Si-Al-Sn合金熔体中块体硅定向生长行为研究

doi:10.15541/jim20150649

无机材料学报 ›› 2016, Vol. 31 ›› Issue (8): 791-796.DOI: 10.15541/jim20150649

Si-Al-Sn合金熔体中块体硅定向生长行为研究

李亚琼¹, 李佳艳², 谭毅², 张立峰¹, 森田一樹³

(1. 北京科技大学冶金与生态工程学院, 北京100083; 2. 大连理工大学材料科学与工程学院, 大连116024; 3. 东京大学工学院, 材料工程学院, 日本东京1538505)

收稿日期:2015-12-25 修回日期:2016-02-04 出版日期:2016-08-20 网络出版日期:2016-07-20
作者简介:李亚琼(1983–), 女, 博士. E-mail: liyq_ustb@163.com
基金资助:
国家自然科学基金(51334002, 51274034, 51404019);中国博士后科学基金(2015M580985)

Directional Growth of Bulk Silicon from Si-Al-Sn Melts

Li Ya-Qiong¹, Li Jia-Yan², Tan Yi², Zhang Li-Feng¹, Morita Kazuki³

(1. School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China; 2. School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China; 3. Department of Materials Engineering, Graduate School of Engineering, The University of Tokyo, Tokyo 1538505, Japan)

Received:2015-12-25 Revised:2016-02-04 Published:2016-08-20 Online:2016-07-20
About author:Li Ya-Qiong. E-mail: liyq_ustb@163.com
Supported by:
National Natural Science Foundation of China (51334002, 51274034, 51404019);China Postdoctoral Science Foundation (2015M580985)

摘要/Abstract

摘要：

为从Si-Al-Sn合金中有效分离初晶硅, 本研究提出并实现了三元合金定向生长块体硅的技术。通过考察冷却速度、合金成分、温度梯度与晶体生长速度比值(G/R)等参数及其影响机制, 确定促进块体硅稳定生长的有利条件; 对比Si-Al、Si-Sn二元合金体系, 采用成分过冷理论分析金属Sn对三元合金中块体硅生长行为的影响; 采用电子探针显微分析仪考察块体硅微观组织形貌与杂质分布。研究结果表明: 定向凝固方法能有效分离块体硅, 同时抑制块体硅内金属夹杂物生成, 并将杂质含量控制在其固溶度范围内, 成为一种有效分离、回收高纯初晶硅的新途径。

关键词: Si-Al-Sn合金, 定向凝固, 块体硅

Abstract:

To separate primary Si from Si-Al-Sn alloy, directional solidification method was applied in this study. The effects and mechanisms of the cooling rate, alloy composition, and G/R ratio on bulk Si growth were investigated for optimizing parameters. By using of the constitutional supercooling criterion for single-phase growth from melts, the effects of Sn addition have been explored as compared with Si-Al and Si-Sn alloys. Finally, with the application of electron probe micro analyzer, the microstructure of Si and the distribution of Al and Sn were analyzed. Based on the obtained results, the directional solidification method is verified to be an effective method to separate Si from Si-Al-Sn alloy without any metal inclusions. The contents of Al and Sn in bulk Si are almost equivalent to the corresponding solid solubility. The obtained results indicate that directional solidification method can be an appropriate and effective technique to separate Si from alloy.

Key words: Si-Al-Sn alloy, directional solidification method, bulk Si

中图分类号:

TF114
TF89

李亚琼, 李佳艳, 谭毅, 张立峰, 森田一樹. Si-Al-Sn合金熔体中块体硅定向生长行为研究[J]. 无机材料学报, 2016, 31(8): 791-796.

Li Ya-Qiong, Li Jia-Yan, Tan Yi, Zhang Li-Feng, Morita Kazuki. Directional Growth of Bulk Silicon from Si-Al-Sn Melts[J]. Journal of Inorganic Materials, 2016, 31(8): 791-796.

图/表 10

表1 实验条件及结果[12]

Table 1 Experimental conditions and results[12]

No.	Composition/mol%			Lowering rate/ (mm•min^-1)	Cooling rate/ (K•min^-1)	G/ (K•mm^-1)	Growth rate ,R/(×10³, mm.min^-1)	(G/R)/ (K∙min•mm^-2)	Bulk Si length/mm	Interface morphology
No.	Si	Al	Sn	Lowering rate/ (mm•min^-1)	Cooling rate/ (K•min^-1)	G/ (K•mm^-1)	Growth rate ,R/(×10³, mm.min^-1)	(G/R)/ (K∙min•mm^-2)	Bulk Si length/mm	Interface morphology
J2-1	30.8	59.2	10	0.02	0.063	3.13	1.05	2980.95	1.81	?
J2-2	28.9	56.1	15	0.02	0.063	3.13	0.67	4671.64	1.16	?
J2-3	26.5	53.5	20	0.02	0.063	3.13	0.63	4968.25	1.09	?
J2-4	22.2	47.8	30	0.02	0.063	3.13	0.88	3556.82	1.52	×
J2-5	26.5	53.5	20	0.02	0.076	3.79	0.92	4119.57	1.21	?
J2-6	24.5	50.5	25	0.02	0.076	3.79	0.95	3989.47	1.24	×
J2-7	22.2	47.8	30	0.02	0.076	3.79	1.01	3752.48	1.33	×
J2-8	30.8	59.2	10	0.02	0.094	4.69	1.15	4078.26	1.28	?
J2-9	26.5	53.5	20	0.02	0.094	4.69	3.87	1211.89	4.33	×
J4-1	28.9	56.1	15	0.04	0.125	3.13	1.76	1778.41	1.52	×
J4-2	26.5	53.5	20	0.04	0.125	3.13	1.71	1830.41	1.47	×
J4-3	33.5	61.5	5	0.04	0.152	3.79	2.13	1779.34	1.4	?
J4-4	26.5	53.5	20	0.04	0.152	3.79	9.51	398.53	6.24	×
J8-1	28.9	56.1	15	0.08	0.250	3.13	1.74	1798.85	0.75	×
J8-2	26.5	53.5	20	0.08	0.250	3.13	13.85	225.99	5.97	×
J8-3	24.5	50.5	25	0.08	0.250	3.13	3.41	917.89	1.47	×
J8-4	22.2	47.8	30	0.08	0.250	3.13	1.55	2019.35	0.67	×

图1 定向凝固设备示意图 (a)石墨坩埚、(b)带有伺服电动机的SiC电阻炉和(c)炉内温度曲线

Fig. 1 Schematic diagram of (a) graphite crucible, (b) SiC electric furnace with stepping motor, and (c) a temperature profile for the center of a hot-zone

图2 (a) J2-3样品横截面照片, (b)界面处样品背散射照片

Fig. 2 Photograph of Sample J2-3 and (b) the backscattered electron image at the interface between Si and Si-Al-Sn alloy

图3 Si-Al-Sn合金熔体中块体硅定向生长示意图

Fig. 3 Schematic of bulk Si growth from Si-Al-Sn alloy by directional solidification process

图4 块体硅生长速度与硅含量关系图

Fig. 4 Relationship between growth rate of bulk Si and Si content of the alloy

图5 Si-Al、Si-Sn和Si-Al-Sn合金中G/R临界值与硅含量关系图

Fig. 5 Bulk Si growth with varying G/R and Si content in Si-Al, Si-Sn and Si-Al-Sn alloys

图6 近快速凝固的研究范畴及其核心问题[7]

Fig. 6 Research category and key problems of near rapid solidification process

图7 1673 K Si-Al 、Si-Sn合金中硅活度计算值

Fig. 7 Activity of Si in Si-Al and Si-Sn alloy at 1673 K

图8 样品J2-8腐蚀后图像

Fig. 8 Image of J2-8 sample after etching

图9 J2-3和J4-2样品块体硅中(a) Al和 (b) Sn含量

Fig. 9 (a) Al and (b) Sn contents in sample J2-3 and J4-2

参考文献 18

[1]	YOSHIKAWA T, MORITA K.Thermodynamics on the Solidification Refining of Silicon with Si-Al Melts. EPD Congress-TMS 2005 Annual Meeting and Exhibition. San Francisco, 2005: 549-558.
[2]	YOSHIKAWA T, MORITA K. Refining of Si by the solidification of Si-Al melt with electromagnetic force. ISIJ International, 2005, 45(7): 967--971.
[3]	MURRAY J, MCALISTER A.The Al-Si (aluminum-silicon) system.Journal of Phase Equilibria, 1984, 5: 74-84.
[4]	LI J Y, LIU Y, TAN Y, et al.Effect of tin addition on primary silicon recovery in Si-Al melt during solidification refining of silicon.Journal of Crystal Growth, 2013, 371: 1-6.
[5]	LI Y Q, TAN Y, LI J Y, et al.Effect of Sn content on microstructure and boron distribution in Si-Al alloy. Journal of Alloy and Compounds, 2014, 583(1): 85-90.
[6]	JACOBS M H G, SPENCER P J. A thermodynamic evaluation of the system Si-Sn.Calphad, 1996, 20: 89-91.
[7]	JIE W Q.Progress of solidification principles and the applications.Materials China, 2014, 6: 321-326.
[8]	KURZ W, FISHER K.Fundamentals of Solidification, Switzerland: Trans Tech Publications, 1986, 91.
[9]	NISHI Y, KANG Y, MORITA K.Control of Si crystal growth during solidification of Si-Al melt.Materials Transactions, 2010, 51(7): 1227-1230.
[10]	MA X D, YOSHIKAWA T, MORITA K.Si growth by directional solidification of Si-Sn alloys to produce solar-grade Si.Journal of Crystal Growth, 2013, 377(0): 192-196.
[11]	OHSHIMA Y, YOSHIKAWA T, MORITA K.Effect of solidification conditions on Si growth from Si-Cu melts.Supplemental Proceedings: Materials Processing and Energy Materials, 2011, 1: 677-684.
[12]	LI Y Q, TAN Y, MORITA K.Directional Growth of Bulk Silicon from Silicon-Aluminum-Tin Melts. EPD Congress 2015-TMS 2015 Annual Meeting and Exhibition. San Francisco, 2015: 197-208.
[13]	KVANDE R, MJ S Y, RYNINGEN B. Growth rate and impurity distribution in multicrystalline silicon for solar cells. Materials Scienc and Engineering:A, 2005, 413-414: 545-549.
[14]	KURODA E, SAITOH T.Growth and characterization of polycrystalline silicon ingots from metallurgical grade source material.Journal of Crystal Growth, 1979, 47(2): 251-260.
[15]	SAFARIAN J, KOLBEINSEN L, TANGSTAD M.Thermodynamic activities in silicon binary melts.Journal of Materials Science, 2012, 47: 5561-5580.
[16]	SAFARIAN J, KOLBEINSEN L, TANGSTAD M.Liquidus of silicon binary systems.Metallurgical and Materials Transactions B, 2011, 42: 852-874.
[17]	YOSHIKAWA T, MORITA K.Solid Solubilities and thermodynamic properties of aluminum in solid silicon.Journal of The Electrochemical Society, 2003, 150(8): 465-468.
[18]	OLESINSHI R W, ABBASCHIAN G J.The Si-Sn (silicon-tin) system.Journal of Phase Equilibria, 1984, 5(3): 273-276.

Si-Al-Sn合金熔体中块体硅定向生长行为研究

Directional Growth of Bulk Silicon from Si-Al-Sn Melts

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 18

相关文章 4

编辑推荐

Metrics

本文评价

[1]	孙鲁超, 周翠, 杜铁锋, 吴贞, 雷一明, 李家麟, 苏海军, 王京阳. 光悬浮区熔定向凝固Al₂O₃/Er₃Al₅O₁₂和Al₂O₃/Yb₃Al₅O₁₂共晶陶瓷的制备与性能研究[J]. 无机材料学报, 2021, 36(6): 652-658.
[2]	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.
[3]	崔春娟,张军,苏海军,王红,刘林,傅恒志. Si-TaSi₂共晶自生复合场发射材料的定向凝固组织特征[J]. 无机材料学报, 2007, 22(5): 1019-1023.
[4]	潘振甦,张惠丰,郭景坤. 定向凝固共晶多相复合陶瓷的研究现状[J]. 无机材料学报, 1999, 14(4): 513-519.