Numerical simulation of chemical vapor deposition in polycrystalline silicon reduction furnace

doi:10.16085/j.issn.1000-6613.2024-0296

Abstract

Abstract:

Polysilicon is a key material for solar panels in the field of photovoltaics, and the modified Siemens method is a common method for preparing polysilicon, with the core equipment being a reduction furnace. The structure of the reduction furnace is complex, and the furnace contains complex physicochemical phenomena. In order to study the polycrystalline silicon vapor deposition characteristics, a reactor model with 12 pairs of rods was established, coupling the vapor phase reaction and surface reaction mechanisms, and the velocity, temperature, and silicon deposition rate distributions under different conditions were discussed in detail. Response surface methodology coupled with two variables, inlet velocity and temperature, was used to explore the combined effects on the average silicon deposition rate and the feedstock conversion rate. The results showed that higher inlet velocity and temperature were favorable to increase the heat and mass transfer rate and the average silicon deposition rate. Temperature was the main factor influencing the process and the effect was significant in the low temperature region. Due to the increase of inlet velocity and the decrease of feedstock conversion, the optimal process conditions were predicted to be 1460—1500K and 25—36m/s, taking into account the effects of average deposition rate (≥10μm/min) and feedstock conversion (≥10%).

Key words: polysilicon, chemical vapor deposition, heat transfer, computational fluid dynamics, optimization

摘要：

多晶硅是光伏领域太阳能电池板的关键材料，改良西门子法是制备多晶硅的常用方法，其核心设备为还原炉。还原炉结构复杂，炉内包含复杂的物理化学现象。为了研究多晶硅气相沉积特性，本文建立了一个12对棒的反应器模型，耦合气相反应及表面反应机理，详细讨论了不同条件下的速度、温度、硅沉积速率分布。采用响应面法耦合入口速度和温度两个变量探究其对硅平均沉积速率以及原料转化率的综合影响。结果表明，较高的入口速度和温度有利于提高传热传质速率，提高硅平均沉积速率。温度为该过程的主要影响因素且在低温区域影响显著。由于入口速度提高，原料转化率降低，兼顾平均沉积速率（≥10μm/min）和原料转化率（≥10%）的影响，预测最佳工艺条件温度为1460~1500K、入口速度为25~36m/s。

关键词: 多晶硅, 化学气相沉积, 传热, 计算流体力学, 优化

CLC Number:

TQ03

WANG Siyi, XU Jianliang, DAI Zhenghua, WU Guoyi, WANG Fuchen. Numerical simulation of chemical vapor deposition in polycrystalline silicon reduction furnace[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 706-716.

王思懿, 许建良, 代正华, 武国义, 王辅臣. 多晶硅还原炉气相沉积反应数值模拟[J]. 化工进展, 2025, 44(2): 706-716.

Figures/Tables 23

序号	反应	A/s^-1	E/cal·mol^-1
G1	SiHCl₃ $\overset{}{̿}$ HCl+SiCl₂	3.162×10¹⁴	72900
G2	SiH₂Cl₂ $\overset{}{̿}$ SiCl₂+H₂	3.162×10¹³	69300
G3	SiH₂Cl₂ $\overset{}{̿}$ SiHCl+HCl	6.918×10¹⁴	75800
G4	H₂ClSiSiCl₃ $\overset{}{̿}$ SiCl₄+SiH₂	1.585×10¹³	55500
G5	H₂ClSiSiCl₃ $\overset{}{̿}$ SiHCl₃+SiHCl	3.162×10¹³	49800
G6	H₂ClSiSiCl₃ $\overset{}{̿}$ SiH₂Cl₂+SiCl₂	6.310×10¹³	44300
G7	Si₂HCl₅ $\overset{}{̿}$ SiCl₄+SiHCl	5.012×10¹³	52300
G8	Si₂HCl₅ $\overset{}{̿}$ SiHCl₃+SiCl₂	7.943×10¹³	45900
G9	Si₂Cl₆ $\overset{}{̿}$ SiCl₄+SiCl₂	1.585×10¹⁴	48800

序号	反应	A/s^-1	E/cal·mol^-1
G1	SiHCl₃ $\overset{}{̿}$ HCl+SiCl₂	3.162×10¹⁴	72900
G2	SiH₂Cl₂ $\overset{}{̿}$ SiCl₂+H₂	3.162×10¹³	69300
G3	SiH₂Cl₂ $\overset{}{̿}$ SiHCl+HCl	6.918×10¹⁴	75800
G4	H₂ClSiSiCl₃ $\overset{}{̿}$ SiCl₄+SiH₂	1.585×10¹³	55500
G5	H₂ClSiSiCl₃ $\overset{}{̿}$ SiHCl₃+SiHCl	3.162×10¹³	49800
G6	H₂ClSiSiCl₃ $\overset{}{̿}$ SiH₂Cl₂+SiCl₂	6.310×10¹³	44300
G7	Si₂HCl₅ $\overset{}{̿}$ SiCl₄+SiHCl	5.012×10¹³	52300
G8	Si₂HCl₅ $\overset{}{̿}$ SiHCl₃+SiCl₂	7.943×10¹³	45900
G9	Si₂Cl₆ $\overset{}{̿}$ SiCl₄+SiCl₂	1.585×10¹⁴	48800

序号	反应	A/s^-1	E/cal·mol^-1
S1	SiHCl₃+4Si(s) $\overset{}{\to}$ Si(b)+SiH(s)+3SiCl(s)	4.1×10^-4	-3800
S2	SiH₂Cl₂+4Si(s) $\overset{}{\to}$ Si(b)+2SiH(s)+2SiCl(s)	1.2×10^-3	-3800
S3	SiCl₄+4Si(s) $\overset{}{\to}$ Si(b)+4SiCl(s)	3.0×10^-5	-3800
S4	SiCl₂+2Si(s) $\overset{}{\to}$ Si(b)+2SiCl(s)	2.2	15000
S5	2SiCl(s)+Si(b) $\overset{}{\to}$ SiCl₂+2Si(s)	4.758×10²²	67000
S6	H₂+2Si(s) $\overset{}{\to}$ 2SiH(s)	0.1	17300
S7	2SiH(s) $\overset{}{\to}$ H₂+2Si(s)	8.606×10²²	57100
S8	HCl+2Si(s) $\overset{}{\to}$ SiH(s)+SiCl(s)	0.07	5000
S9	SiH(s)+SiCl(s) $\overset{}{\to}$ 2Si(s)+HCl	4.0×10²⁵	71500
S10	SiHCl+2Si(s) $\overset{}{\to}$ Si(b)+SiH(s)+SiCl(s)	0.06	5000

序号	反应	A/s^-1	E/cal·mol^-1
S1	SiHCl₃+4Si(s) $\overset{}{\to}$ Si(b)+SiH(s)+3SiCl(s)	4.1×10^-4	-3800
S2	SiH₂Cl₂+4Si(s) $\overset{}{\to}$ Si(b)+2SiH(s)+2SiCl(s)	1.2×10^-3	-3800
S3	SiCl₄+4Si(s) $\overset{}{\to}$ Si(b)+4SiCl(s)	3.0×10^-5	-3800
S4	SiCl₂+2Si(s) $\overset{}{\to}$ Si(b)+2SiCl(s)	2.2	15000
S5	2SiCl(s)+Si(b) $\overset{}{\to}$ SiCl₂+2Si(s)	4.758×10²²	67000
S6	H₂+2Si(s) $\overset{}{\to}$ 2SiH(s)	0.1	17300
S7	2SiH(s) $\overset{}{\to}$ H₂+2Si(s)	8.606×10²²	57100
S8	HCl+2Si(s) $\overset{}{\to}$ SiH(s)+SiCl(s)	0.07	5000
S9	SiH(s)+SiCl(s) $\overset{}{\to}$ 2Si(s)+HCl	4.0×10²⁵	71500
S10	SiHCl+2Si(s) $\overset{}{\to}$ Si(b)+SiH(s)+SiCl(s)	0.06	5000

参数	数值
反应器高度/mm	3500
反应器直径/mm	1600
入口直径/mm	20
出口直径/mm	200
硅棒高度/mm	2300
硅棒直径/mm	110
硅棒间距/mm	235

参数	数值
入口	入口速度(18m/s、36m/s)
出口	出口压力
原料摩尔比	H₂∶TCS=4∶1 (413K)
硅棒表面温度	1423K，1523K
炉壁温度	500K
操作压力	6atm
表面反射率	硅棒0.7，其他0.5

来源	反应器规模	沉积表面温度/K	操作压力/atm	H₂∶TCS原料摩尔比	单根硅棒产量/kg
夏小霞等^[18]	单根棒	1373	6	4∶1	122
张胜涛^[19]	9对棒	1323	6	2.5∶1	260
Li等^[20]	12对棒	1148	3	2.8∶1	135
倪昊尹等^[21]	12对棒	1473	3	3.1∶1	340
张弘^[22]	24对棒	1353	5	3.5∶1	93
王体虎等^[23]	48对棒	1223	4	4∶1	125
本文	12对棒	1423	6	4∶1	148

变量	水平
变量	-1	0	1
A-温度T/K	1150	1350	1550
B-入口速度v/m·s^-1	10	30	50

运行次数	温度T/K	入口速度v/m·s^-1	沉积速率 /μm·min^-1	原料转化率
1	1350	50	8.180	0.053
2	1550	30	11.204	0.121
3	1350	30	7.462	0.081
4	1550	50	11.919	0.077
5	1150	30	0.352	0.004
6	1350	10	5.648	0.183
7	1350	30	7.462	0.081
8	1150	50	0.318	0.002
9	1350	30	7.462	0.081
10	1350	30	7.462	0.081
11	1550	10	9.142	0.297
12	1350	30	7.462	0.081
13	1150	10	0.309	0.010

方差来源	平方和	自由度	均方差	F	P	显著性
总模型	180.39	5	36.08	426.41	<0.0001	显著
A	163.13	1	163.13	1927.97	<0.0001	显著
B	4.72	1	4.72	55.73	0.0001	显著
AB	1.92	1	1.92	22.64	0.0021	显著
A²	6.99	1	6.99	82.67	<0.0001	显著
B²	0.5720	1	0.5720	6.76	0.0354	显著
残差	0.5923	7	0.0846
失拟项	0.5923	3	0.1974
纯误差	0.0000	4	0.0000
总和	180.99	12
R²=0.9967，R²(校正)=0.9944

方差来源	平方和	自由度	均方差	F	P	显著性
总模型	0.0745	5	0.0149	71.60	<0.0001	显著
A	0.0382	1	0.0382	183.88	<0.0001	显著
B	0.0213	1	0.0213	102.58	<0.0001	显著
AB	0.0112	1	0.0112	53.79	0.0002	显著
A²	0.0011	1	0.0011	5.24	0.0559	不显著
B²	0.0036	1	0.0036	17.14	0.0043	显著
残差	0.0015	7	0.0002
失拟项	0.0.0015	3	0.0005
纯误差	0.0759	4	0.0000
总和	180.99	12
R²=0.9808，R²(校正)=0.9671

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