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Thermodynamic Simulation of Polysilicon Production in Si-H-Cl System by Modified Siemens Process

DOI:10.1252/jcej.16we180 出版年份:2017 更新时间:2025-09-23 15:22:29
摘要: A study on thermodynamics of the various steps involved in the polysilicon manufacture in the Siemens process is presented in this paper. The synthesis of SiHCl3 (TCS), silicon deposition from SiHCl3 and hydrogenation of by-production SiCl4 (STC) for recycle are the main processes studied in this paper. Based on the thermodynamic data for related pure substances, the relation of (nCl/nH)Eq (i.e. the mole ratio of Si to Cl at equilibrium) and the feeding mole ratio of Cl to H (nCl/nH) was plotted in the Si-Cl-H system. Then, the effects of temperature, pressure and feed fraction on TCS selectivity in the synthesis of SiHCl3 process, polysilicon yield in the silicon deposition process and SiCl4 conversion ratio in the SiCl4 hydrogenation process have been studied. Useful conclusions for improving these processes have been drawn. Finally, the optimum conditions have been obtained and compared with limited published data in the literature. The results show that comparison with the limited reported values in the literature indicates that the operating conditions are close to those predicted by the thermodynamics for all three reactions. However, the reported conversion or yield is lower. It is hoped that this paper makes a contribution as future polysilicon plants move to higher capacity and seek a reduction in the cost of production.
作者: Yang-min Zhou,Yan-qing Hou,Zhi-feng Nie,Gang Xie,Wen-hui Ma,Yong-nian Dai,Palghat A. Ramachandran
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To study the thermodynamics of the various steps involved in polysilicon manufacture in the Siemens process, including the synthesis of SiHCl3, silicon deposition from SiHCl3, and hydrogenation of by-product SiCl4 for recycle, to provide insights for improving these processes and reducing production costs.

Optimum conditions for TCS synthesis (550-600 K, 2-3 MPa, H/Cl ratio ~100), silicon deposition (1400 K, 0.1 MPa, H2/SiHCl3 ratio 15), and STC hydrogenation (high temp: 1323 K, 0.3 MPa, H2/SiCl4 ratio 4; low temp: 850 K, 1.5 MPa, H/Cl ratio 10) are identified. Theoretical yields are higher than actual, suggesting kinetic and reactor design improvements are needed. Future work should focus on reactor modeling, process synthesis, and heat integration.

The study is based on thermodynamic equilibrium, which may not account for kinetic limitations, non-steady conditions, homogeneous reactions, silicon deposition on walls, or practical reactor design challenges. Actual conversion yields are lower than theoretical predictions, indicating areas for optimization in kinetics and reactor models.

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