Fig. 3 Dendritic inclusions in Bi12GeO20 crystal observed by optical microscope(100×)

图4 Bi12GeO20晶体中枝蔓包裹体的SEM形貌(a, c, e)和EDS图谱(b, d, f)

Fig. 4 SEM images (a, c, e) and EDS spectra (b, d, f) of dendritic inclusions in Bi12GeO20 crystals

表1 Bi12GeO20晶体中枝蔓包裹体的SEM-EDS成分分析结果(原子分数）

Table 1 SEM-EDS composition analysis results of dendritic inclusions in Bi12GeO20 crystal (in atomic)

Spectrum	Pt/%	Bi/%	Ge/%	O/%	Bi/Ge
1	6.85	39.57	3.15	50.43	12.56
2	100.0	0	0	0	-
3	88.20	2.08	0	9.72	-
Matrix	0	36.27	3.11	60.62	11.66

图5 Bi12GeO20晶体中枝蔓包裹体的SEM-EDS元素分布图

Fig. 5 Elemental mappings of the dendritic inclusions in Bi12GeO20 crystal at the microstructural level by scanning electron microscope (SEM) with energy dispersive X-ray spectrometry (EDS) (a, c) Mappings of Bi, Pt, O, Ge; (b, d) Respective mappings of Bi, Pt, O, Ge

图6 典型Pt坩埚渗漏(a)和晶锭中Pt析晶(b)的照片

Fig. 6 Typical photos for the leakage of Pt crucibles (a) and Pt deposition (b) in as-grown crystal boule

图7 Bi12GeO20晶锭尾端的光学显微镜照片

Fig. 7 Optical morphology of as-grown Bi12GeO20 crystal boule on the tail end

图8 ϕ35 mm (a)和55 mm×55 mm (b)截面的Bi12GeO20晶锭的照片

Fig. 8 Pictures of as-grown Bi12GeO20 crystal boules with cross-sections of ϕ35 mm (a), and 55 mm×55 mm (b)

图9 工艺改进前后生长Bi12GeO20晶体的光学透过谱图

Fig. 9 Transmittance spectra of Bi12GeO20 crystals grown before and after growth parameters optimization Light path: 1 mm

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坩埚下降法生长大尺寸Bi₁₂GeO₂₀晶体的宏观缺陷

Macroscopic Defects of Large Bi₁₂GeO₂₀ Crystals Grown Using Vertical Bridgman Method

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