SiH4/H2等离子体气相生长硅薄膜的动力学模型

文书堂; 张红卫; 张丽伟; 陈改荣; 卢景霄

doi:10.7498/aps.59.4901

摘要

在化学气相沉积微晶硅薄膜过程中,为了降低成本,必须提高生长速率,但薄膜的微观结构和光电性能则随之降低,原因是成膜先驱物在薄膜表面上的扩散长度降低了. 本文利用量子化学的反应动力学理论建立有关成膜先驱物SiH3和H的反应平衡方程,求解薄膜生长速率和成膜先驱物的扩散长度,并找出影响生长速率与扩散长度的微观参数,发现生长速率不仅与流向衬底的SiH3的通量密度有关,而且与H的通量密度有关;SiH3的扩散长度与衬底温度和薄膜表面的硅氢键的形态有关,当

关键词:

Abstract

During the process of plasma enhanced chemical vapor deposition, the growth rate of microcrystalline silicon films must be improved to reduce manufacture cost. With the increase of growth rate, the photoelectrical properties of such films will be greatly decreased. The main cause is the diffusion length of the precursors on the film surface decreases. In this study, a quantitative kinetic model was developed and the reaction balance equations of SiH3 and H were constructed, and the deposition rate, diffusion length and their influencing factors were obtained. We find that the deposition rate is determined by the fluxes of both SiH3 and H. The diffusion length of precursors is determined by the substrate temperature and the configuration of the surface silicon-hydrogen bonds. The diffusion length has a higher value when the growing film surface is covered by mono-hydrides, it has a smaller value when covered by tri-hydride, and it has a value close to zero when covered by dangling bonds.

Keywords:

plasma enhanced chemical vapor deposition /
growth mechanism /
diffusion length

作者及机构信息

(1)新乡学院化学与化工学院,新乡 453003; (2)新乡学院化学与化工学院,新乡 453003; 郑州大学材料物理教育部重点实验室,郑州 450052; (3)新乡学院化学与化工学院,新乡 453003; 郑州师专物理系,郑州 450005; (4)郑州大学材料物理教育部重点实验室,郑州 450052

基金项目: 国家重点基础研究发展计划(批准号:2006CB202601)资助的课题.

Authors and contacts

(1)Key Laboratory of Material Physics of Ministry of Education, Zhengzhou University, Zhengzhou 450052, China; (2)Key Laboratory of Material Physics of Ministry of Education, Zhengzhou University, Zhengzhou 450052, China; Department of Physics, Zhengzhou Teachers College, Zhengzhou 450005, China; (3)School of Chemistry and Chemical Engineering, Xinxiang University, Xinxiang 453003, China; (4)School of Chemistry and Chemical Engineering, Xinxiang University, Xinxiang 453003, China; Key Laboratory

参考文献

[1]	Zhang Q Y, Ma T C, Pan Z Y, Tang J Y 2000 Acta Phys. Sin. 49 297 (in Chnese) [张庆瑜、马腾才、潘正瑛、汤家镛 2000 49 297]
[2]	Yang N, Chen G H, Zhang Y, Gong W B, Zhu H S 2000 Acta Phys. Sin. 49 2225 (in Chinese) [杨宁、陈光华、张阳、公维宾、朱鹤孙 2000 49 2225]
[3]	Ma T B, Hu Y Z, Wang H 2007 Acta Phys. Sin. 56 480 (in Chinese) [马天宝、胡元中、王慧 2007 56 480]
[4]	Liu Z L, Wei H L, Wang H W, Wang J Z 1999 Acta Phys. Sin. 48 1302 (in Chinese) [刘祖黎、魏合林、王汉文、王均震 1999 48 1302]
[5]	Pflüger A, Schroder B, Bartaa H J 2003 Thin Solid Films 430 73
[6]	Zhang P F, Zheng X P, He D Y 2003 Sci. Chin. Ser. G 33 340 (in Chinese)[张佩峰、郑小平、贺德衍 2003 中国科学, G 辑 33 340]
[7]	Bogaerts A, Bleecker K, Kolev I, Madani M 2005 Surf. Coat. Tech. 200 62
[8]	Hua G S, Lou Y M, Christofides P D 2008 Chem. Eng. Sci. 63 1800
[9]	Nishimoto T, Takai M, Kondo M, Matsuda A 2000 Proc. 28th IEEE PVSC (Anchorage: IEEE Press) p876
[10]	Wen S T, Lu J X, Li Y X, Wang H Y, Zhang H W, Wen L W 2008 Mod. Phys. Lett. B 22 1727
[11]	Wen S T, Zhang L W, Lu J X, Li Y X, Du Z Y 2008 Korean J. Chem. Eng. 25 1539
[12]	Crandall J R, Luft W 1995 Prog. Photovoltaics 3 315
[13]	Street R A 1991 Hydrogenated Amorphous Silicon (New York: Cambridge University Press) p229
[14]	Gupta A 2001 (Ph. D. Dissertation) (Raleigh: North Carolina State University)
[15]	Bray K R, Parsons G N 2001 Phys. Rev. B 65 35311
[16]	Gupta A, Parsons G N 2000 J. Vac. Sci. Technol. B 18 1764
[17]	Robertson J 2000 J. Appl. Phys. 87 2608
[18]	Kessels W M M, Smets A H, Marra D C, Aydil E S, Schram D C, Sanden M C M 2001 Thin Solid Films 383 154
[19]	Doren D J 1996 Advances in Chemical Physics (New York: John Wiley & Sons Inc) p124
[20]	Ramalingam S, Maroudas D, Aydil E S 1999 J. Appl. Phys. 86 2872
[21]	Dewarrat R, Robertson J 2002 J. Non-Cryst. Solids 299 48
[22]	Keudell A, AbeIson J R 1999 Phys. Rev. B 59 5791
[23]	Dinger A, Lutterloh C, Kuppers J 1999 Chem. Phys. Lett. 311 202
[24]	Buntin S A 1996 J. Chem. Phys. 105 2066
[25]	Widdra W, Yi S I, Maboudian R, Briggs G A D, Weinberg W H 1995 Phys. Rev. Lett. 74 2074
[26]	Koleske D D, Gates S M, Jackson B 1994 J. Chem. Phys. 101 3301
[27]	Koleske D D, Gates S M, Schultz J A 1993 J. Chem. Phys. 99 5619
[28]	Sinniah K, Sherman M G, Lewis L B, Weinberg W H, Yates J T, Janda K C 1990 J. Chem. Phys. 92 5700
[29]	Ramalingarn S, Maroudas D, Aydil E S, Walch S P 1998 Surf. Sci. 418 L8
[30]	Perrin I, Shiratani M, Kae-Nune P, Videlot H, Jolly J, Guillon J 1998 J. Vac. Sci. Tech. A 16 278
[31]	Keudell A, Abelson J R 1999 Phys. Rev. B 59 5791
[32]	Kitahar K, Murakami S, Hara A, Joshi C 1998 Appl. Phys. Lett. 72 19
[33]	Itabashi N, Nishiwaki N, Magane M, Goto T, Matsuda A, Yamada C, Hirota E 1990 Jpn. J.Appl. Phys. 29 585
[34]	Tachibana K, Mukai T, Harima H 1991 Jpn. J. Appl. Phys. 30 L1208
[35]	Wen S T, Zhang L W, Lu J X, Feng X L, Guo X J, Shen C H, Xu Y H, Li B S 2008 Int. J. Mod. Phys. B 23 1147
[36]	Gao X Y, Li R, Chen Y S, Lu J X, Liu P, Feng T H, Wang H J, Yang S E 2006 Acta Phys. Sin. 55 98 (in Chinese) [郜小勇、李瑞、陈永生、卢景霄、刘萍、冯团辉、王红娟、杨仕娥 2006 55 98]
[37]	Zhang X D, Zhao Y, Gao Y T, Chen F, Zhu F, Wei C C, Sun J, Geng X H, Xiong S Z 2006 Acta Phys. Sin. 55 6698 (in Chinese) [张晓丹、赵颖、高艳涛、陈飞、朱锋、魏长春、孙建、耿新华、熊绍珍 2006 55 6698]

施引文献

[1]	Zhang Q Y, Ma T C, Pan Z Y, Tang J Y 2000 Acta Phys. Sin. 49 297 (in Chnese) [张庆瑜、马腾才、潘正瑛、汤家镛 2000 49 297]
[2]	Yang N, Chen G H, Zhang Y, Gong W B, Zhu H S 2000 Acta Phys. Sin. 49 2225 (in Chinese) [杨宁、陈光华、张阳、公维宾、朱鹤孙 2000 49 2225]
[3]	Ma T B, Hu Y Z, Wang H 2007 Acta Phys. Sin. 56 480 (in Chinese) [马天宝、胡元中、王慧 2007 56 480]
[4]	Liu Z L, Wei H L, Wang H W, Wang J Z 1999 Acta Phys. Sin. 48 1302 (in Chinese) [刘祖黎、魏合林、王汉文、王均震 1999 48 1302]
[5]	Pflüger A, Schroder B, Bartaa H J 2003 Thin Solid Films 430 73
[6]	Zhang P F, Zheng X P, He D Y 2003 Sci. Chin. Ser. G 33 340 (in Chinese)[张佩峰、郑小平、贺德衍 2003 中国科学, G 辑 33 340]
[7]	Bogaerts A, Bleecker K, Kolev I, Madani M 2005 Surf. Coat. Tech. 200 62
[8]	Hua G S, Lou Y M, Christofides P D 2008 Chem. Eng. Sci. 63 1800
[9]	Nishimoto T, Takai M, Kondo M, Matsuda A 2000 Proc. 28th IEEE PVSC (Anchorage: IEEE Press) p876
[10]	Wen S T, Lu J X, Li Y X, Wang H Y, Zhang H W, Wen L W 2008 Mod. Phys. Lett. B 22 1727
[11]	Wen S T, Zhang L W, Lu J X, Li Y X, Du Z Y 2008 Korean J. Chem. Eng. 25 1539
[12]	Crandall J R, Luft W 1995 Prog. Photovoltaics 3 315
[13]	Street R A 1991 Hydrogenated Amorphous Silicon (New York: Cambridge University Press) p229
[14]	Gupta A 2001 (Ph. D. Dissertation) (Raleigh: North Carolina State University)
[15]	Bray K R, Parsons G N 2001 Phys. Rev. B 65 35311
[16]	Gupta A, Parsons G N 2000 J. Vac. Sci. Technol. B 18 1764
[17]	Robertson J 2000 J. Appl. Phys. 87 2608
[18]	Kessels W M M, Smets A H, Marra D C, Aydil E S, Schram D C, Sanden M C M 2001 Thin Solid Films 383 154
[19]	Doren D J 1996 Advances in Chemical Physics (New York: John Wiley & Sons Inc) p124
[20]	Ramalingam S, Maroudas D, Aydil E S 1999 J. Appl. Phys. 86 2872
[21]	Dewarrat R, Robertson J 2002 J. Non-Cryst. Solids 299 48
[22]	Keudell A, AbeIson J R 1999 Phys. Rev. B 59 5791
[23]	Dinger A, Lutterloh C, Kuppers J 1999 Chem. Phys. Lett. 311 202
[24]	Buntin S A 1996 J. Chem. Phys. 105 2066
[25]	Widdra W, Yi S I, Maboudian R, Briggs G A D, Weinberg W H 1995 Phys. Rev. Lett. 74 2074
[26]	Koleske D D, Gates S M, Jackson B 1994 J. Chem. Phys. 101 3301
[27]	Koleske D D, Gates S M, Schultz J A 1993 J. Chem. Phys. 99 5619
[28]	Sinniah K, Sherman M G, Lewis L B, Weinberg W H, Yates J T, Janda K C 1990 J. Chem. Phys. 92 5700
[29]	Ramalingarn S, Maroudas D, Aydil E S, Walch S P 1998 Surf. Sci. 418 L8
[30]	Perrin I, Shiratani M, Kae-Nune P, Videlot H, Jolly J, Guillon J 1998 J. Vac. Sci. Tech. A 16 278
[31]	Keudell A, Abelson J R 1999 Phys. Rev. B 59 5791
[32]	Kitahar K, Murakami S, Hara A, Joshi C 1998 Appl. Phys. Lett. 72 19
[33]	Itabashi N, Nishiwaki N, Magane M, Goto T, Matsuda A, Yamada C, Hirota E 1990 Jpn. J.Appl. Phys. 29 585
[34]	Tachibana K, Mukai T, Harima H 1991 Jpn. J. Appl. Phys. 30 L1208
[35]	Wen S T, Zhang L W, Lu J X, Feng X L, Guo X J, Shen C H, Xu Y H, Li B S 2008 Int. J. Mod. Phys. B 23 1147
[36]	Gao X Y, Li R, Chen Y S, Lu J X, Liu P, Feng T H, Wang H J, Yang S E 2006 Acta Phys. Sin. 55 98 (in Chinese) [郜小勇、李瑞、陈永生、卢景霄、刘萍、冯团辉、王红娟、杨仕娥 2006 55 98]
[37]	Zhang X D, Zhao Y, Gao Y T, Chen F, Zhu F, Wei C C, Sun J, Geng X H, Xiong S Z 2006 Acta Phys. Sin. 55 6698 (in Chinese) [张晓丹、赵颖、高艳涛、陈飞、朱锋、魏长春、孙建、耿新华、熊绍珍 2006 55 6698]

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