Thermodynamic analysis of manufacturing polysilicon from SiHCl3, SiCl4 and H2

doi:10.1016/j.cjche.2014.03.005

Chinese Journal of Chemical Engineering ›› 2015, Vol. 23 ›› Issue (4): 681-688.DOI: 10.1016/j.cjche.2014.03.005

Thermodynamic analysis of manufacturing polysilicon from SiHCl₃, SiCl₄ and H₂

Peilong Li, Tiefeng Wang

Beijing Key Laboratory of Green Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

收稿日期:2013-12-03 修回日期:2014-03-13 出版日期:2015-04-28 发布日期:2015-05-13
通讯作者: Tiefeng Wang
基金资助:
Supported by the Beijing New Star Project on Science & Technology of China (2009B35) and the Program for New Century Excellent Talents in University (NCET-12-0297).

Thermodynamic analysis of manufacturing polysilicon from SiHCl₃, SiCl₄ and H₂

Peilong Li, Tiefeng Wang

Beijing Key Laboratory of Green Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Received:2013-12-03 Revised:2014-03-13 Online:2015-04-28 Published:2015-05-13
Contact: Tiefeng Wang
Supported by:
Supported by the Beijing New Star Project on Science & Technology of China (2009B35) and the Program for New Century Excellent Talents in University (NCET-12-0297).

摘要/Abstract

摘要： Production of polysilicon by chemical vapor deposition of SiHCl₃ with a fluidized bed reactor is a competitive technology. As equilibrium conversion can be approached in a fluidized bed reactor, a reliable thermodynamic analysis is very important. However, inconsistent thermodynamic analysis results have been reported in the literature. The present work studied the effects of thermodynamic data and species selection, and recommended that JANAF was the best Cp data source and the minimum set of species included the following eight species: H₂, HCl, SiCl₄, SiCl₂, SiHCl₃, SiH₂Cl₂, SiH₃Cl and Si. Then, the influence of operating conditions on the equilibrium was studied. For the SiHCl₃-H₂ system, both the yield of silicon and selectivity to silicon reached their maximum at (up to 1100 ℃), and low pressure and high H₂ feed ratiowere of benefit for silicon production. For the SiHCl₃- SiCl₄-H₂ system, silicon could be produced only at 900-1400 ℃, and reducing pressure and increasing H₂ feed ratio enhanced the yield of silicon.Meanwhile, the operation map for zero net by-production of SiCl₄ by directly recycling the produced SiCl₄ was determined.

关键词: Thermodynamics, Polysilicon, Fluidized bed, Trichlorosilane, Silicon tetrachloride

Abstract: Production of polysilicon by chemical vapor deposition of SiHCl₃ with a fluidized bed reactor is a competitive technology. As equilibrium conversion can be approached in a fluidized bed reactor, a reliable thermodynamic analysis is very important. However, inconsistent thermodynamic analysis results have been reported in the literature. The present work studied the effects of thermodynamic data and species selection, and recommended that JANAF was the best Cp data source and the minimum set of species included the following eight species: H₂, HCl, SiCl₄, SiCl₂, SiHCl₃, SiH₂Cl₂, SiH₃Cl and Si. Then, the influence of operating conditions on the equilibrium was studied. For the SiHCl₃-H₂ system, both the yield of silicon and selectivity to silicon reached their maximum at (up to 1100 ℃), and low pressure and high H₂ feed ratiowere of benefit for silicon production. For the SiHCl₃- SiCl₄-H₂ system, silicon could be produced only at 900-1400 ℃, and reducing pressure and increasing H₂ feed ratio enhanced the yield of silicon.Meanwhile, the operation map for zero net by-production of SiCl₄ by directly recycling the produced SiCl₄ was determined.

Key words: Thermodynamics, Polysilicon, Fluidized bed, Trichlorosilane, Silicon tetrachloride

Peilong Li, Tiefeng Wang. Thermodynamic analysis of manufacturing polysilicon from SiHCl₃, SiCl₄ and H₂[J]. Chinese Journal of Chemical Engineering, 2015, 23(4): 681-688.

Peilong Li, Tiefeng Wang. Thermodynamic analysis of manufacturing polysilicon from SiHCl₃, SiCl₄ and H₂[J]. Chin.J.Chem.Eng., 2015, 23(4): 681-688.

参考文献

[1] J.O. Odden, G. Halvorsen, H.M. Rong, R. Gløckner, Comparison of the energy consumption in different production processes for solar grade silicon, Silicon for the Chemical and Solar Industry IX, Oslo, 2008, pp. 75-90.

[2] J.L. Li, G.H. Chen, P. Zhang,W.W.Wang, J.H. Duan, Technical challenges and progress in fluidized bed chemical vapor deposition of polysilicon, Chin. J. Chem. Eng. 19 (5) (2011) 747-753.

[3] D.Weidhaus, E. Schindlbeck, K. Hesse, Trichlorosilane based silicon feedstock for the photovoltaic industry, Silicon for the Chemical and Solar Industry VII, Norway, 2004, pp. 189-200.

[4] C.J. Wang, T.F. Wang, Z.W. Wang, Manufacture of granular polysilicon from trichlorosilane in a fluidized-bed reactor, Chem. Eng. Technol. 35 (5) (2012) 893-898.

[5] E. Sirtl, L.P. Hunt, D.H. Sawyer, High-temperature reactions in silicon-hydrogen-chlorine system, J. Electrochem. Soc. 121 (7) (1974) 919-925.

[6] I. Niederkorn, A.Wohl, Thermodynamic study on advanced purification of silicon. I, Rev. Roum. Chim. 11 (1) (1966) 85-101.

[7] L.I. Chernyavsky, V.A. Titov, S.V. Sysoev, S.V. Ryzhenkov, Thermodynamic simulation of silicon deposition from the gas phase of Si-Cl-H system, Inorg. Mater. 45 (5) (2009) 463-467.

[8] M. Diana, L. Demarino, L. Mastrantuono, R. Rossi, Thermodynamic analysis of the reduction of silicon chlorides with hydrogen in the 300-4500-K temperature-range, Rev. Int. Hautes Temp. Refract. 18 (3) (1981) 203-213.

[9] K.D. Allen, H.H. Sawin, Thermodynamics of the silicon-chlorine-hydrogen system: chemical potential for homogeneous nucleation, J. Electrochem. Soc. 133 (2) (1986) 421-425.

[10] W. Malcolm, NIST-JANAF Thermochemical Tables, Fourth edition ACS & AIP & NIST, U.S.A., 1998

[11] C.L. Yaws,Matheson Gas Data Book, Seventh edition McGraw-Hill, Parsippany, 2001.

[12] M. Binneries, E. Milke, Thermochemical Data of Elements and Compounds, Second, Revised and Extended Edition Wiley-VCH, 2002.

[13] T.E. Daubert, R.P. Danner, Data Compilation Tables of Properties of Pure Compounds, Design Institute for Physical Property Data & American Institute of Chemical Engineers, New York, 1985.

[14] L. Gmelin, Gmelin Handbook of Inorganic and Organometallic Chemistry, Verlag Chemie, Weinheim, 1973.

[15] D.L. Ye, J.H. Hu, Practical Handbook of Thermodynamic Data for Inorganic Compounds, 2th edition Metallurgical Insustry Press, Beijing, 2002.

[16] K.K. Kelley, Critical Evaluation of High-temperature Heat Capacities of Inorganic Compound, Bureau of Mines Publications, U.S.A., 1949

[17] C.B. Alcock, O. Kubaschewski, Metallurgical Thermochemistry, 5th edition Pergamon Press, 1979.

[18] G.D. Li, X.L. Zhang, Y.D. Hu, Thermodynamic analysis of production technology of electronic grade polycrys talline silicon, Chin. J. Process. Eng. 7 (3) (2007) 520-525 (in Chinese).

[19] Q.Y. Kang, W.J. Ding, W.D. Xiao, J.M. Yan, M. Luo, Thermodynamic analysis of cohydrogenation of silicon tetrachloride and silicon, Inorg. Chem. Ind. 44 (11) (2012) 26-29 (in Chinese).

[20] R.Z. Peng, X.H. Yu, G. Xie, Y. Yao, Thermodynamic study on trichlorosilane synthesis, Nonferrous Met. (Extr. Metall.) (9) (2012) 55-59 (in Chinese).

[21] E. He, G. Xie, Y.Q. Hou, Y. Lin, X.H. Xu, Thermodynamic analysis of SiHCl₃ hydrogen reduction process, Chem. Eng. 39 (11) (2011) 39-43 (in Chinese).

[22] B.K. Xu, M.Y. Zhao, A thermodynamical analysis of carbon contamination in silicon epitaxial growth from SiCl₄, Chin. J. Semicond. 3 (5) (1982) 343-350 (in Chinese).

[23] J.J. Miao, S.C. Chen, K.Q. Qiu, Thermodynamic study on production of multicrystalline silicon by Siemens process, Chin. J. Inorg. Chem. 23 (5) (2007) 795-801 (in Chinese).

[24] C.J. Wang, Study of Preparing Solar Grade Polysilicon Granules in a Fluidized Bed Reactor(Ph. D. Thesis) Tsinghua University, Beijing, 2012. (in Chinese).

[25] C.J.Wang, T.F. Wang, P.L. Li, Z.W. Wang, Recycling of SiCl₄ in the manufacture of granular polysilicon in a fluidized bed reactor, Chem. Eng. J. 220 (2013) 81-88.

[26] D.W. Woodruff, R.A. Sanchez-martinez, Experimental-study of equilibrium conditions in the Si-H-Cl system, J. Electrochem. Soc. 132 (3) (1985) 706-708.

[27] P. Guo, Analysis on comprehensive utilization and recycle economy of polysilicon by-product, Nonferrous Met. Process. 38 (4) (2009) 49-52 (in Chinese).

[28] G.J. Ding, Effects of the mixing of SiHCl₃ and SiCl₄ on the silicon process production, Sichuan Nonferrous Met. 3 (1998) 14-19 (in Chinese).

[29] H. Walter, G. Roewer, K. Bohmhammel, Mechanism of the silicide-catalysed hydrodehalogenation of silicon tetrachloride to trichlorosilane, J. Chem. Soc. Faraday Trans. 92 (22) (1996) 4605-4608.

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