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Thermodynamic Simulation of Polycrystalline Silicon Chemical Vapor Deposition in Si–Cl–H System

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Abstract—

Based on thermodynamic data for related pure substances, the relations of (nCl/nH)Eq and (nCl/nH)o have been plotted in the Si–Cl–H system. The results show that the difference of (nSi/nCl)o and (nSi/nCl)Eq is the driving force for polycrystalline silicon chemical vapor deposition (CVD). SiHCl3 is preferred for polycrystalline silicon deposition to SiCl4. SiH2Cl2 would be even better, but it is not stable as a gas and hence it is less frequently used. Then, thermodynamic simulation of polycrystalline silicon CVD in the Si–H–Cl system has been investigated. The pressure has a negative effect on polycrystalline silicon yield. The optimum temperature is 1400 K, at which the kinetic rate of rate-determining step for the main reaction is large enough. The excess hydrogen is necessary for polycrystalline silicon CVD in the Si–Cl–H system. However, the silicon deposition rate increases then decreases with increasing H2 molar fraction. The optimum H2 molar fraction should be determined by considering thermodynamics and transport phenomena simultaneously. Finally, the optimum conditions have been obtained as 1400 K, about 0.1 MPa, and H2 to SiHCl3 ratio of 15, which are close to the limited reported values in the open literature. Under the optimum conditions, the silicon yield ratio is 34.82% against 20% reported in the open literature.

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Funding

This research is supported by the National Natural Science Foundation of China (21566015) and Applied Basic Research Projects of Yunnan (2015FB126).

NOTATION

K

equilibrium constant

K

kinetic constant, S–1

N

molar quantity, mol

P

pressure, Pa

R

gas constant, J mol–1 K–1

T

temperature, K

v

stoichiometric coefficient

x

polycrystalline silicon yield, %

y

molar fraction, mol %

SUBSCRIPTS AND SUPERSCRIPTS

0

initial value

1

SiHCl3

2

H2

3

HCl

4

Si

5

SiCl4

6

SiCl3

7

SiCl2

8

SiCl

9

SiH2Cl2

10

SiH3

11

SiH4

Cl

chlorine

eq, Eq

equilibrium value

H

hydrogen

i

numbers of components

j

numbers of reactions

Si

silicon

t

total value

Author information

Authors and Affiliations

  1. State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming, China

    Yangmin Zhou, Yanqing Hou, Zhifeng Nie, Gang Xie, Wenhui Ma & Yongnian Dai

  2. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, China

    Yangmin Zhou, Zhifeng Nie, Wenhui Ma & Yongnian Dai

  3. Kunming Metallurgical Research Institute, Kunming, China

    Yangmin Zhou & Gang Xie

  4. Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, MO, USA

    Palghat A. Ramachandran

Authors
  1. Yangmin Zhou
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  2. Yanqing Hou
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  3. Zhifeng Nie
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  4. Gang Xie
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  7. Palghat A. Ramachandran
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Correspondence to Yanqing Hou.

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Yangmin Zhou, Hou, Y., Nie, Z. et al. Thermodynamic Simulation of Polycrystalline Silicon Chemical Vapor Deposition in Si–Cl–H System. Theor Found Chem Eng 53, 1048–1056 (2019). https://doi.org/10.1134/S0040579519060162

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  • DOI: https://doi.org/10.1134/S0040579519060162

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