直拉法单晶硅制备过程控氧技术研究进展

摘要/Abstract

摘要： 随着我国光伏行业的快速发展,直拉(CZ)法制备的单晶硅朝着大尺寸、高品质、低成本的方向发展,然而随着单晶硅尺寸越来越大,其内部氧杂质含量偏高的问题也越来越突出。本文在介绍CZ法制备单晶硅过程中氧杂质传输机理的基础上,归纳总结了单晶硅生产过程的控氧技术现状,分析了热场结构优化、工艺优化、掺杂元素、氩气流场优化以及新型CZ技术对单晶硅氧杂质含量的影响规律,并对控氧技术的发展方向提出了展望。

关键词: 直拉法, 单晶硅, 控氧技术, 热场结构, 工艺参数, 连续直拉法

Abstract: The single-crystal silicon prepared by Czochralski (CZ) method is showing a development trend toward larger size, higher quality, and lower cost with the rapidly development of China's photovoltaic industry. Nevertheless, the issue of high oxygen impurity content in single-crystal silicon is increasingly drawing attention as the size of the single-crystal silicon size increases. In this paper, based on the introduction of oxygen impurity transport mechanism during the process of preparing single-crystal silicon by CZ method, the current state of oxygen control technology in the production of single-crystal silicon was summarized. Furthermore, the influence laws of thermal field structure optimization, process optimization, doping elements, argon flow field optimization and new CZ technology on the oxygen impurity content of single-crystal silicon were analyzed, and the development direction of oxygen control technology in the future was put forward.

Key words: Czochralski method, single-crystal silicon, oxygen control technology, thermal field structure, process parameter, continuous Czochralski method

中图分类号:

O782⁺.5

张梦宇, 李太, 杜汕霖, 黄振玲, 赵亮, 吕国强, 马文会. 直拉法单晶硅制备过程控氧技术研究进展[J]. 硅酸盐通报, 2022, 41(9): 3259-3271.

ZHANG Mengyu, LI Tai, DU Shanlin, HUANG Zhenling, ZHAO Liang, LYU Guoqiang, MA Wenhui. Research Progress on Oxygen Control Technology During Preparation of Czochralski Single-Crystal Silicon[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(9): 3259-3271.

参考文献

[1] 丁怡婷,寇江泽.我国建成世界最大清洁发电体系[N].人民日报海外版,2021-09-06.
DING Y T, KOU J Z, China has built the world's largest clean power generation system[N]. People's Daily Overseas Edition, 2021-09-06 (in Chinese).
[2] 梁启超,乔芬,杨健,等.太阳能电池的研究现状与进展[J].中国材料进展,2019,38(5):505-511.
LIANG Q C, QIAO F, YANG J, et al. Present research status and progress of solar cells full text replacement[J]. Materials China, 2019, 38(5): 505-511 (in Chinese).
[3] 严大洲,刘艳敏,万烨,等.晶硅太阳能在“双碳”经济中的作用与影响[J].中国有色冶金,2021,50(5):1-6.
YAN D Z, LIU Y M, WAN Y, et al. Effect and impact of crystalline silicon solar energy in the “double carbon” economy[J]. China Nonferrous Metallurgy, 2021, 50(5): 1-6 (in Chinese).
[4] DASH W C. Silicon crystals free of dislocations[J]. Journal of Applied Physics, 1958, 29(4): 736-737.
[5] HURLE D T J. Control of diameter in Czochralski and related crystal growth techniques[J]. Journal of Crystal Growth, 1977, 42: 473-482.
[6] VORONKOV V V. The mechanism of swirl defects formation in silicon[J]. Journal of Crystal Growth, 1982, 59(3): 625-643.
[7] SERIES R W, HURLE D T J. The use of magnetic fields in semiconductor crystal growth[J]. Journal of Crystal Growth, 1991, 113(1/2): 305-328.
[8] PUZANOV N I, EIDENZON A M, PUZANOV D N. Modelling microdefect distribution in dislocation-free Si crystals grown from the melt[J]. Journal of Crystal Growth, 1997, 178(4): 468-478.
[9] KANDA I, SUZUKI T, KOJIMA K. Influence of crucible and crystal rotation on oxygen-concentration distribution in large-diameter silicon single crystals[J]. Journal of Crystal Growth, 1996, 166(1/2/3/4): 669-674.
[10] HOSHIKAWA K, HUANG X M. Oxygen transportation during Czochralski silicon crystal growth[J]. Materials Science and Engineering: B, 2000, 72(2/3): 73-79.
[11] LUO J P, ZHOU C Y, LI Q H, et al. Diffusion coefficients of carbon, oxygen and nitrogen in silicon melt[J]. Journal of Crystal Growth, 2022, 580: 126476.
[12] BOND W L, KAISER W. Interstitial versus substitutional oxygen in silicon[J]. Journal of Physics and Chemistry of Solids, 1960, 16(1/2): 44-45.
[13] ONO T, SUGIMURA W, KIHARA T, et al. Wafer strength and slip generation behavior in 300 mm wafers[J]. ECS Transactions, 2006, 2(2): 109-122.
[14] ZENG Z D, MA X Y, CHEN J H, et al. Effect of oxygen precipitates on dislocation motion in Czochralski silicon[J]. Journal of Crystal Growth, 2010, 312(2): 169-173.
[15] 苏文佳,李九龙,杨伟,等.直拉法单晶硅中位错影响因素研究进展[J].硅酸盐学报,2021,49(4):723-735.
SU W J, LI J L, YANG W, et al. Research progress on influencing factors of dislocation in Czochralski silicon[J]. Journal of the Chinese Ceramic Society, 2021, 49(4): 723-735 (in Chinese).
[16] FUKUSHIMA W, HARADA H, MIYAMURA Y, et al. Effect of oxygen on dislocation multiplication in silicon crystals[J]. Journal of Crystal Growth, 2018, 486: 45-49.
[17] BINNS M J, KEARNS J, GOOD E A. Impact of oxygen-related defects on lifetime degradation in N-type CCZ/CZ mono-crystalline silicon during cell processing[J]. ECS Transactions, 2014, 60(1): 1233-1238.
[18] HWANG J M, SCHRODER D K. Recombination properties of oxygen-precipitated silicon[J]. Journal of Applied Physics, 1986, 59(7): 2476-2487.
[19] LI J Y, LIU Y J, TAN Y. Characterisation of single crystalline silicon grown by Czochralski method[J]. Materials Research Innovations, 2012, 16(6): 425-428.
[20] NIEWELT T, SCHÖN J, WARTA W, et al. Degradation of crystalline silicon due to boron-oxygen defects[J]. IEEE Journal of Photovoltaics, 2017, 7(1): 383-398.
[21] CHEN L, YU X G, CHEN P, et al. Effect of oxygen precipitation on the performance of Czochralski silicon solar cells[J]. Solar Energy Materials and Solar Cells, 2011, 95(11): 3148-3151.
[22] LIN A M R, DUTTON R W, ANTONIADIS D A, et al. The growth of oxidation stacking faults and the point defect generation at Si-SiO interface during thermal oxidation of silicon[J]. Journal of the Electrochemical Society, 1981, 128(5): 1121-1130.
[23] SADAMITSU S, OKUI M, KOJISUEOKA, et al. A model for the formation of oxidation-induced stacking faults in Czochralski silicon[J]. Japanese Journal of Applied Physics, 1995, 34: L597-L599.
[24] SINNO T, BROWN R A, VON AMMON W, et al. Point defect dynamics and the oxidation-induced stacking-fault ring in Czochralski-grown silicon crystals[J]. Journal of the Electrochemical Society, 1998, 145(1): 302-318.
[25] KAISER W, FRISCH H L, REISS H. Mechanism of the formation of donor states in heat-treated silicon[J]. Physical Review, 1958, 112(5): 1546-1554.
[26] CORBETT J W, FRISCH H L, SNYDER L C. On the thermal donors in silicon[J]. Materials Letters, 1984, 2(3): 209-210.
[27] WAGNER P, HAGE J. Thermal double donors in silicon[J]. Applied Physics A, 1989, 49(2): 123-138.
[28] MIYAMURA Y, HARADA H, NAKANO S, et al. Do thermal donors reduce the lifetimes of Czochralski-grown silicon crystals?[J]. Journal of Crystal Growth, 2018, 489: 1-4.
[29] OLSEN E, HELANDER M I, MEHL T, et al. Spectral characteristics and spatial distribution of thermal donors in N-type Czochralski-silicon wafers[J]. Physica Status Solidi, 2020, 217(6): 1900884.
[30] 王伟.石英坩埚中碱金属含量对硅单晶拉制的影响[C]//第十届中国太阳能光伏会议论文集.常州,2008:243-246.
WANG W. Effect of alkali metal content in quartz crucible on the pulling of silicon single crystal[C]//Proceedings of the 10th China Solar Photovoltaic Conference. Changzhou, 2008: 243-246 (in Chinese).
[31] HANSEN R L, DRAFALL L E, MCCUTCHAN R M, et al. Surface-treated crucibles for improved zero dislocation performance: US5976247[P]. 1999-11-02.
[32] HANSEN R L, DRAFALL L E, MCCUTCHAN R M, et al. Methods for improving zero dislocation yield of single crystals: US5980629[P]. 1999-11-09.
[33] 莫宇,张颖武,韩焕鹏,等.石英坩埚对大直径直拉硅单晶生长的影响[J].电子工艺技术,2021,42(1):46-49.
MO Y, ZHANG Y W, HAN H P, et al. Effects of quartz crucible on growth of large diameter Czochralski silicon[J]. Electronics Process Technology, 2021, 42(1): 46-49 (in Chinese).
[34] STURM F, TREMPA M, SCHUSTER G, et al. Material evaluation for engineering a novel crucible setup for the growth of oxygen free Czochralski silicon crystals[J]. Journal of Crystal Growth, 2022, 584: 126582.
[35] 高农农,葛林.加热器直径对200 mm太阳能级单晶硅加热效率、能耗和氧含量的影响[J].硅酸盐通报,2015,34(12):3658-3662.
GAO N N, GE L. Influence of heater diameter on heating efficiency, power consumption and oxygen concentration in the solar-grade single silicon[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(12): 3658-3662 (in Chinese).
[36] ZHOU B, CHEN W L, LI Z H, et al. Reduction of oxygen concentration by heater design during Czochralski Si growth[J]. Journal of Crystal Growth, 2018, 483: 164-168.
[37] 郝玉清.拉晶埚位对直拉硅单晶氧含量的影响[C]//全国半导体硅材料学术会议论文集.上海,1998:75-76.
HAO Y Q. Effect of pulling pot position on oxygen content of czochralski silicon single crystal[C]//National Conference on Semiconductor Silicon Materials. Shanghai, 1998: 75-76 (in Chinese).
[38] 任丽,罗晓英,李宁,等.初始埚位对单晶少子寿命的影响[J].半导体技术,2011,36(10):782-785.
REN L, LUO X Y, LI N, et al. Study on the CZ-Si growth process of high minority carrier lifetime[J]. Semiconductor Technology, 2011, 36(10): 782-785 (in Chinese).
[39] 高忙忙,朱博,李进,等.加热器/坩埚相对位置对?200 mm单晶硅生长过程中温度场和晶体质量的影响[J].硅酸盐通报,2016,35(11):3607-3612.
GAO M M, ZHU B, LI J, et al. Influence of heater/crucible position on the thermal field and crystal quality in the preparation of single crystal silicon with ?200 mm[J]. Bulletin of the Chinese Ceramic Society, 2016, 35(11): 3607-3612 (in Chinese).
[40] ZULEHNER W. Czochralski growth of silicon[J]. Journal of Crystal Growth, 1983, 65(1/2/3): 189-213.
[41] CHEN J C, TENG Y Y, WUN W T, et al. Numerical simulation of oxygen transport during the CZ silicon crystal growth process[J]. Journal of Crystal Growth, 2011, 318(1): 318-323.
[42] POPESCU A, BELLMANN M P, VIZMAN D. Effect of crucible rotation on the temperature and oxygen distributions in Czochralski grown silicon for photovoltaic applications[J]. CrystEngComm, 2021, 23(2): 308-316.
[43] 牟伟明.直拉硅单晶工艺参数对热场的影响研究[D].西安:西安理工大学,2015:20-25.
MOU W M. Influence of Czochralski silicon single crystal process parameters on thermal field[D]. Xi’an: Xi’an University of Technology, 2015: 20-25 (in Chinese).
[44] 杨凤艳.直拉法硅单晶中晶转对杂质含量的影响[J].大陆桥视野,2016(14):112-113.
YANG F Y. Influence of crystal transfer on impurity content in Czochralski single crystal[J]. New Silk Road Horizon, 2016(14): 112-113 (in Chinese).
[45] BORGHESI A, PIVAC B, SASSELLA A, et al. Oxygen precipitation in silicon[J]. Journal of Applied Physics, 1995, 77(9): 4169-4244.
[46] MACHIDA N, SUZUKI Y, ABE K, et al. The effects of argon gas flow rate and furnace pressure on oxygen concentration in Czochralski-grown silicon crystals[J]. Journal of Crystal Growth, 1998, 186(3): 362-368.
[47] KALAEV V V, EVSTRATOV I Y, MAKAROV Y N. Gas flow effect on global heat transport and melt convection in Czochralski silicon growth[J]. Journal of Crystal Growth, 2003, 249(1/2): 87-99.
[48] TENG Y Y, CHEN J C, HUANG C C, et al. Numerical investigation of the effect of heat shield shape on the oxygen impurity distribution at the crystal-melt interface during the process of Czochralski silicon crystal growth[J]. Journal of Crystal Growth, 2012, 352(1): 167-172.
[49] PEARCE C W, JACCODINE R J, FILO A J, et al. Oxygen content of heavily doped silicon[J]. Applied Physics Letters, 1985, 46(9): 887-889.
[50] BORGHESI A, GEDDO M, GUIZZETTI G, et al. Interstitial oxygen determination in heavily doped silicon[J]. Journal of Applied Physics, 1990, 68(4): 1655-1660.
[51] WIJARANAKULA W. Oxygen diffusion in carbon-doped silicon[J]. Journal of Applied Physics, 1990, 68(12): 6538-6540.
[52] WIJARANAKULA W. Oxygen precipitation and defects in heavily doped Czochralski silicon[J]. Journal of Applied Physics, 1992, 72(7): 2713-2723.
[53] NOZAKI T, ITOH Y, MASUI T, et al. Behavior of oxygen in the crystal formation and heat treatment of silicon heavily doped with antimony[J]. Journal of Applied Physics, 1986, 59(7): 2562-2565.
[54] HUANG X M, TERASHIMA K, IZUNOME K, et al. Effect of antimony-doping on the oxygen segregation coefficient in silicon crystal growth[J]. Journal of Crystal Growth, 1995, 149(1/2): 59-63.
[55] GUPTA S, MESSOLORAS S, SCHNEIDER J R, et al. Oxygen precipitation in carbon-doped silicon[J]. Semiconductor Science and Technology, 1992, 7(1): 6-11.
[56] SCALA R, PORRINI M, VORONKOV V. Impact of arsenic and phosphorus concentration on oxygen content in heavily doped silicon single crystal[J]. Journal of Crystal Growth, 2020, 548: 125820.
[57] WANG C, ZHANG H, WANG T H, et al. A continuous Czochralski silicon crystal growth system[J]. Journal of Crystal Growth, 2003, 250(1/2): 209-214.
[58] XU H, TIAN X R. Minority carrier lifetime of N-type mono-crystalline silicon produced by continuous Czochralski technology and its effect on hetero-junction solar cells[J]. Energy Procedia, 2016, 92: 708-714.
[59] JAFRI I H, PRASAD V, ANSELMO A P, et al. Role of crucible partition in improving Czochralski melt conditions[J]. Journal of Crystal Growth, 1995, 154(3/4): 280-292.
[60] KITASHIMA T, LIU L J, KITAMURA K, et al. Effects of shape of an inner crucible on convection of lithium niobate melt in a double-crucible Czochralski process using the accelerated crucible rotation technique[J]. Journal of Crystal Growth, 2004, 267(3/4): 574-582.
[61] ZHAO W H, LI J C, LIU L J. Control of oxygen impurities in a continuous-feeding Czochralski-silicon crystal growth by the double-crucible method[J]. Crystals, 2021, 11(3): 264.
[62] NGUYEN T H T, CHEN J C, LO S C. Effects of different partition depths on heat and oxygen transport during continuous Czochralski (CC_z) silicon crystal growth[J]. Journal of Crystal Growth, 2022, 583: 126546.
[63] 阙端麟.硅材料科学与技术[M].杭州:浙江大学出版社,2000:39.
QUE D L. Silicon materials science and technology[M]. Hangzhou: Zhejiang University Press, 2000: 39 (in Chinese).
[64] HIRATA H, HOSHIKAWA K. Silicon crystal growth in a cusp magnetic field[J]. Journal of Crystal Growth, 1989, 96(4): 747-755.
[65] 宇慧平,隋允康,张峰翊,等.?300 mm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.
YU H P, SUI Y K, ZHANG F Y, et al. Numerical simulation of a Czochralski silicon crystal growth with a large diameter ?300 mm under a cusp magnetic field[J]. Journal of Inorganic Materials, 2005, 20(2): 453-458 (in Chinese).
[66] 常麟,周旗钢,戴小林,等.CUSP磁场对直拉硅单晶氧浓度分布影响的数值模拟[J].稀有金属,2011,35(6):909-915.
CHANG L, ZHOU Q G, DAI X L, et al. Numerical simulation of CUSP magnetic field on oxygen concentration distribution in CZ-Si crystal growth[J]. Chinese Journal of Rare Metals, 2011, 35(6): 909-915 (in Chinese).
[67] CHEN J C, GUO P C, CHANG C H, et al. Numerical simulation of oxygen transport during the Czochralski silicon crystal growth with a cusp magnetic field[J]. Journal of Crystal Growth, 2014, 401: 888-894.