CaF2晶体热交换坩埚下降法生长固液界面演变及热质输运机制

doi:10.15541/jim20260179

无机材料学报

• 研究论文 •

CaF₂晶体热交换坩埚下降法生长固液界面演变及热质输运机制

刘洋^1,2, 张中晗^1,2, 张晓辉^1,2, 姜大朋¹, 寇华敏^1,2, 苏良碧^1,2

1.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 201899;
2.中国科学院大学材料科学与光电工程中心, 北京 100049

收稿日期:2026-04-24 修回日期:2026-06-15
通讯作者: 张中晗, 副研究员. E-mail: zhangzhonghan@mail.sic.ac.cn; 苏良碧, 研究员. E-mail: suliangbi@mail.sic.ac.cn
作者简介:刘洋(2000-), 男, 硕士研究生. E-mail: liuyang234@mails.ucas.ac.cn
基金资助:
国家自然科学基金(52450255, W2412088); 中国科学院稳定支持基础研究领域青年团队(YSBR-024)

Interface Evolution and Heat-mass Transfer Mechanisms during CaF₂ Crystal Growth by the Heat Exchanger-Bridgman Method

LIU Yang^1,2, ZHANG Zhonghan^1,2, ZHANG Xiaohui^1,2, JIANG Dapeng¹, KOU Huamin^1,2, SU Liangbi^1,2

1. State Key Laboratory of Functional Crystals and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China;
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2026-04-24 Revised:2026-06-15
Contact: ZHANG Zhonghan, associate professor. E-mail: zhangzhonghan@mail.sic.ac.cn; SU Liangbi, professor. E-mail: suliangbi@mail.sic.ac.cn
About author:LIU Yang (2000-), male, Master candidate. E-mail: liuyang234@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China (52450255, W2412088); CAS Project for Young Scientists in Basic Research(YSBR-024)

摘要/Abstract

摘要： 晶体生长是一个典型的多场耦合的跨尺度过程,其中晶体生长基元的成核相变、晶体缺陷的形成与演变均在晶体生长界面处发生。晶体生长界面的原位观测与精准描述仍是晶体生长领域尚未解决的核心难题,导致目前晶体生长工艺优化仍严重依赖试错,制约大尺寸、低缺陷晶体制备技术发展。本研究针对CaF₂晶体生长过程中固液界面难以直接观测、演变机制不清的问题,采用原位观测与数值模拟相结合的方法开展研究。利用界面可视化热交换坩埚下降法晶体生长装置,在恒定主控温度1850 K条件下获得固液界面位置与形态的演变信息,并建立相应的晶体生长数值模拟模型,对界面演变过程进行分析。结果表明：固液界面位置呈现“下移—稳定—上移”的阶段性演变规律,界面形态经历由凹形向凸形转变并伴随“M”型过渡态。界面位置演变主要受熔体顶部吸热与等径侧壁散热竞争关系控制,界面形态演变与界面位置变化及熔体流动结构演变密切相关。原位观测与数值模拟结果吻合良好,验证了模型的可靠性。研究结果为CaF₂晶体生长过程中的界面调控提供了依据。

关键词: CaF₂晶体, 热交换坩埚下降法, 固液界面, 原位观测, 数值模拟

Abstract: Crystal growth is a typical cross-scale process with multi-field coupling, in which the nucleation and phase transition of crystal growth units, as well as the formation and evolution of crystal defects, all occur at the crystal growth interface. Unfortunately, the in-situ observation and accurate characterization of the crystal growth interface remain a core challenge in the field of crystal growth. This results in the current optimization of crystal growth processes still relying on trial and error efforts, which constrains the technological development for the preparation of large-size and low-defect crystals. Aiming at the difficulties in direct observation and the ambiguity of the evolution mechanism of the solid-liquid interface during CaF₂ crystal growth, this study adopts a combined method of in-situ observation and numerical simulation. By utilizing a visualized interfacial heat exchanger-Bridgman crystal growth apparatus, the evolution information regarding the position and morphology of the solid-liquid interface is acquired under a constant main control temperature of 1850 K. Meanwhile, a corresponding numerical simulation model for crystal growth is established to analyze the interfacial evolution process. The results show that the interface position exhibits a stage-wise evolution characterized by downward movement, stabilization, and upward movement, while the interface morphology changes from a concave shape to a convex shape with an intermediate M-shaped transition. The evolution of interface position is mainly governed by the competition between heat absorption at the melt top and heat dissipation through the cylinder sidewall, whereas the evolution of interface morphology is closely related to interface-position variation and melt-flow-structure evolution. Good agreement between in-situ observation and numerical simulation confirms the reliability of the model. These results provide a basis for interface control during CaF₂ crystal growth.

Key words: CaF₂ crystal, heat exchanger-Bridgman method, solid-liquid interface, in-situ observation, numerical simulation

中图分类号:

TQ174

刘洋, 张中晗, 张晓辉, 姜大朋, 寇华敏, 苏良碧. CaF₂晶体热交换坩埚下降法生长固液界面演变及热质输运机制[J]. 无机材料学报, DOI: 10.15541/jim20260179.

LIU Yang, ZHANG Zhonghan, ZHANG Xiaohui, JIANG Dapeng, KOU Huamin, SU Liangbi. Interface Evolution and Heat-mass Transfer Mechanisms during CaF₂ Crystal Growth by the Heat Exchanger-Bridgman Method[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260179.

参考文献

[1] AZUMI M.Study of haze in artificially grown single crystal CaF₂. Proceedings of SPIE, 2007, 6720: 67201N.
[2] WANG X L, TAO P P, WANG Q Q,et al. Trends in photoresist materials for extreme ultraviolet lithography: a review. Materials Today, 2023, 67: 299.
[3] HAHN D.Calcium fluoride and barium fluoride crystals in optics.Optik & Photonik, 2014, 9(4): 45.
[4] GAUNT L.The Focal Guide to Lenses. London: Focal Press, 1977: 138.
[5] SENGUTTUVAN N, AOSHIMA M, SUMIYA K,et al. Oriented growth of large size calcium fluoride single crystals for optical lithography. Journal of Crystal Growth, 2005, 280: 462.
[6] FRIEDRICH J, MÜLLER G. Erlangen—an important center of crystal growth and epitaxy: major scientific results and technological solutions of the last four decades.Crystal Research and Technology, 2020, 55: 1900053.
[7] WANG J, MAIER R L, BRUNING J H.Surface characterization of optically polished CaF₂ crystal by quasi-Brewster-angle technique. Proceedings of SPIE, 2003, 5188: 1.
[8] ZANUTTA A, CRISTIANI S, ATKINSON D,et al. CUBES phase a design overview. Experimental Astronomy, 2023, 55: 241.
[9] LEVITON D B, MILLER K H, QUIJADA M A, et al. Temperature-dependent refractive index measurements of CaF₂, Suprasil 3001, and S-FTM16 for the Euclid near-infrared spectrometer and photometer. Proceedings of SPIE, 2015, 9578: 95780M.
[10] LIU X, CHEN W, CHEN K, et al. Orbit design and analysis for the Earth 2.0 (ET) space mission. Proceedings of SPIE, 2025, 13964: 139640J.
[11] BEN-AMI S, SHVARTZVALD Y, WAXMAN E, et al. The scientific payload of the Ultraviolet Transient Astronomy Satellite (ULTRASAT). Proceedings of SPIE, 2022, 12181: 1.
[12] HONG B Z, ZHANG S, ZHENG L L,et al. Controlling nucleation during unseeded THM growth of CdZnTe crystal. Journal of Crystal Growth, 2020, 534: 125966.
[13] DERBY J J, YECKEL A.Heat Transfer Analysis and Design for Bulk Crystal Growth: Perspectives on the Bridgman method//Handbook of Crystal Growth. Amsterdam: Elsevier, 2015: 793-843.
[14] HONG O Y, WEI S Y.Numerical simulation of CdTe vertical Bridgman growth.Journal of Crystal Growth, 1997, 173(3/4): 352.
[15] LIU F, CHEN K, XUE D.How to fast grow large-size crystals?The Innovation, 2024, 4: 104580.
[16] WANG Y X, WANG S Z, WANG J Y,et al. High-efficiency ～2 μm CW laser operation of LD-pumped Tm³⁺:CaF₂ single-crystal fibers. Optics Express, 2020, 28(5): 6684.
[17] SHI Y, WANG P, MU H,et al. Advances of interface, flow, and stress control for VB crystal growth: an overview. Progress in Crystal Growth and Characterization of Materials, 2023, 69(2/3/4): 100605.
[18] POLACCI M, COLTORTI M, DI GENOVA D,et al. Crystallisation in basaltic magmas revealed via in situ 4D synchrotron X-ray microtomography. Scientific Reports, 2018, 8: 8377.
[19] SONG Z, ZHANG L, LIU Y,et al. Revealing growth mechanisms of faceted Al₂Cu intermetallic compounds via high-speed synchrotron X-ray tomography. Acta Materialia, 2022, 231: 117903.
[20] TREMSIN A S, MAKOWSKA M G, PERRODIN D,et al. In situ diagnostics of the crystal-growth process through neutron imaging: application to scintillators. Journal of Applied Crystallography, 2016, 49: 743.
[21] TREMSIN A S, PERRODIN D, ADRIAN S L,et al. Real-time crystal growth visualization and quantification by energy-resolved neutron imaging. Scientific Reports, 2017, 7: 46275.
[22] TREMSIN A S, PERRODIN D, ADRIAN S L,et al. In situ observation and analysis of solid-state diffusion and liquid migration in a crystal growth system: a segregation-driven diffusion couple. Acta Materialia, 2020, 186: 434.
[23] ZHANG N, YECKEL A, BURGER A,et al. Anomalous segregation during electrodynamic gradient freeze growth of cadmium zinc telluride. Journal of Crystal Growth, 2011, 325(1): 10.
[24] ROY U, WEILER S, STEIN J.Growth and interface study of 2 in diameter CdZnTe by THM technique.Journal of Crystal Growth, 2010, 312(19): 2840.
[25] ABROSIMOV N, LÜDGE A, RIEMANN H,et al. Lateral photovoltage scanning (LPS) method for the solid-liquid interface visualization of Si₁-_xGe_x single crystals. Journal of Crystal Growth, 2002, 237: 356.
[26] MU H H, WANG P F, SHI Y F,et al. Large-size CeF₃ crystal growth by heat exchanger-Bridgman method: thermal field design and optimization. Journal of Inorganic Materials, 2023, 38(3): 288.
[27] WANG P F, ZHANG Z H, WU Q H,et al. Numerical investigation of the VB growth of CaF₂ crystal with supercooled crucible wall. Journal of Crystal Growth, 2023, 617: 127232.
[28] BERGMAN T L.Fundamentals of Heat and Mass Transfer. New York: John Wiley & Sons, 2011.
[29] VOLLER V R, PRAKASH C.A fixed grid numerical modelling methodology for convection-diffusion mushy region phase-change problems.International Journal of Heat and Mass Transfer, 1987, 30(8): 1709.
[30] DEMINA S, BYSTROVA E, POSTOLOV V,et al. Use of numerical simulation for growing high-quality sapphire crystals by the Kyropoulos method. Journal of Crystal Growth, 2008, 310(7/8/9): 1443.
[31] CROCHET M, DUPRET F, RYCKMANS Y,et al. Numerical simulation of crystal growth in a vertical Bridgman furnace. Journal of Crystal Growth, 1989, 97(1): 173.

CaF₂晶体热交换坩埚下降法生长固液界面演变及热质输运机制

Interface Evolution and Heat-mass Transfer Mechanisms during CaF₂ Crystal Growth by the Heat Exchanger-Bridgman Method

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	赵丽娟, 谭哲, 张晓光, 蒋国赛, 陶然, 潘德安. 废加氢催化剂颗粒分级数值模拟研究[J]. 无机材料学报, 2025, 40(12): 1387-1394.
[2]	王旭, 李翔, 寇华敏, 方伟, 吴庆辉, 苏良碧. 不同浓度Y³⁺离子掺杂对CaF₂晶体性能的影响[J]. 无机材料学报, 2024, 39(9): 1029-1034.
[3]	郝永鑫, 秦娟, 孙军, 杨金凤, 李清连, 黄贵军, 许京军. 坩埚底角形状对提拉法生长同成分铌酸锂晶体的影响[J]. 无机材料学报, 2024, 39(10): 1167-1174.
[4]	陈昆峰, 胡乾宇, 刘锋, 薛冬峰. 多尺度晶体材料的原位表征技术与计算模拟研究进展[J]. 无机材料学报, 2023, 38(3): 256-269.
[5]	史艳磊, 孙聂枫, 徐成彦, 王书杰, 林朋, 马春雷, 徐森锋, 王维, 陈春梅, 付莉杰, 邵会民, 李晓岚, 王阳, 秦敬凯. 半密封直拉法生长6英寸磷化铟单晶热场研究[J]. 无机材料学报, 2023, 38(3): 335-342.
[6]	孙晗, 李文俊, 贾子璇, 张岩, 殷利迎, 介万奇, 徐亚东. ACRT技术对大尺寸ZnTe晶体溶液法制备及其性能影响[J]. 无机材料学报, 2023, 38(3): 310-315.
[7]	穆宏赫, 王鹏飞, 施宇峰, 张中晗, 武安华, 苏良碧. 热交换坩埚下降法制备大尺寸氟化铈晶体的热场设计与优化[J]. 无机材料学报, 2023, 38(3): 288-295.
[8]	逄思远, 钱小波, 吴庆辉, 于浩, 徐家跃, 苏良碧. Sc掺杂Nd:CaF₂激光晶体的结构及其光谱性能参数[J]. 无机材料学报, 2018, 33(8): 873-876.
[9]	陈文波, 陈伦江, 刘川东, 程昌明, 童洪辉, 朱海龙. 射频热等离子体制备球形氧化铝粉末的数值模拟及实验研究[J]. 无机材料学报, 2018, 33(5): 550-556.
[10]	何益锋, 薛艳艳, 刘文庆, 苏良碧, 唐飞, 王静雅. Yb掺杂Ca_1-_xR_xF₂₊_x(R=La, Gd)激光晶体的结构与光谱性能参数的研究[J]. 无机材料学报, 2017, 32(8): 857-862.
[11]	赵爽, 杨自春, 周新贵. 不同界面SiC/SiC复合材料的断裂行为研究[J]. 无机材料学报, 2016, 31(1): 58-62.
[12]	王晓媛, 闫亚宾, 嶋田隆広, 北村隆行. 纳米铁电材料铁电性及其力电耦合特性的原子尺度模拟研究[J]. 无机材料学报, 2015, 30(6): 561-570.
[13]	刘光霞, 王圣来, 丁建旭, 孙云, 刘文洁, 朱胜军. 转速对KDP晶体成帽影响的数值模拟研究[J]. 无机材料学报, 2013, 28(06): 665-670.
[14]	孙天拓, 林健, 魏恒勇, 冯昭彬. 银纳米晶掺杂玻璃基片对Er³⁺/Yb³⁺共掺碲酸盐薄膜的荧光增强及其数值模拟[J]. 无机材料学报, 2011, 26(11): 1215-1220.
[15]	魏玺,成来飞,张立同,徐永东. C/SiC复合材料等温化学气相浸渗过程的数值模拟研究[J]. 无机材料学报, 2006, 21(5): 1179-1184.