半密封直拉法生长6英寸磷化铟单晶热场研究

doi:10.15541/jim20220645

无机材料学报 ›› 2023, Vol. 38 ›› Issue (3): 335-342.DOI: 10.15541/jim20220645 CSTR: 32189.14.10.15541/jim20220645

所属专题：【信息功能】大尺寸功能晶体(202409)

半密封直拉法生长6英寸磷化铟单晶热场研究

史艳磊¹^,²(), 孙聂枫²(), 徐成彦¹, 王书杰², 林朋², 马春雷², 徐森锋², 王维², 陈春梅², 付莉杰², 邵会民², 李晓岚², 王阳², 秦敬凯¹()

1.哈尔滨工业大学（深圳）材料科学与工程学院, 索维奇智能材料实验室, 深圳518055
2.中国电子科技集团公司第十三研究所, 专用集成电路重点实验室, 石家庄 050051

收稿日期:2022-11-01 修回日期:2022-12-14 出版日期:2023-03-20 网络出版日期:2023-01-17
通讯作者: 孙聂枫, 研究员. E-mail: snf2015@126.com;
秦敬凯, 讲师. E-mail: jk.qin@hit.edu.cn
作者简介:史艳磊(1986-), 男, 高级工程师. E-mail: shiyanlei100@163.com

Thermal Field of 6-inch Indium Phosphide Single Crystal Growth by Semi-sealed Czochralski Method

SHI Yanlei¹^,²(), SUN Niefeng²(), XU Chengyan¹, WANG Shujie², LIN Peng², MA Chunlei², XU Senfeng², WANG Wei², CHEN Chunmei², FU Lijie², SHAO Huimin², LI Xiaolan², WANG Yang², QIN Jingkai¹()

1. Sauvage Laboratory for Smart Materials, School of Materials Science and Engineering, Harbin Institute of Technology (Shenzhen), Shenzhen 518055, China
2. National Key Laboratory of ASIC, The 13th Research Institute of China Electronic Technology Group Corporation, Shijiazhuang 050051, China

Received:2022-11-01 Revised:2022-12-14 Published:2023-03-20 Online:2023-01-17
Contact: SUN Niefeng, professor. E-mail: snf2015@126.com;
QIN Jingkai, lecturer. E-mail: jk.qin@hit.edu.cn
About author:SHI Yanlei (1986-), male, senior engineer. E-mail: shiyanlei100@163.com
Supported by:
National Natural Science Foundation of China(51871202);National Natural Science Foundation of China(51401186);S&T Program of Hebei(20311001D)

摘要/Abstract

摘要：

磷化铟(InP)是一种重要的化合物半导体材料。InP由于性能优异，在高频电子器件及红外光电器件领域的应用日趋增多。目前，磷化铟器件的价格远高于砷化镓器件，其主要原因是磷化铟单晶成品率低，以及晶圆尺寸较小造成外延和器件工艺成本居高不下。增大InP单晶的直径对降低晶圆及半导体工艺成本至关重要。制备大尺寸InP单晶的主要难点是提高晶体的成品率和降低晶体的应力。目前行业内通常使用垂直梯度凝固(Vertical gradient freeze, VGF)法和液封直拉(Liquid Encapsulated Czochralski, LEC)法制备InP。 VGF法在制备6英寸(15.24 cm)InP方面鲜有建树， LEC法制备的晶体往往具有更高的应力和位错密度。本研究展示了半密封直拉(Semi-Sealed Czochralski, SSC)法在生长大直径化合物半导体材料方面的优势，采用数值模拟方法分析了LEC法和SSC法中熔体、晶体、氧化硼和气氛中的温度分布，重点分析了SSC技术的温度分布。模拟结果中，SSC法晶体中的温度梯度为17.4 K/cm，明显低于LEC法中的温度梯度28.7 K/cm。在等径阶段SSC法晶体肩部附近气氛温度比LEC法高504 K。根据模拟结果对SSC法热场进行了优化后，本研究得到了低缺陷密度、无裂纹的6英寸S掺杂InP单晶，证实了SSC法应用于大尺寸InP单晶生长的优势。

关键词: 磷化铟, 半密封直拉, 数值模拟, 热场

Abstract:

Indium phosphide (InP) is a kind of important compound semiconductor material, now increasingly used in high frequency electronic devices and infrared optoelectronic devices. Currently, the price of InP devices is much higher than that of GaAs devices, mainly because of its low yield of single crystals and increase of epitaxy, and device process cost due to smaller wafer diameter. Increasing the diameter of InP single crystals is critical to reducing wafer and semiconductor process costs. The main difficulties in preparing large diameter InP single crystals are increasing crystal yield and reducing stress in the crystal. The vertical gradient freeze (VGF) and the liquid encapsulated Czochralski (LEC) methods are commonly used in the industry to prepare InP, while the VGF method has little success in preparing 6-inch InP crystals, and the crystals prepared by the LEC method tend to have higher stress and dislocation density. Here we reported a semi-sealed Czochralski (SSC) method to grow large diameter InP crystals. Numerical simulations were used to analyze the temperature distribution in melt, crystal, boron oxide, and atmosphere in LEC and SSC method, with emphasis on temperature field of the SSC method. As a simulation result, the temperature gradient in the crystal of SSC method is 17.4 K/cm, significantly lower thanthat of 28.7 K/cm in the LEC method. And temperature of atmosphere near the crystal shoulder in the diameter control stage of the SSC method is 504 K higher than that of the LEC method. Then the used thermal field of SSC method was optimized according to the simulation results, and 6-inch (1 inch=2.54 cm) S doped InP single crystals with low defect density and no cracks were prepared by this optimized method, which confirmed that the optimized SSC method is promising for growing large-size InP single crystals.

Key words: indium phosphide, semi-sealed Czochralski, numerical simulation, thermal field

中图分类号:

TQ174

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.

SHI Yanlei, SUN Niefeng, XU Chengyan, WANG Shujie, LIN Peng, MA Chunlei, XU Senfeng, WANG Wei, CHEN Chunmei, FU Lijie, SHAO Huimin, LI Xiaolan, WANG Yang, QIN Jingkai. Thermal Field of 6-inch Indium Phosphide Single Crystal Growth by Semi-sealed Czochralski Method[J]. Journal of Inorganic Materials, 2023, 38(3): 335-342.

图/表 8

Fig. 1 Schematic of the processes of semi-sealed Czochralski method (a) Seeding and shoulder stage; (b) Diameter-controlling stage; (c) Crystal raised from the melt

Fig. 2 Thermal field distributions in the seeding stages with different methods (a) SSC method; (b) VCZ method; (c) LEC method

Fig. 3 Temperature distribution in the melt at the front of the solid-liquid interface (a) Sampling position in the melt; (b) Temperature distribution in the melt at the front of solid-liquid interface; (c) Schematic of heat flow in VCZ method

Fig. 4 Temperature distribution in the crystal (a) Schematic diagram of the temperature sampling points in the crystal; (b) Temperature distribution in the crystal from the solid-liquid interface to the seed-crystal interface

Fig. 5 Temperature distribution in the melt, B2O3 and atmosphere around the crystal (a) Location of sampling points; (b) Comparison of temperature distributions by using different methods

Table 1 Location, temperature and temperature gradient of each section

Method	Item	Melt	B₂O₃	Gas 1		Gas 2	Gas 3
	Node	Start point	Node 1	Node 2	Node 3	Node 4	End point
	Distance/mm	0.0	11.0	52.0	55.0	70.0	76.0
SSC	Temperature/K	1340.0	1338.1	1221.4	1190.7	1185.8	1148.4
SSC	Temperature gradient/(K·mm^-1)	-0.2	-2.8	-10.2		-0.3	-6.2
LEC	Temperature/K	1344.5	1340.3	1127.6	877.7	808.7	644.4
LEC	Temperature gradient/(K·mm^-1)	-0.4	-5.2	-62.5		-6.9	-16.4

Fig. 6 Digital photographs of 6-inch InP crystal and cutting wafer (a) LEC-grown InP crystal; (b) SSC-grown InP crystal; (c) Cracked cutting wafer of LEC-grown crystal

Fig. 7 Dislocation densities of crystal tails by LEC and SSC methods (a) Crystal dislocation density by LEC method; (b) Crystal dislocation density by SSC method

参考文献 14

[1]	HAMADA H, TSUTSUMI T, SUGIYAMA H, et al. Millimeter- wave InP Device technologies for ultra-high speed wireless communications toward beyond 5G. Proceedings of IEEE International Electron Devices Meeting (IEDM), San Francisco, 2019.
[2]	AJAYAN J, NIRMAL D. A review of InP/InAlAs/InGaAs based transistors for high frequency applications. Superlattices and Microstructures, 2015, 86: 1. DOI URL
[3]	FANG Y Q, CHEN W, AOT H, et al. InGaAs/InP single-photon detectors with 60% detection efficiency at 1550 nm. Review of Scientific Instruments, 2020, 91(8): 083102. DOI URL
[4]	WANG S. Recent research progress of THz InP HEMT and HBT technologies. Micronanoelectronic Technology, 2018, 55(6): 381.
[5]	MOUTANABBIR O, GOSELE U. Heterogeneous integration of compound semiconductors. Annual Review of Materials Research, 2010, 40: 469. DOI URL
[6]	MONBERG E M, GAULT W A, DOMINGUEZ F. The growth and characterization of large size, high quality, InP single crystals. Journal of the Electrochemical Society, 1988, 135(2): 500. DOI
[7]	JORDAN A S, VONNEIDA A R, CARUSOTHE R. The theory and practice of dislocation reduction in GaAs and InP. Journal of Crystal Growth, 1984, 70(1): 555. DOI URL
[8]	IWASAKI K, SATO K, AOYAMA K. 6-in diameter InP single crystals grown by the hot-wall LEC method and the mirror wafers. IEEE Transactions on Semiconductor Manufacturing, 2003, 16(3): 360. DOI URL
[9]	SHAO H, SUN N, ZHANG X, et al. High quality 6-inch InP single crystal grown by LEC method. Semiconductor Technology, 2020, 45(8): 617.
[10]	ODA O, KAINOSHO K, KOHIRO K, et al. Development of high quality InP bulk crystals. Journal of Electronic Materials, 1991, 20(12): 1007. DOI URL
[11]	KOHIRO K, OHTA M, ODA O. Growth of long-length 3 inch diameter Fe-doped InP single crystal. Journal of Crystal Growth, 1996, 158(3): 197. DOI URL
[12]	KOHIRO K, KAINOSHO K, ODA O, et al. Growth of low dislocation density InP single crystals by the phosphorus vapor controlled LEC method. Journal of Electronic Materials, 1991, 20(12): 1013. DOI URL
[13]	HOSOKAWA Y, YABUHARA Y, NAKAI R, et al. Development of 4-inch diameter InP single crystal with low dislocation density using VCZ method. 10th Intern. Conf. on Indium Phosphide and Related Materials, Tsukuba, 1998.
[14]	NODA A, SUZUKI K, ARAKAWA A, et al. 4-inch InP crystals grown by phosphorous vapor controlled LEC method. 14th Indium Phosphide and Related Materials Conference, Stockholm, 2002.

半密封直拉法生长6英寸磷化铟单晶热场研究

Thermal Field of 6-inch Indium Phosphide Single Crystal Growth by Semi-sealed Czochralski Method

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 14

相关文章 11

编辑推荐

Metrics

本文评价

[1]	秦娟, 梁丹丹, 孙军, 杨金凤, 郝永鑫, 李清连, 张玲, 许京军. 提拉法生长平肩同成分铌酸锂晶体的研究[J]. 无机材料学报, 2023, 38(8): 978-986.
[2]	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.
[3]	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.
[4]	杨锁龙, 王晓方, 蒋春丽, 赵雅文, 曾荣光, 王怀胜, 赖新春. InP量子点的掺杂及其光学性能[J]. 无机材料学报, 2016, 31(10): 1051-1057.
[5]	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.
[6]	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.
[7]	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.
[8]	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.
[9]	常旭,唐春安,张后全,张永彬,张亚芳. 层状复合陶瓷增韧机理的数值模拟[J]. 无机材料学报, 2005, 20(2): 459-464.
[10]	宇慧平,隋允康,张峰翊,常新安,安国平. φ300mm的大直径直拉单晶硅勾形磁场下生长的数值模拟[J]. 无机材料学报, 2005, 20(2): 453-458.
[11]	张海斌,沈定中,任国浩,宫波. 坩埚下降法晶体生长中输运过程的数值模拟的研究进展[J]. 无机材料学报, 2002, 17(5): 910-914.