Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
권호 표지

Preparation of Polysilicon for Solar Cells

태양전지용 폴리실리콘 제조

  • Kim, Hee Young (Advanced Chem-Tech Division, Korea Research Institute of Chemical Technology)
  • 김희영 (한국화학연구원 신화학연구단)
  • Received : 2007.10.31
  • Accepted : 2008.01.07
  • Published : 2008.02.28
Download PDF
⟨ Previous Next ⟩

Abstract

Recent rapid progress in the photovoltaic industry has seriously been retarded by limited supply of polysilicon used as the feedstock for silicon wafer-based solar cells. It is thus believed that development of a competitive process for preparing polysilicon with the quality required for solar cells can greatly enhance the competitiveness and extent of the photovoltaic application. Technologies currently available for preparing the silicon feedstock are reviewed with the recent fluidized bed silicon deposition process being discussed in more details in terms of key technical barriers.

태양전지 기판의 원료인 폴리실리콘의 공급부족은 태양광발전산업의 비약적인 발전에 있어 최대 걸림돌이 되고 있다. 태양전지 제조에 충분한 순도로 폴리실리콘을 값싸게 제조할 수 있게 하는 공정기술의 개발은 태양광발전의 가격 경쟁력과 활용범위를 크게 증가시키는 중요한 계기가 될 수 있다. 본 총설에서는 태양전지용 폴리실리콘 제조를 위해 현재 이용 가능한 기술들을 정리해보고, 최근에 주목받고 있는 유동층 석출공정기술과 관련하여 응용범위 확대를 가로막고 있는 주요 기술적 장애요인에 대하여 중점적으로 소개하고자 한다.

Keywords

Acknowledgement

Supported by : 산업자원부

References

  1. Rogol, M., SOLA ANNUAL 2007-Big Things in a Small Package, Photon Consulting, Solar Verlag GmbH(2007).
  2. Jaeger-Waldau, A., "PV Status Report 2006: Research, Solar Cell Production and Market Implementation of Photovoltaics," EUR- 22346 EN, European Commission, DG Joint Research Center, August(2006).
  3. Mueller, A., Ghosh, M., Sonnenshein, R. and Woditsch, P., "Silicon for Photovoltaic Application," Materials Science and Engineering B, 134, 257-261(2006). https://doi.org/10.1016/j.mseb.2006.06.054
  4. Tsuo, Y. S., Gee, J. M., Menna, P., Strebkov, D. S., Pinov, A. and Zadde, V., "Environmentally Benign Solar Cell Manufacturing," the 2nd World Conference and Exhibition on Photovoltaic Solar Energy Conversion, Wien, Austria, July 6-10(1998).
  5. Rull, G., "Issues and Opportunities for the PV Industry," Micronews, 61, 4-6, September(2007).
  6. Flynn, H. and Bradford, T., POLYSILICON-Supply, Demand and Implications for the PV Industry, Prometheus Institute fir Sustainable Development(2006).
  7. PV TEAM-Report (Abstract): PhotoVoltaic Technologies, Equipments, Applications & Materials,Yole Developpment (2007) http://www.yole.fr/pagesAn/products/Report_sample/pv.pdf.
  8. Ceccaroli, B. and Lohne, O., "Solar Grade Silicon Feedstock," in Luque, A. and Hegedus, S. (Eds), Handbook of Photovoltaic Science and Engineering, John Wiley & Sons Ltd., Chichester, England, 154-204(2003).
  9. Rogol, M., "Silicon and the Solar Sector: Outlook through 2010," 3rd Solar Silicon Conference, Apr. 3, Munich(2006).
  10. Tremblay, J.-F., "Solar Market Powers Silicon," Chemical & Engineering News, 84(40), 30-34(2006).
  11. Kuramoto, M., "Development History of Granular Polycrystalline Silicon and Problems in Their Use," Chem. Eng. (Japan), 55(11), 86-867(1991).
  12. Fath, P. and Mozer, A., "Design Criteria for PolySilicon Factories," 3rd Solar Silicon Conference, Apr. 3, Munich(2006).
  13. Kim, H. Y., "Technology for Preparing Semiconductor-grade Polycrystalline Silicon," Chem. Ind. & Tech. (Kor.), 14(1), 50-58 (1996).
  14. Gribov, B. G. and Zinov'ev, K. V., "Preparation of High-Purity Silicon for Solar Cells," Inorganic Materials, 39(7) 653-662(2003). https://doi.org/10.1023/A:1024553420534
  15. Woditsch, P., "A Bright Futire: Why Crystalline Silicon Will Continue to Deliver," PV-Industrieforum 2006, June 21(2006)[http:// www.renewable-energy-world.com/articles/article_display.cfm? ARTICLE_ID=273237&p=121].
  16. O'Mara, W. C., Herring, R. B. and Hunt, L. P.(Eds), Handbook of Semiconductor Silicon Technology, Noyes Publications, NJ, USA(1990).
  17. Araki, I., Yamamoto, T., Tokuda, Y. and Momose, H., "Comparison among Several Suppliers of Metallurgical Silicon," 197-200, in Oye, H. A., Rong, H. M., Nygaard, L., Schussler, G. and Tuset, J. Kr. (Eds), Silicon for the Chemical Industry VI, Loen, Norway, June 17-21(2002).
  18. Andersen, G. J., Hoel, J.-O., Roe, T., Oye, H. A. and Rong, H. M., "Influence of Manganese in the Production of Trichlorosilane," 163-176, in Oye, H. A., Holas, A. and Nygaard, L. (Eds), Silicon for the Chemical Industry VII, MS Trollfyord, Tromso-Bergen, Norway, Sept. 21-24(2004).
  19. Andersen, G. J., Hoel, J.-O., Rong, H. M. and Roe, T., "Method for Production of Trichlorosilane and Silicon for Use in the Production of Trichlorosilane," WO 2007/035108 A1(2007).
  20. Kuerschner, U., Paetzold, U., Hesse, K. and Lieske, H., "Studies on Trichlorosilane Synthesis," 177-188, in Oye, H. A., Holas, A. and Nygaard, L. (Eds), Silicon for the Chemical Industry VII, MS Trollfyord, Tromso-Bergen, Norway, Sept. 21-24(2004).
  21. Kotzsch, H.-J. and Vahlensieck, H.-J., "Process for the Hydrochlorination of Elemental Silicon," US Patent No. 4,044,109(1977).
  22. Sakata, K. and Hirota, K., "Process for Producing Trichlorosilane," US Patent No. 5,871,705(1999).
  23. Wineland, J. D., "Silicon Crusher Dust Explosion Hazards," 183-189, in Oye, H. A., Rong, H. M., Nygaard, L., Schussler, G. and Tuset, J. Kr. (Eds), Silicon for the Chemical Industry VI, Loen, Norway, June 17-21(2002).
  24. Barker, Jr., T. H., "Process for Preparing Chlorosilanes from Silicon and Hydrogen Chloride Using an Oxygen Promoter," US Patent No. 4,585,643(1986).
  25. Gansauge, J., Muschi, J. and Freudlsperger, H., "Fluidized Bed Reactor," US Patent No. 4,176,710(1979).
  26. Noda, S., Tanabe, K., Yahiro, T., Osawa, T. and Komiyama, H., "Reaction of Si with HCl to Form Chlorosilanes," J. Electrochem. Soc., 151(6), C399-C404(2004). https://doi.org/10.1149/1.1737386
  27. Ruff, K., "Method for Increasing the Yield of Trichlorosilane in the Fluidized-bed Hydrochlorination of Silicon," US Patent No. 5,063,040(1991).
  28. Braunsperger, J., Lang, W. and Zainer, T., "Process for the Manufacture of Trichlorosilane and Silicon Tetrachloride," US Patent No. 4,130,632(1978).
  29. Blocher, Jr., J. M. and Browning, M. F., "Process for Silicon and Trichlorosilane Production," US Patent No. 4,117,094(1978).
  30. Kroupa, M. G., "High Boiling Residue Recovery Process for the Synthesis of Trichlorosilane," 201-208, in Oye, H. A., Rong, H. M., Nygaard, L., Schussler, G. and Tuset, J. Kr. (Eds), Silicon for the Chemical Industry VI, Loen, Norway, June 17-21(2002).
  31. Union Carbide Corp., "Low Cost Solar Array Project-Feasibility of the Silane Process for Producing Semiconductor-Grade Silicon," JPL contract No. 954334, Final Report, June(1979).
  32. Mui, J. Y. P. and Seyferth, D., "Investigation of the Hydrogenation of SiCl4," JPL Contract No. 955 382, Final Report, April 15 (1981).
  33. Block(1), H.-D., Mleczko, L., Leimkuehler, H.-J., Weber, R., Werner, K., Schwanke, D., Schaefer, J.-P. and Wagner, G., "Method for Production of High Purity Silicon," US Patent No. 6,887,448 (2005).
  34. Block(2), H.-D., Leimkuehler, H.-J., Mueller, D., Schaefer, J.-P. and Ronge, G., "Method and System for Producing Silane," US Patent No. 6,905,576(2005).
  35. Sundermeyer, W., "Monosilane and Methylsilanes-A New Titanium Mediated Synthesis for (Periodical) Evergreens," 265-270, in Oye, H. A., Rong, H. M., Nygaard, L., Schussler, G., and Tuset, J. K. (Eds), Silicon for the Chemical Industry V, Tromsoe, Norway, May 29-June 2(2000).
  36. Padovani, F. A., Miller, M. B., Moore, J. A., Fowler, J. H., June, M. N., Mattews, J. D., Morton, T. R., Stotko, N. A. and Palmer, L. B., "Process of Refining Impure Silicon to Produce Purified Electronic Grade Silicon," US Patent No. 4,092,446(1978).
  37. Weigert, W., "Process for the Production of Chlorosilanes," US Patent No. 4,165,363(1979), 4,217,334(1980).
  38. Roever, I., Acker, J., Bohmhammel, K., Roewer, G., Hesse, K. and Paetzold, U., "The Catalytic Hydrogenation of Chlorosilanes- the Crucial Point of Production of Electronic-grade Silicon," 209-224, in Oye, H. A., Rong, H. M., Nygaard, L., Schussler, G. and Tuset, J. Kr. (Eds), Silicon for the Chemical Industry VI, Loen, Norway, June 17-21(2002).
  39. Roewer, G., Paetzold, U. and Walter, H., "Catalytic Hydrodehalogenation of Halogen-containing Compounds of Group IV Elements," US Patent No. 5,716,590(1998).
  40. Sarma, K. R. and Rice, Jr., M. J., "High Pressure Plasma Hydrogenation of Silicon Tetrachloride," US Patent No. 4,309,259(1982).
  41. Ingle, W. M., Preffley, M. S. and Setty, H. S. N., "Trichlorosilane Production Process," US Patent No.4,526,769(1985).
  42. Hamster, H. and Koeppl, F., "Device for Treating Gases at High Temperatures," US Patent No. 4,536,642(1985).
  43. Griesshammer, R., Koeppl, F., Lang, W., Muehlhofer, E. and Schwab, M., "Process for Processing Waste Gases Resulting During the Production of Silicon," US Patent No. 4,515,762(1985).
  44. Bakay, C. J., "Process for Making Silane," US Patent No. 3,968,199(1976).
  45. Litteral, C. J., "Disproportionation of Chlorosilane," US Patent No. 4,113,845(1978).
  46. Breneman, W. C., "High Purity Silane and Silicon Production," US Patent No. 4,676,967(1987).
  47. Jung, I. N., Cho K. D., Lim, J. C. and Yoo, B.-R., "Hydrogenation Catalyst and Methods for Its Preparation and Use to Convert Silicon Tetrachloride to Chlorosilane and Silane," US Patent No. 4,701,430(1987).
  48. Block, H.-D., Mleczko, L., Bulan, A., Weber, R., Buchholz, S. and Sill, T., "Method for Producing Silane," US Patent No. 6,852,301(2005).
  49. Keck, D. W., Nagai, K., Yatsurugi, Y., Morihara, H. and Izawa, J., "Production of High-purity Polycrystalline Silicon Rod for Semiconductor Applications," US Patent Nos. 5,382,419 and 5,478,396(1995) and 5,545,387(1996).
  50. Weidhaus, D. and Hayduk, A., "Radiation-Heated Fluidized-bed Reactor," US Patent No. 7,029,632(2006).
  51. Wacker Chemie AG FACT BOOK 2007, Investor Relations, July(2007).
  52. Solarbuzz News, "Wacker Builds Granular Solar Polysilicon Plant," July 16(2007); http://www.solarbuzz.com/News/NewsEUMA175.htm.
  53. Weidhaus, D., Schindlbeck, E. and Hesse, K., "Trichlorosilane Based Silicon Feedstock for the Photovoltaic Industry," 189-200, in Oye, H. A., Holas, A. and Nygaard, L. (Eds), Silicon for the Chemical Industry VII, MS Trollfyord, Tromso-Bergen, Norway, Sept. 21-24(2004).
  54. Weidhaus, D., Crossmann, I. and Schreieder, F., "Dust-Free and Pore-Free, High-Purity Granulated Polysilicon," US Patent Application Publication No. 0135986(2005).
  55. Weidhaus, D., Schindlbeck, E., Hesse, K. and Domberger, E., "Pilot Production of Granular Polysilicon from Trichlorosilane Using a Fluidized Bed-Type Reactor," 20th European Photovoltaic Solar Energy Conference, Proceedings 623-626, June 6-10, Barcelona, Spain(2005).
  56. Kim, H. Y., "Process for Preparing Polysilicon Using Exothermic Reaction," US Patent No. 6,395,248(2002).
  57. Kim, H. Y. and Park, Y.-K., "Method and Apparatus for Preparing Polysilicon Granules," US Patent No. 6,541,377(2003).
  58. Kim, H. Y., Yoon, K. K., Park, Y. K. and Choi, W. C., "Method for Preparing Polycrystalline Silicon Using Fluidized Bed Reactor," Korea Patent 10-0961284(2007).
  59. Kim, H. Y., Yoon, K. K., Park, Y. K. and Choi, W. C., "High- Pressure Fluidized Bed Reactor for Preparing Polycrystalline Silicon," Korea Patent 10-0756310(2007).
  60. Kim, H. Y., Yoon, K. K., Park, Y. K., Choi, W. C. and Kim, H. K., "Process Development for Continual Preparation of Silicon Feedstock for Solar Cells," Proceedings, 256-263, GreenSarang Workshop, COEX, Seoul, Oct. 5, 2007
  61. Age, S., "Manufacturing High Purity/low Chlorine Content Silicon by Feeding Chlorosilane into a Fluidized Bed of Silicon Particles," US Patent 5,077,028(1991).
  62. Schreieder, F. and Kim, H. Y., "Process for Preparing Highly Pure Silicon Granules," US Patent 6,007,869(1999).
  63. Hunt, L. P. and Sirtl, E., "A Through Thermodynamic Evaluation of the Silicon-Hydrogen-Chlorine System," J. Electrochem. Soc.: Solid-State Sci. & Tech., 119(12), 1741-1745(1972).
  64. Lund, C. P., Zhang, W., Jennings, P. J. and Singh, P., "Production of Lower-Cost Solar Cells from Silica," 249-263, in Oye, H. A., Rong, H. M., Nygaard, L., Schussler, G., and Tuset, J. K. (Eds), Silicon for the Chemical Industry V, Tromsoe, Norway, May 29- June 2(2000).
  65. REC Group, "Analyst Silicon Field Trip," March 28(2007).
  66. Block, H.-D. and Wagner, G., "Technical Progress on the Bayer Route to Low Cost Solar Grade Silicon," 271-280, in Oye, H. A., Rong, H. M., Nygaard, L., Schussler, G., and Tuset, J. K. (Eds), Silicon for the Chemical Industry V, Tromsoe, Norway, May 29- June 2(2000).
  67. DeLuca, J. P., "Closed Loop Process for Producing Polycrystalline Silicon and Fumed Silica," US Patent No. 5,910,295(1999).
  68. Hsu, G., Hogle, R., Rohatgi, N. and Morrison, A., "Fines in Fluidized Bed Silane Pyrolysis," J. Electrochem. Soc.: Solid-State Sci. & Tech., 131(3), 660-663(1984).
  69. Farrow, R. F. C., "The Kinetic of Silicon Deposition on Silicon by Pyrolysis of Silane," J. Electrochem. Soc.: Solid-State Sci. & Tech., 121(7), 899-907(1974).
  70. Iya, S. K., Flagella, R. N. and DiPaolo, F. S., "Heterogeneous Decomposition of Silane in a Fixed Bed Reactor," J. Electrochem. Soc.: Solid-State Sci. & Tech., 129(7), 1531-1535(1982).
  71. Caussat, B., Hemati, M. and Couderc, J. P., "Local Modeling of Mass Transfer with Chemical Vapor Deposition in a Gas-solid Fluidized Bed: Application to the Chemical Vapor Deposition of Silicon from Silane," Powder Technology, 101, 43-44(1999). https://doi.org/10.1016/S0032-5910(98)00122-3
  72. Caussat, B., Hemati, M. and Couderc, J. P., "Silicon Deposition from Silane or Disilane in a Fluidized Bed-Part I: Experimental Study," Chem. Eng. Sci., 50(22), 3615-3624(1995). https://doi.org/10.1016/0009-2509(95)00172-2
  73. Caussat, B., Hemati, M. and Couderc, J. P., "Silicon Deposition from Silane or Disilane in a Fluidized Bed-Part II: Theoretical Analysis and Modeling," Chem. Eng. Sci., 50(22), 3625-3635(1995). https://doi.org/10.1016/0009-2509(95)00173-3
  74. Kouadri-Mostefa, S., Serp., P., Hemati, M. and Caussat, B., "Silicon Chemical Deposition(CVD) on Microporous Powder in a Fluidized Bed," Powder Technology, 120, 82-87(2001). https://doi.org/10.1016/S0032-5910(01)00351-5
  75. Allen, R. H. and Boone, J. E., "Process for Preparing Polysilicon with Diminished Hydrogen Content by Using a Fluidized Bed with a Two-step Heating Process," US Patent No. 5,242,671 (1993); and "Process for Preparing Polysilicon with Diminished Hydrogen Content by Using a Two-step Heating Process," US Patent No. 5,326,547(1994).
  76. Flagella, R. N., "Fluidized Bed for Production of Polycrystalline Silicon," US Patent No. 5,139,762(1992).
  77. Flagella, R. N., "Fluidized Bed with Heated Liners and a Method for Its Use," US Patent No. 4,906,441(1990).
  78. Gautreaux, M. F., Lawrence, Jr., W. W., Daniels, G. A. and Hughmark, G. A., "Chemical Vapor Deposition Reactor and Process," US Patent No. 4,981,102(1991).
  79. Clary, D. W. and Wikman, A. O., "Device for the Magnetic Inductive Heating of Vessels," US Patent No. 5,260,538(1993).
  80. Lord, S. M. and Milligan, R. J., "Method for Silicon Deposition," US Patent No. 5,798,137(1998); "Silicon Deposition Reactor Apparatus," US Patent No. 5,810,934(1998).
  81. Koenig, T., Pfaffelhuber, M., Herold, H., Holdenried, G. and Mleczko, L., "Method for Producing Highly-Pure Granular Silicon," US Patent No. 6,849,244(2005).
  82. Mueller, A., Sonnenschein, R., Sill, T., Goelz, A. and Adler, P., "New Process for Cost Effective Solar Grade Silicon from Silane," 20th European Photovoltaic Solar Energy Conference, Proceedings 623-626, June 6-10, Barcelona, Spain(2005).
  83. Runyan, W. R., Silicon Semiconductor Technology, 6-15, McGraw- Hill Book Co., N.Y.(1965).
  84. Geerligs, B., "Direct Carbothermal Reduction to Low-cost Solar Grade Silicon," 3rd Solar Silicon Conference, Munich, April 3 (2006).
  85. Nepomnyaschikh, A. I., Fedosenko, V. A., Eremin, V. P. and Krasin, B. A., "Low Cost Multicrystalline Silicon for Solar Cells," 17-21, in Oye, H. A., Rong, H. M., Nygaard, L., Schussler, G. and Tuset, J. Kr. (Eds), Silicon for the Chemical Industry VI, Loen, Norway, June 17-21(2002).
  86. Dehloff, C., "Update on Elkem's Solar-Grade Silicon Development- the Metallurgical Route," 3rd Solar Silicon Conference, Munich, April 3(2006).
  87. Dow Corning Product Highlight, "A Breakthrough in Silicon Feedstock: Dow Corning PV 1101 SoG Silicon," http://www.dowcorning. com/content/solar/solarmetal/default.asp.