碳热还原歧化法制备高品质硅的实验研究
|
摘要
目前正在研究用冶金法制备太阳能级多晶硅的国内外的公司和科研院所较多,其工艺路线不尽相同,但基本原理都是利用硅和硅中杂质之间的物理化学性质,把凝固除杂、真空高温蒸发除杂、氧化除杂、酸浸除杂、造渣除杂、电解还原等方法中的一种或几种有机的组合起来形成一种工艺路线,达到提纯制备太阳能级硅的目的。
本研究工艺路线为：采用自行设计的中频感应炉加热,以经过预处理的碳和二氧化硅作为原料,在自行设计的高纯石墨坩埚中发生碳热还原反应,获得高纯度的一氧化硅气体,并在一定温度条件下使一氧化硅气体发生歧化反应获得高纯硅和高纯二氧化硅,分离二氧化硅后再进行真空定向凝固可获得多晶硅。
本文利用了X射线衍射仪(XRD)、拉曼光谱仪、扫描电子显微镜(SEM)、电感耦合等离子发射光谱仪(ICP)等设备,研究了歧化生成物的微观结构、生成机理、物相成分、产物的纯度及提纯机理。
通过研究获得以下研究结果：(1)实验中的歧化生成物由直径几百纳米的纳米线和纳米球组成,纳米线和纳米球内部为硅,表面附着SiO2,对这些歧化物球磨后,可以采用酸浸的方式分离出歧化生成物中的二氧化硅,获得高纯度的硅；(2)HF酸酸浸可以完全去除歧化生成物中的二氧化硅和B杂质元素,但对纯度较低的P、Fe、Al杂质元素的去除效果不大,分析了B被去除的机理；(3)通过碳热还原歧化法制备的高纯硅中,ICP检测结果表明,B杂质元素含量检测不到,B杂质元素的去除率接近100%,而P、Fe、Al杂质元素的含量和原料相比,降低了一到两个数量级,且原料纯度越高,产物纯度也越高。
At present, there are many companies and universities which are researching a new way to get solar grade silicon by metallurgical technology. In spite of these new techniques have many differences, physical or chemical characters of silicon are used in the metallurgy process. Purification aim can be achieved by direction solidification, vacuum distillation at high temperature, oxidizing impurities, carbothermic reduction and so on.
Process route in this study is shown as follow. Experimental equipment is self-designed intermediate frequency induction furnace. Pretreated silica wastes and charcoal wastes are used as raw material. High purity SiO gas can be formed by carbothermic reduction at high temperature, and SiO gas will be disproported into high purity silicon and silicon dioxide in the self-designed high purity graphite crucible when temperature go down, then solar grade silicon can be achieved after separating silicon dioxide in HF acid and directional solidification in vacuum.
In this paper micromechanism and generation mechanism of the sample prepared by carbothermic reduction and disproportionation method are studied by scanning electron microscope(SEM). Phase composition of the sample is studied by X-Ray diffraction instrument(XRD) and raman spectrum instrument. Purity of the sample are studied by inductive coupled plasma spectrometer(ICP).
From the study we can get the following results:(1) Sample prepared by disproportionation method is made up of nanowires and nanospheres whose diameter from 100 nanometer to 600 nanometer, and nanowires and nanospheres are made up of silicon and silicon dioxide which locate on the surface of the silicon, as a result silicon dioxide can be absolutely removed by acid leaching; (2) Silicon dioxide and B element can be absolutely removed by acid leaching,and has bad effect on removing P, Fe,Al element. B element absolutely removing mechanism is analysed;(3) Impurities such as B, P, Fe, Al content in the high purity silicon by carbothermic reduction and disproportionation method is lower than the raw materials, especially B content in the production is close to 0 ppmw. If raw material has high purity, then the production has higher purity.
本研究工艺路线为：采用自行设计的中频感应炉加热,以经过预处理的碳和二氧化硅作为原料,在自行设计的高纯石墨坩埚中发生碳热还原反应,获得高纯度的一氧化硅气体,并在一定温度条件下使一氧化硅气体发生歧化反应获得高纯硅和高纯二氧化硅,分离二氧化硅后再进行真空定向凝固可获得多晶硅。
本文利用了X射线衍射仪(XRD)、拉曼光谱仪、扫描电子显微镜(SEM)、电感耦合等离子发射光谱仪(ICP)等设备,研究了歧化生成物的微观结构、生成机理、物相成分、产物的纯度及提纯机理。
通过研究获得以下研究结果：(1)实验中的歧化生成物由直径几百纳米的纳米线和纳米球组成,纳米线和纳米球内部为硅,表面附着SiO2,对这些歧化物球磨后,可以采用酸浸的方式分离出歧化生成物中的二氧化硅,获得高纯度的硅；(2)HF酸酸浸可以完全去除歧化生成物中的二氧化硅和B杂质元素,但对纯度较低的P、Fe、Al杂质元素的去除效果不大,分析了B被去除的机理；(3)通过碳热还原歧化法制备的高纯硅中,ICP检测结果表明,B杂质元素含量检测不到,B杂质元素的去除率接近100%,而P、Fe、Al杂质元素的含量和原料相比,降低了一到两个数量级,且原料纯度越高,产物纯度也越高。
At present, there are many companies and universities which are researching a new way to get solar grade silicon by metallurgical technology. In spite of these new techniques have many differences, physical or chemical characters of silicon are used in the metallurgy process. Purification aim can be achieved by direction solidification, vacuum distillation at high temperature, oxidizing impurities, carbothermic reduction and so on.
Process route in this study is shown as follow. Experimental equipment is self-designed intermediate frequency induction furnace. Pretreated silica wastes and charcoal wastes are used as raw material. High purity SiO gas can be formed by carbothermic reduction at high temperature, and SiO gas will be disproported into high purity silicon and silicon dioxide in the self-designed high purity graphite crucible when temperature go down, then solar grade silicon can be achieved after separating silicon dioxide in HF acid and directional solidification in vacuum.
In this paper micromechanism and generation mechanism of the sample prepared by carbothermic reduction and disproportionation method are studied by scanning electron microscope(SEM). Phase composition of the sample is studied by X-Ray diffraction instrument(XRD) and raman spectrum instrument. Purity of the sample are studied by inductive coupled plasma spectrometer(ICP).
From the study we can get the following results:(1) Sample prepared by disproportionation method is made up of nanowires and nanospheres whose diameter from 100 nanometer to 600 nanometer, and nanowires and nanospheres are made up of silicon and silicon dioxide which locate on the surface of the silicon, as a result silicon dioxide can be absolutely removed by acid leaching; (2) Silicon dioxide and B element can be absolutely removed by acid leaching,and has bad effect on removing P, Fe,Al element. B element absolutely removing mechanism is analysed;(3) Impurities such as B, P, Fe, Al content in the high purity silicon by carbothermic reduction and disproportionation method is lower than the raw materials, especially B content in the production is close to 0 ppmw. If raw material has high purity, then the production has higher purity.
引文
[1]杨德仁编著.太阳电池材料[M].北京：化学工业出版社,2006.10
[2]张耀明.阳光经济和能源革命[J].江苏科技信息,2004(4)：1-4
[3]赵玉文.太阳能技术对我国未来减排CO2的贡献[J].太阳能,2003(3)：3-4
[4]C P. Khattack, D B. Joyce, F. Schmid. A simple process to remove boron from
metallurgical grade silicon[J. Solar Energy Materials & Solar Cells,2002,74:77-89
[5]S. Rousseau, M. Benmansour, D. Morvan, J. Amouroux. Purification of MG silicon by thermal plasma process coupled to DC bias of the liquid bath[J]. Solar Energy Materials & Solar Cells,2007,91:1906-1915
[6]吕东,马文会,伍继君,杨斌,戴永年.冶金法制备太阳能级硅新工艺原理及研究进展[J].材料导报,2009,(3)：30
[7]阙端麟主编.硅材料科学与技术[M].浙江：浙江大学出版社,2000
[8]戴永年.二元合金相图集[M].北京：科学出版社,2009
[9]Solar Silicon Conference April 3,2006. Munich, Germany
[10]刘馨.中国光伏：凤凰涅槃[J].新材料产业,2009, (4)：2
[11]Dominique Sarti, Roland Einhaus. Silicon feedstock for the multi-crystalline photovoltaic industry [J]. Solar Energy Materials & Solar cells.2002,72:27-40
[12]戴永年.金属及矿产品深加工[M].北京：冶金工业出版社.2007：447-470.
[13]Peter Wodisch, Wolfgang Koch. Solar grade silicon feedstock supply for PV industry[J]. Solar Energy Materials & Solar Cells,2002,71:11-26
[14]能源使用合理化硅制造过程开发.日本NEDO报告.2001
[15]蒋荣华.国内外半导体硅材料最新发展状况[J].新材料产业,2002(7)：47-52
[16]梁骏吾,周廉,阙端麟.关于打破垄断、政府主导、多方融资建设多晶硅厂的计划.工程院院士建议(内部资料)
[17]张椿.太阳能用多晶硅的现状和发展[C].多晶硅材料十一五科技发展战略研讨会论文集.北京.2005：38-34
[18]马春.世界半导体硅材料发展现状[J].上海有色金属.2005,26(3)：145-148
[19]杨晓婵.日本半导体硅市场[J].现代材料动态.2004(6)：14
[20]王家楫,王铮.半导体硅材料技术与市场[J].集成电路应用.2002(9)：9-15
[21]Moller H J, Funke C, Rinio M et al. Multicrystalline silicon for solar cells[J]. Thin Solid Films.2005,487:179-187
[22]蒋荣华,肖顺珍.国内外多晶硅发展现状[J].半导体技术.2001,26(11)：7-10
[23]郭瑾,李积和.国内外多晶硅工业现状[J].上海有色金属.2007,28(1):20-26
[24]http://www.51invest.com/report/2008.pdf全球视角的多晶硅行业分析之二
[25]Workshop "Silicon for PV Applications"[C]. Roadmap Meeting.2002,19
[26]New process for cost effective solar grade silicon from silane[C].20th EPVSEC. 2006,6. Barcelona
[27]A Goetzberger, C Hebling. Solar energy materials[J]. Solar cells.2001,62:1
[28]席珍强,陈君,杨德仁.太阳能电池发展现状及展望[J].新能源.2000(12)：100-102
[29]冯瑞华,马廷灿,姜山等.太阳能级多晶硅制备技术与工艺[J].新材料产业2007,(5)：59
[30]MULLER A, GHOSH M. Silicon for photovohaic applications[J]. Materials Science and Engineering,2006, (7):1
[31]K.Morita, T.Miki. Thermodynamics of solar-grade-silicon refining[J]. Intermeta-llics,2003,(11):1111
[32]Xu Wen-ting,Ma Wen-hui et al. Thermodynamic Fundamental of Purification of Silicon[J]. ACTA SCIENTIARUM NATURALIUM UNIVERSITATIS SUNYATS-ENI,2007,46(6):88
[33]胡赓祥,蔡殉主编.材料科学与基础[M].上海：上海交通大学出版社,2000.11
[34]戴永年,杨斌编著.有色金属材料的真空冶金[M].北京：冶金工业出版社2000.3
[35]WEI Kui-xian, MA Wen-Hui et al. Vacuum distillation refining of metallurgical grade silicon(Ⅰ)—Thermodynamics on removal of phosphorus from metallurgical grade silicon[J]. Trans. Nonferrous Met.Soc.2007,17:1022
[36]吴亚萍.太阳能级多晶硅的冶金制备研究[D].大连：大连理工大学,2006.12
[37]Wu Jijun,Ma Wenhui,Dai Yongnian,Wei Kuixian. Removing boron from metallurgical grade silicon by vacuum oxidation refining[A].Proceedings of the 8th Vacuum Metallurgy and Surface Engineering Conference.2007,(6):51
[38]Chandra P. Khattack, David B.Joyce,Frederick Schmid. A simple process to remove boron from metallurgical grade silicon[J]. Solar Energy Materials Solar Cells,2002,74:77
[39]Khattack C P, Joyce D B, Schmid F. Production of Solar Grade (SoG) Silicon by Refining Liquid Metallurgical Grade (MG) Silicon[R].
[40]Yu Zhan-liang, Ma Wen-hui et al. Removal of iron and aluminum impurities from metallurgical grade-silicon with hydrometallurgical route[J]. Trans. Nonferrous Met.Soc.China 2007,17:1030
[41]Sakata T,Miki T, Morita K. J Jpn Inst Metals 2002,66:4599.
[42]K.Yasuda et al., Direct electrolytic reduction of solid SiO2 in molten CaCl2 for the production of solar grade silicon[J]. Electrochim. Acta,2007:1
[43]LIU Yi-ke, MA Wen-hui,YANG Bin, DAI Yong-nian. Investigation of Direct Electrolytic Reduction of Solid SiO2 to Si with High Purity[J]. ACTA SCIENTIARUM NATURALIUM UNIVERSITATIS SUNYATSENI,2007, 46(6):333
[44]Yasuhiko SAKAGUCHI et al. Production of High Putity Silicon by Carbothermic Reduction of Silica Using Ac-arc Furnace With Heated Shaft[J]. ISIJ International, 1992,32(5):643
[45]K.B. Tynyshtykbaev et al. Direct catbothermal receiving of solar grade silicon. Materials Science and Engineering[J],2006,134:296
[46]L.J. Geerligs et al. Solar-grade silicon by a direct route based on carbothermic reduction of silica:requirements and production technology[J]. http://www.ecn.nl/ docs/library/report/2002/rx 02042.pdf
[47]史博士,物理法多晶硅英雄榜：北美篇之http://blog.sina.com.cn/s/blog_4afdca 8c01009n 63.html
[48]埃尔凯姆有限公司.太阳能电池的硅原料.200480039417.3[p].2007.01.24
[49]A.F.B. Braga, S.P. Moreira et al. New processes for the production of solar-grade polycrystal-line silicon:A review[J]. Solar Energy Materials & Solar Cells, 2008,92:418
[50]S.Rousseau, M.Benmansour,D, Morvan, J.Amouroux. Purification of MG silicon by thermal plasma process coupled to DC bias of the liquid bath[J]. Solar Energy Materials & Solar Cells,2007,91:1906
[51]马文会,戴永年,杨斌等.一种制备太阳能级多晶硅的方法：中国,ZL200710066017.7[p]
[52]T. NOHIRA, K. YASUDA, Y. ITO. Pinpoint and bulk electrochemical reduction of insulating silicon dioxide to silicon[J]. Nature Materials,2003,2:397
[63]马文会,戴永年,杨斌等.由光纤预制棒废料制备太阳能级硅的方法：中国.200710065906.1[p].2007.10.24
[54]Aulich,H.A.,Eisenrit,K.H.,Scgulze,F.W.,Strake,B.,Urbach,H.P..6thE.C.Photovoltai c Energy Conf. London:Commun.Eur.Communities Rep,EUR10025,(1985):951
[55]李洪桂.冶金原理.北京：科学出版社,2005
[56]杨斌,戴永年.真空冶炼法提取金属锂的研究.昆明：云南科技出版社,1999
[57]何允平,王金绎.工业硅科技新进展[M].北京：冶金工业出版社,2003,7
[58]STEFANO E. Ab initio study of C4O4 in Td symmetry [J]. Chem Phys Lett,1996, 259(3/4):261
[59]JAMES O J. Vibrational frequencies and structural determination of Ge4O4 [J]. Spectrochim Acta Part A:Mol & Biomol Spectrosc,2005,61:3108
[60]张萱,曾祥华,郭云,徐秀莲.一氧化硅四聚体的结构、振动频率和光谱研究. 扬州大学学报(自然科学版),11(1)：24
[61]唐元洪.硅纳米线及硅纳米管[M].北京：化学工业出版社.2007
[62]苏英,周永恒,黄武,顾真安.石英玻璃与HF酸反应动力学的研究.硅酸盐学报,32(3)：287
[2]张耀明.阳光经济和能源革命[J].江苏科技信息,2004(4)：1-4
[3]赵玉文.太阳能技术对我国未来减排CO2的贡献[J].太阳能,2003(3)：3-4
[4]C P. Khattack, D B. Joyce, F. Schmid. A simple process to remove boron from
metallurgical grade silicon[J. Solar Energy Materials & Solar Cells,2002,74:77-89
[5]S. Rousseau, M. Benmansour, D. Morvan, J. Amouroux. Purification of MG silicon by thermal plasma process coupled to DC bias of the liquid bath[J]. Solar Energy Materials & Solar Cells,2007,91:1906-1915
[6]吕东,马文会,伍继君,杨斌,戴永年.冶金法制备太阳能级硅新工艺原理及研究进展[J].材料导报,2009,(3)：30
[7]阙端麟主编.硅材料科学与技术[M].浙江：浙江大学出版社,2000
[8]戴永年.二元合金相图集[M].北京：科学出版社,2009
[9]Solar Silicon Conference April 3,2006. Munich, Germany
[10]刘馨.中国光伏：凤凰涅槃[J].新材料产业,2009, (4)：2
[11]Dominique Sarti, Roland Einhaus. Silicon feedstock for the multi-crystalline photovoltaic industry [J]. Solar Energy Materials & Solar cells.2002,72:27-40
[12]戴永年.金属及矿产品深加工[M].北京：冶金工业出版社.2007：447-470.
[13]Peter Wodisch, Wolfgang Koch. Solar grade silicon feedstock supply for PV industry[J]. Solar Energy Materials & Solar Cells,2002,71:11-26
[14]能源使用合理化硅制造过程开发.日本NEDO报告.2001
[15]蒋荣华.国内外半导体硅材料最新发展状况[J].新材料产业,2002(7)：47-52
[16]梁骏吾,周廉,阙端麟.关于打破垄断、政府主导、多方融资建设多晶硅厂的计划.工程院院士建议(内部资料)
[17]张椿.太阳能用多晶硅的现状和发展[C].多晶硅材料十一五科技发展战略研讨会论文集.北京.2005：38-34
[18]马春.世界半导体硅材料发展现状[J].上海有色金属.2005,26(3)：145-148
[19]杨晓婵.日本半导体硅市场[J].现代材料动态.2004(6)：14
[20]王家楫,王铮.半导体硅材料技术与市场[J].集成电路应用.2002(9)：9-15
[21]Moller H J, Funke C, Rinio M et al. Multicrystalline silicon for solar cells[J]. Thin Solid Films.2005,487:179-187
[22]蒋荣华,肖顺珍.国内外多晶硅发展现状[J].半导体技术.2001,26(11)：7-10
[23]郭瑾,李积和.国内外多晶硅工业现状[J].上海有色金属.2007,28(1):20-26
[24]http://www.51invest.com/report/2008.pdf全球视角的多晶硅行业分析之二
[25]Workshop "Silicon for PV Applications"[C]. Roadmap Meeting.2002,19
[26]New process for cost effective solar grade silicon from silane[C].20th EPVSEC. 2006,6. Barcelona
[27]A Goetzberger, C Hebling. Solar energy materials[J]. Solar cells.2001,62:1
[28]席珍强,陈君,杨德仁.太阳能电池发展现状及展望[J].新能源.2000(12)：100-102
[29]冯瑞华,马廷灿,姜山等.太阳能级多晶硅制备技术与工艺[J].新材料产业2007,(5)：59
[30]MULLER A, GHOSH M. Silicon for photovohaic applications[J]. Materials Science and Engineering,2006, (7):1
[31]K.Morita, T.Miki. Thermodynamics of solar-grade-silicon refining[J]. Intermeta-llics,2003,(11):1111
[32]Xu Wen-ting,Ma Wen-hui et al. Thermodynamic Fundamental of Purification of Silicon[J]. ACTA SCIENTIARUM NATURALIUM UNIVERSITATIS SUNYATS-ENI,2007,46(6):88
[33]胡赓祥,蔡殉主编.材料科学与基础[M].上海：上海交通大学出版社,2000.11
[34]戴永年,杨斌编著.有色金属材料的真空冶金[M].北京：冶金工业出版社2000.3
[35]WEI Kui-xian, MA Wen-Hui et al. Vacuum distillation refining of metallurgical grade silicon(Ⅰ)—Thermodynamics on removal of phosphorus from metallurgical grade silicon[J]. Trans. Nonferrous Met.Soc.2007,17:1022
[36]吴亚萍.太阳能级多晶硅的冶金制备研究[D].大连：大连理工大学,2006.12
[37]Wu Jijun,Ma Wenhui,Dai Yongnian,Wei Kuixian. Removing boron from metallurgical grade silicon by vacuum oxidation refining[A].Proceedings of the 8th Vacuum Metallurgy and Surface Engineering Conference.2007,(6):51
[38]Chandra P. Khattack, David B.Joyce,Frederick Schmid. A simple process to remove boron from metallurgical grade silicon[J]. Solar Energy Materials Solar Cells,2002,74:77
[39]Khattack C P, Joyce D B, Schmid F. Production of Solar Grade (SoG) Silicon by Refining Liquid Metallurgical Grade (MG) Silicon[R].
[40]Yu Zhan-liang, Ma Wen-hui et al. Removal of iron and aluminum impurities from metallurgical grade-silicon with hydrometallurgical route[J]. Trans. Nonferrous Met.Soc.China 2007,17:1030
[41]Sakata T,Miki T, Morita K. J Jpn Inst Metals 2002,66:4599.
[42]K.Yasuda et al., Direct electrolytic reduction of solid SiO2 in molten CaCl2 for the production of solar grade silicon[J]. Electrochim. Acta,2007:1
[43]LIU Yi-ke, MA Wen-hui,YANG Bin, DAI Yong-nian. Investigation of Direct Electrolytic Reduction of Solid SiO2 to Si with High Purity[J]. ACTA SCIENTIARUM NATURALIUM UNIVERSITATIS SUNYATSENI,2007, 46(6):333
[44]Yasuhiko SAKAGUCHI et al. Production of High Putity Silicon by Carbothermic Reduction of Silica Using Ac-arc Furnace With Heated Shaft[J]. ISIJ International, 1992,32(5):643
[45]K.B. Tynyshtykbaev et al. Direct catbothermal receiving of solar grade silicon. Materials Science and Engineering[J],2006,134:296
[46]L.J. Geerligs et al. Solar-grade silicon by a direct route based on carbothermic reduction of silica:requirements and production technology[J]. http://www.ecn.nl/ docs/library/report/2002/rx 02042.pdf
[47]史博士,物理法多晶硅英雄榜：北美篇之http://blog.sina.com.cn/s/blog_4afdca 8c01009n 63.html
[48]埃尔凯姆有限公司.太阳能电池的硅原料.200480039417.3[p].2007.01.24
[49]A.F.B. Braga, S.P. Moreira et al. New processes for the production of solar-grade polycrystal-line silicon:A review[J]. Solar Energy Materials & Solar Cells, 2008,92:418
[50]S.Rousseau, M.Benmansour,D, Morvan, J.Amouroux. Purification of MG silicon by thermal plasma process coupled to DC bias of the liquid bath[J]. Solar Energy Materials & Solar Cells,2007,91:1906
[51]马文会,戴永年,杨斌等.一种制备太阳能级多晶硅的方法：中国,ZL200710066017.7[p]
[52]T. NOHIRA, K. YASUDA, Y. ITO. Pinpoint and bulk electrochemical reduction of insulating silicon dioxide to silicon[J]. Nature Materials,2003,2:397
[63]马文会,戴永年,杨斌等.由光纤预制棒废料制备太阳能级硅的方法：中国.200710065906.1[p].2007.10.24
[54]Aulich,H.A.,Eisenrit,K.H.,Scgulze,F.W.,Strake,B.,Urbach,H.P..6thE.C.Photovoltai c Energy Conf. London:Commun.Eur.Communities Rep,EUR10025,(1985):951
[55]李洪桂.冶金原理.北京：科学出版社,2005
[56]杨斌,戴永年.真空冶炼法提取金属锂的研究.昆明：云南科技出版社,1999
[57]何允平,王金绎.工业硅科技新进展[M].北京：冶金工业出版社,2003,7
[58]STEFANO E. Ab initio study of C4O4 in Td symmetry [J]. Chem Phys Lett,1996, 259(3/4):261
[59]JAMES O J. Vibrational frequencies and structural determination of Ge4O4 [J]. Spectrochim Acta Part A:Mol & Biomol Spectrosc,2005,61:3108
[60]张萱,曾祥华,郭云,徐秀莲.一氧化硅四聚体的结构、振动频率和光谱研究. 扬州大学学报(自然科学版),11(1)：24
[61]唐元洪.硅纳米线及硅纳米管[M].北京：化学工业出版社.2007
[62]苏英,周永恒,黄武,顾真安.石英玻璃与HF酸反应动力学的研究.硅酸盐学报,32(3)：287