冶金法制备太阳能级多晶硅的耦合除杂研究

doi:10.15541/jim20160324

无机材料学报 ›› 2017, Vol. 32 ›› Issue (3): 281-286.DOI: 10.15541/jim20160324

冶金法制备太阳能级多晶硅的耦合除杂研究

李鹏廷^1,2, 王凯^1,2, 姜大川^1,2, 任世强^1,2, 谭毅^1,2, 安广野³, 张磊³, 郭校亮³, 王峰³

(1. 大连理工大学材料科学与工程学院, 大连116024; 2. 大连理工大学辽宁省太阳能光伏系统重点实验室, 大连116024; 3. 大工(青岛)新能源材料技术研究院有限公司, 青岛266200)

收稿日期:2016-05-17 修回日期:2016-07-05 出版日期:2017-03-20 网络出版日期:2017-02-24
作者简介:李鹏廷(1986–)，男，博士. E-mail:ptli@dlut.edu.cn
基金资助:
国家自然科学基金(51404053);中国博士后科学基金(2014M551076)

Coupling of Metallurgical Method to Remove Impurities in Solar Grade Polycrystalline Silicon

LI Peng-Ting^1,2, WANG Kai^1,2, JIANG Da-Chuan^1,2, REN Shi-Qiang^1,2, TAN-Yi^1,2, AN Guang-Ye³, ZHANG Lei³, GUO Xiao-Liang³, WANG Feng³

(1. School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China; 2. Key Laboratory for Solar Energy Photovoltaic System of Liaoning Province, Dalian 116024, China; 3. New Energy Materials and Technology Institute Co. Ltd. of Dalian University of Technology (Qingdao), Qingdao 266200, China)

Received:2016-05-17 Revised:2016-07-05 Published:2017-03-20 Online:2017-02-24
About author:LI Peng-Ting. E-mail:ptli@dlut.edu.cn
Supported by:
National Natural Science Foundation of China (51404053);China Postdoctoral Science Foundation (2014M551076)

摘要/Abstract

摘要：

以工业硅为原料,利用介质熔炼、定向凝固和电子束熔炼三种熔体处理技术对工业硅中的B、P和金属杂质进行了去除,制备出了99.9999%级多晶硅材料,其中,杂质B和P的含量分别低于0.20 ppmw（parts per million (weight),百万分之一质量）,金属杂质总含量（TM）低于0.23 ppmw。研究发现,介质熔炼去除杂质B的过程中,熔体中发生氧化还原反应可以有效去除大部分的杂质Al和Ca;电子束熔炼过程中,利用饱和蒸气压原理可以有效去除挥发性杂质P、Al、Ca,同时降束诱导多晶硅定向凝固,可将其他金属杂质进一步去除。本研究通过各技术间的耦合除杂,减少了冶金法提纯多晶硅的工序,为连续化、规模化生产提供了技术支撑。

关键词: 工业硅, 介质熔炼, 定向凝固, 电子束熔炼

Abstract:

Preparation of 6N grade polycrystalline silicon materials using raw materials of industrial silicon was explored by medium melting, directional solidification and electron beam melting. The contents of impurities B and P in the samples are both lower than 0.20 ppmw, while the total content of metal impurity (TM) is less than 0.23 ppmw. During the process of removing B by medium melting, a large proportion of Al and Ca is simultaneously removed through the redox reaction. During the process of electron beam melting, volatile impurities including P, Al and Ca are further effectively removed by using saturated vapor pressure. Meanwhile, other metal impurities are removed by decreasing beam power, which induces the occurrence of directional solidification. Coupling of metallurgical methods reduces the purification process of polycrystalline silicon, and provides the technical support for continuous and large-scale production.

Key words: industrial silicon, medium melting, directional solidification, electron beam melting

中图分类号:

TF89

李鹏廷, 王凯, 姜大川, 任世强, 谭毅, 安广野, 张磊, 郭校亮, 王峰. 冶金法制备太阳能级多晶硅的耦合除杂研究[J]. 无机材料学报, 2017, 32(3): 281-286.

LI Peng-Ting, WANG Kai, JIANG Da-Chuan, REN Shi-Qiang, TAN-Yi, AN Guang-Ye, ZHANG Lei, GUO Xiao-Liang, WANG Feng. Coupling of Metallurgical Method to Remove Impurities in Solar Grade Polycrystalline Silicon[J]. Journal of Inorganic Materials, 2017, 32(3): 281-286.

图/表 13

图1 两种熔炼设备的示意图

Fig. 1 Schematic diagram of two melting equipments(a) Directional solidification melting equipment; (b) Electron beam melting equipment

表1 工业硅成分检测结果（ppmw）

Table1 Component test results of industrial silicon (ppmw)

Element	B	P	Al	Ca	Fe	Mg	Na	TM
Concentration	1.55	6.67	149.15	154.00	300.73	0.60	0.84	1059.06

图2 冶金法制备6N级多晶硅工艺流程图

Fig. 2 Flowchart of 6N grade polycrystalline silicon prepared by metallurgical method

表2 介质熔炼后成分检测结果（ppmw）

Table 2 Component test results of silicon after medium melting (ppmw)

Element	B	P	Al	Ca	Fe	Mg	Na	TM
First	0.60	6.84	0.67	15.96	461.00	1.21	563.36	1154.92
Second	0.26	7.61	0.36	2.38	525.00	4.68	468.16	967.46
Third	0.21	8.13	0.46	0.56	918.00	8.18	352.36	811.32

表3 定向凝固后铸锭成分检测结果（ppmw）

Table3 Component test results of silicon ingot after directional solidification (ppmw)

Solidification ratio	B	P	Al	Ca	Fe	Mg	Na	TM
0.98	0.22	7.84	9.00	29.16	3986.00	29.69	5.76	8131.96
0.90	0.18	6.33	2.61	13.64	393.68	8,17	2.06	746.46
0.86	0.16	5.96	0.13	0.18	0.36	0.13	0.20	2.29
0.78	0.15	5.16	0.21	0.68	0.31	0.08	0.45	1.09
0.62	0.12	5.19	0.21	0.13	0.42	0.10	0.20	0.97
0.42	0.11	5,87	0.20	0.30	0.27	0.07	0.28	0.67
0.22	0.12	4.96	0.16	0.24	0.21	0.08	0.16	0.56
0.06	0.08	4.13	0.08	0.61	0.26	0.07	0.17	0.53
0.02	0.11	4.46	0.09	0.18	0.21	0.06	0.19	0.47

图3 定向凝固处理后TM含量分布

Fig. 3 Distribution of TM concentration after directional solidification process

图4 硅锭顶部微观组织照片

Fig. 4 Microstructure of the top of silicon ingot

图5 冶金法工艺流程下杂质含量的变化

Fig. 5 Change of impurity content in metallurgical process

表4 电子束熔炼后成分检测结果（ppmw）

Table 4 Component test results of silicon after electron beam melting (ppmw)

Element	B	P	Al	Ca	Fe	Mg	Na	TM
Concentration	0.180	0.190	0.019	0.027	0.026	0.003	0.008	0.228

图6 氧化物的自由能图

Fig. 6 Ellingham diagram of oxide

图7 固液界面浓度分布原理图

Fig. 7 Schematic diagram of the concentration distribution of the solid-liquid interface

图8 硅及其杂质元素的蒸汽压曲线

Fig. 8 Vapor pressure curves of silicon and impurities

图9 电子束熔炼耦合定向凝固除杂原理图

Fig. 9 Schematic diagram of electron beam melting coupling directional solidification of removing impurities

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冶金法制备太阳能级多晶硅的耦合除杂研究

Coupling of Metallurgical Method to Remove Impurities in Solar Grade Polycrystalline Silicon

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