硅基薄膜太阳能电池材料的制备与性能研究
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摘要
非晶硅、多晶硅太阳能电池具有很高的性比价优势。本论文通过优化薄膜沉积的工艺参数，用磁控溅射技术制备硅薄膜，以期能够得到高质量的器件级硅薄膜材料。磁控溅射技术是一种简单、低温、快速的生长薄膜的方法，能够在不使用有毒气体和可燃性气体的情况下进行掺杂和沉积薄膜，用掺杂靶材直接用溅射法沉积成膜，这一方法节能、高效、环保。磁控溅射法与其它技术相比，它的最大优势在于薄膜的沉积速率快，成膜效率和经济效益太阳能电池行业是近些年发展的极其火热的一个朝阳产业。在硅系太阳能电池中，非常诱人，该技术有希望大幅度降低太阳能电池的成本。
随着第三代太阳能电池，即薄膜太阳能电池研究的不断深入，制备高质量的多晶硅薄膜是提高多晶硅薄膜太阳能电池的光伏转换效率，这是从本质上解决问题的一个途径。本论文对高质量的多晶硅薄膜的制备方面做了一些探索性的工作，采用金属铝诱导的方法成功制备了质量较高的多晶硅薄膜。首先用射频磁控溅技术在玻璃衬底上沉积非晶硅薄膜和铝薄膜，然后在Ar气氛中对样品进行退火处理，最后通过原子力显微镜和X射线仪对退火前后的磁控溅射法制备的硅薄膜进行了分析。
The solar cells is a new industry in China, which developing very sharply in recent years. The higherperformance price ratio of a-Si and poly-Si thin film solar cells in silicon based solar cells was verifiedthrough the development of this field. The silicon thin films have been prepared by magnetron sputteringmethod in order to get scientific datum needed in the process to deposit high quality device-1evel films byoptimizing the processing conditions. The magnetron sputtering is a simple, fast film. The depositionmethod, which can deposit doped silicon thin films without the usage of toxic or flammable gases, instead,use the polycrystalline as target to deposit films by Ar+sputtering．Compared to other film-depositiontechniques, the magnetron sputtering is a promising silicon thin film solar cells fabricating method for itshigh deposition rate and thus induced captivating economic efficiency. In the eyes of the author, thismethod is hopeful to reduce the cost of solar cells dramatically.
With the further research into the third generation solar cells—thin film solar cells, to fabricate highquality polycrystalline silicon(poly-Si)thin films is a most straight approach to improve the photovoltaicconversion efficiency. In this thesis, the fabrication of high quality poly-Si thin films is investigated．In thisdissertation, poly-Si thin films were successfully fabricated using aluminum induced crystallization (AIC).At the start, amorphous silicon(a-Si)thin films were prepared by the radiofrequency magnetron sputteringon glass substrates, after that, aluminum thin film Was deposited over a-Si min films using theradiofrequency magnetron sputtering, then the samples were annealed in Ar atmosphere with variousannealing parameters．The silicon thin films deposited by the magnetron sputtering are characterized byAFM and X-ray diffraction before and after annealing．
随着第三代太阳能电池，即薄膜太阳能电池研究的不断深入，制备高质量的多晶硅薄膜是提高多晶硅薄膜太阳能电池的光伏转换效率，这是从本质上解决问题的一个途径。本论文对高质量的多晶硅薄膜的制备方面做了一些探索性的工作，采用金属铝诱导的方法成功制备了质量较高的多晶硅薄膜。首先用射频磁控溅技术在玻璃衬底上沉积非晶硅薄膜和铝薄膜，然后在Ar气氛中对样品进行退火处理，最后通过原子力显微镜和X射线仪对退火前后的磁控溅射法制备的硅薄膜进行了分析。
The solar cells is a new industry in China, which developing very sharply in recent years. The higherperformance price ratio of a-Si and poly-Si thin film solar cells in silicon based solar cells was verifiedthrough the development of this field. The silicon thin films have been prepared by magnetron sputteringmethod in order to get scientific datum needed in the process to deposit high quality device-1evel films byoptimizing the processing conditions. The magnetron sputtering is a simple, fast film. The depositionmethod, which can deposit doped silicon thin films without the usage of toxic or flammable gases, instead,use the polycrystalline as target to deposit films by Ar+sputtering．Compared to other film-depositiontechniques, the magnetron sputtering is a promising silicon thin film solar cells fabricating method for itshigh deposition rate and thus induced captivating economic efficiency. In the eyes of the author, thismethod is hopeful to reduce the cost of solar cells dramatically.
With the further research into the third generation solar cells—thin film solar cells, to fabricate highquality polycrystalline silicon(poly-Si)thin films is a most straight approach to improve the photovoltaicconversion efficiency. In this thesis, the fabrication of high quality poly-Si thin films is investigated．In thisdissertation, poly-Si thin films were successfully fabricated using aluminum induced crystallization (AIC).At the start, amorphous silicon(a-Si)thin films were prepared by the radiofrequency magnetron sputteringon glass substrates, after that, aluminum thin film Was deposited over a-Si min films using theradiofrequency magnetron sputtering, then the samples were annealed in Ar atmosphere with variousannealing parameters．The silicon thin films deposited by the magnetron sputtering are characterized byAFM and X-ray diffraction before and after annealing．
引文
[1] Hamakawa Y. Solar PV energy conversion and the21st century's civilization. Solar Energy[J] Materialsand Solar Cells.2002:345-352
[2] Green M. A. Photovoltaics: coming of age: Photovoltaic Specialists Conference[C], Conference Recordof the Twenty First IEEE Photovoltaic Specialists Conference1990,5:1-8
[3] Chapin D. M., Fuller C.S., Pearson G. L., A New Silicon P-N Junction Photocell for Converting SolarRadiation into Electrical Power[J]. Journal of Applied Physics.1954,1:676-677
[4]高敏苓，贾金平，宋文华，薄膜太阳能电池的研究现状与分析[J].资源节约与保护.2011，4：68-69
[5] Jeffrey yang，Baojie yan, Subhendu Guha. Amorphous and nanocrystalline silicon-based multi-junctionsolar cells[J].Thin solid films，2005,487：162-169
[6]刘本锋.磁控溅射法沉积硅薄膜的研究[D].武汉:武汉理工大学，2009,5：5-6
[7] Rech B. Wangner H. Potential of amorphous silicon for solar cells[J]. Applied physics A.1999,69:155-167
[8]雷勇泉,万群.新能源材料[M].天津:天津大学出版社，2000:58-62
[9]林鸿溢.非晶硅和微晶硅的生长机理与结构模型研究[J].电子显微学报.2005，3：46-52
[10] Jeffrey yang, Arindam banerjec,Subbendu guha. Amorphous silicon based photovoltaic from earth tothe ‘final frontier’[J]. Solar energy materials＆solarcells.2003,78:597-612.
[11]陈治明.非晶态半导体材料与器件[M].北京：科学出版社。1991：67-70
[12]布罗德斯基M.M.，朱琼瑞，余秉才等.非晶态半导体[M].北京：国防工业出版社，1985：36-74
[13]毛友德.非晶态半导体[M].上海：上海交通大学出版社，1986：56
[14] R Martins Fcrnira H. et al. Engineering of a-Si:H device stability by suitable of interface[J]. Solarenergy materials＆solar cells,2002,73(I)
[15]黄创君，林璇英，林揆训等.低温制备高质量多晶硅薄膜技术及其应用[J].功能材料，2001，32（6）：561-563
[16] Konno T.J. Sinclair R. Crystallization of silicon in aluminum/amorphous-silicon multilayers[J]. Philos.Mag. B,1992(66):749-765
[17]刘刚，余岳辉，史济群等.半导体器件、敏感、光子微波器件[M].北京：电子工业出版社，2004：198
[18]曲喜新，杨邦朝，姜节俭，张怀武.电子薄薄膜材料[M].北京：科学出版社，1989：304
[19]许开方.高效单晶硅硅太阳电池工艺技术之研究[J].新能源，1994，4：16
[20]刘恺.非晶硅薄膜太阳电池光电转换效率的数值研究[D].硕士学位论文，宁夏大学，2010,3：7
[21]黄锡坚.硅太阳电池及其应用[M].北京：北京铁道出版社，1985：38-39
[22] Shah A, Torres P, Tschamer R, et. Photovoltaic Technology[J]. The Case for Thin-Film Solar Cells.Science,1999,7:692-698
[23]田民波。薄膜技术与薄膜材料（M）北京：清华大学出版社，2006：484-516
[24]刘本锋.磁控溅射法沉积硅薄膜的研究[D].武汉：武汉理工大学，2009,5：17
[25]郑伟涛.薄膜材料与薄膜技术[M].北京：化学工业出版社，2004:68-99
[26]王力衡，黄运添，郑伟涛.薄膜技术[M].北京：清华大学出版社,1991:18
[27] Klein S. Microcrystalline silicon prepared by Hot Wire CVD-preparation and characterization ofmaterial and solar cells.[PhD thesis][M].TechnischeUneversity,2004:893-908
[28] Kunru M. Development of thin-film Cu(In,Ga)Se2and CdTe solar cells[J] Thin Solid Films.1991,(198):75
[29] Ruckh M． Hariskos D． Rfihle U． et al. Applications of ZnO in Cu(In,Ga)Se2sloarcells[R]．Proceeding of the25th IEEE Photovoltaic Specialists Conference(IEEE，Washington，D．C．，1996):825
[30] Veprek,.S.Sarott F. Iqbal A Z.Effect of grain boundaries on the Raman spectra, optical absorption, andelastic light scattering in nanometer-sized crystalline,[J].Phys. Rev. B,1987(36):3344-3350
[31] Webb J.B．Effect of hydrogen on the deposition rate for planar rf magnetron sputtering ofhydrogenated amorphous silicon[J]．Appl．Phys，1982，53：9043．
[32] Savvides..N. Deposition parameters and film properties of hydrogenated amorphous silicon preparedby high rate dc planar magnetron reactive sputtering,[J]．Appl．Phys，1984，55：4232
[33] Girginoudi Girginoudi,.D. Thanailakis S.A. et al. Stability of structural defect of polycrystallinesilicon grown by rapid thermal annealing of amorphous silicon films[J]. Thin SolidFilms,1995,268(1):1-4
[34] CorradoSpinella, Salvatore Lombardo. Crystal grain nucleation in amorphous silicon[J]. Journal ofApplied Physics,1998,84(10):5383-5412
[35] Brotherton.S.D. Ayres J.R. Edwards M.J. et al. Laser crystallized poly-Si TFTs for AMLCDs[J]. ThinSolid Films,1999,337:189-195
[36] Nast,.O. Hartmann A.J. Influence of interface and Al structure on layer exchange duringaluminum-induce crystallization of amorphous silicon[J]. Appl. Phys.,2000,(88):716-724
[37] Hultman L. A. Robertsson, H.T Hentzell G. I.Engstr m, Psaras P.A. Crystallization of amorphoussilicon during thin-film gold reaction, J.Appl.Phys,1987(62):3647-3655
[38] Konno T..Sinclair J.R Metal-contact Induced Crystallization of Semiconductors, Mater.Sci.Eng.A.,Al179/Al180,1994:426-432
[39] Jang J. Oh J.-Y. Kim S.-K. Choi Y.-J..Yoon S.-Y Kim C.-O.Electric-field-enhanced crystallization ofamorphous silicon, Nature,1998(395):481-483
[40] Jinz, Bhat G A, Yeung M, et al. Nickel induced crystallization of amorphous silicon thin films[J].J.Appl. Phys,1998,84(1):194-200
[41] Kishore R. Hotz C. Naseem H.H. et al. Aluminum-Induced Crystallization of AmorphousSilicon(a-Si:H) at150℃[J].Electrochemical and Solid-State Letters,2001,4(2):14-16
[42] J.Schneider, J.Klein, M.Muske, et al. Aluminum-induced crystallization of amorphous silicon:preparation effect on growth kinetics [J]. Journal of Non-crystalline Solids,2004,338-340:127-130
[43] E. pihan, A. Slaoui, P. RocaiCabarrocas et al. Polycrystalline silicon films byaluminum-induced crystallization: growth process vs. silicon deposition method [J]. Thin Solid Films,2004,451-452:328-333
[44] W. Cai, D. Wan. Induced crystallization of amorphous silicon film in contact with aluminum, ThinSolid Films,1992,219:1-3
[45]黄国银.多晶硅薄膜的制备和表征[D].浙江：浙江大学，2006：9-14
[46]张塍.等离子清洗的应用与技术[J].电子工业专用设备，2006，6：21-27
[47] Terrence G. Vargo,Patrick M. Thompson, Louis J. Gerenser,et al．Monolayer Chemical Lithographyand Characterization ofFluoropolymer Films. Langmuir1992,8,:130-134
[48] T. Ochiai, M. Kiboku, Y Iriyama et al. Formation of Methanol by Microwave-Plasma Reduction ofCO2with H2O[J]. Thin Solid Film,1996,287:169
[49] Kang E. T. Tan K. L. Surface Modification and Functionalization of Polytetrafluoroethylene Films[J].Macromolecules,1996,29(21):6872–6879
[50] Momose, Y., Tamura, Y., Ogino, M., et al. Chemical reactivity between Teflon surfaces subjected toargon plasma treatment and atmospheric oxygen[J]. Journal of Vacuum Science&Technology A:Vacuum, Surfaces, and Films,1992,10(1):229-238
[51] Piekoszewki J., Werner Z., Langner J. et al. Modification of the surface properties of materials bypulsed plasma beams[J]. Surface and Coatings Technology,1998,106:228-233
[2] Green M. A. Photovoltaics: coming of age: Photovoltaic Specialists Conference[C], Conference Recordof the Twenty First IEEE Photovoltaic Specialists Conference1990,5:1-8
[3] Chapin D. M., Fuller C.S., Pearson G. L., A New Silicon P-N Junction Photocell for Converting SolarRadiation into Electrical Power[J]. Journal of Applied Physics.1954,1:676-677
[4]高敏苓，贾金平，宋文华，薄膜太阳能电池的研究现状与分析[J].资源节约与保护.2011，4：68-69
[5] Jeffrey yang，Baojie yan, Subhendu Guha. Amorphous and nanocrystalline silicon-based multi-junctionsolar cells[J].Thin solid films，2005,487：162-169
[6]刘本锋.磁控溅射法沉积硅薄膜的研究[D].武汉:武汉理工大学，2009,5：5-6
[7] Rech B. Wangner H. Potential of amorphous silicon for solar cells[J]. Applied physics A.1999,69:155-167
[8]雷勇泉,万群.新能源材料[M].天津:天津大学出版社，2000:58-62
[9]林鸿溢.非晶硅和微晶硅的生长机理与结构模型研究[J].电子显微学报.2005，3：46-52
[10] Jeffrey yang, Arindam banerjec,Subbendu guha. Amorphous silicon based photovoltaic from earth tothe ‘final frontier’[J]. Solar energy materials＆solarcells.2003,78:597-612.
[11]陈治明.非晶态半导体材料与器件[M].北京：科学出版社。1991：67-70
[12]布罗德斯基M.M.，朱琼瑞，余秉才等.非晶态半导体[M].北京：国防工业出版社，1985：36-74
[13]毛友德.非晶态半导体[M].上海：上海交通大学出版社，1986：56
[14] R Martins Fcrnira H. et al. Engineering of a-Si:H device stability by suitable of interface[J]. Solarenergy materials＆solar cells,2002,73(I)
[15]黄创君，林璇英，林揆训等.低温制备高质量多晶硅薄膜技术及其应用[J].功能材料，2001，32（6）：561-563
[16] Konno T.J. Sinclair R. Crystallization of silicon in aluminum/amorphous-silicon multilayers[J]. Philos.Mag. B,1992(66):749-765
[17]刘刚，余岳辉，史济群等.半导体器件、敏感、光子微波器件[M].北京：电子工业出版社，2004：198
[18]曲喜新，杨邦朝，姜节俭，张怀武.电子薄薄膜材料[M].北京：科学出版社，1989：304
[19]许开方.高效单晶硅硅太阳电池工艺技术之研究[J].新能源，1994，4：16
[20]刘恺.非晶硅薄膜太阳电池光电转换效率的数值研究[D].硕士学位论文，宁夏大学，2010,3：7
[21]黄锡坚.硅太阳电池及其应用[M].北京：北京铁道出版社，1985：38-39
[22] Shah A, Torres P, Tschamer R, et. Photovoltaic Technology[J]. The Case for Thin-Film Solar Cells.Science,1999,7:692-698
[23]田民波。薄膜技术与薄膜材料（M）北京：清华大学出版社，2006：484-516
[24]刘本锋.磁控溅射法沉积硅薄膜的研究[D].武汉：武汉理工大学，2009,5：17
[25]郑伟涛.薄膜材料与薄膜技术[M].北京：化学工业出版社，2004:68-99
[26]王力衡，黄运添，郑伟涛.薄膜技术[M].北京：清华大学出版社,1991:18
[27] Klein S. Microcrystalline silicon prepared by Hot Wire CVD-preparation and characterization ofmaterial and solar cells.[PhD thesis][M].TechnischeUneversity,2004:893-908
[28] Kunru M. Development of thin-film Cu(In,Ga)Se2and CdTe solar cells[J] Thin Solid Films.1991,(198):75
[29] Ruckh M． Hariskos D． Rfihle U． et al. Applications of ZnO in Cu(In,Ga)Se2sloarcells[R]．Proceeding of the25th IEEE Photovoltaic Specialists Conference(IEEE，Washington，D．C．，1996):825
[30] Veprek,.S.Sarott F. Iqbal A Z.Effect of grain boundaries on the Raman spectra, optical absorption, andelastic light scattering in nanometer-sized crystalline,[J].Phys. Rev. B,1987(36):3344-3350
[31] Webb J.B．Effect of hydrogen on the deposition rate for planar rf magnetron sputtering ofhydrogenated amorphous silicon[J]．Appl．Phys，1982，53：9043．
[32] Savvides..N. Deposition parameters and film properties of hydrogenated amorphous silicon preparedby high rate dc planar magnetron reactive sputtering,[J]．Appl．Phys，1984，55：4232
[33] Girginoudi Girginoudi,.D. Thanailakis S.A. et al. Stability of structural defect of polycrystallinesilicon grown by rapid thermal annealing of amorphous silicon films[J]. Thin SolidFilms,1995,268(1):1-4
[34] CorradoSpinella, Salvatore Lombardo. Crystal grain nucleation in amorphous silicon[J]. Journal ofApplied Physics,1998,84(10):5383-5412
[35] Brotherton.S.D. Ayres J.R. Edwards M.J. et al. Laser crystallized poly-Si TFTs for AMLCDs[J]. ThinSolid Films,1999,337:189-195
[36] Nast,.O. Hartmann A.J. Influence of interface and Al structure on layer exchange duringaluminum-induce crystallization of amorphous silicon[J]. Appl. Phys.,2000,(88):716-724
[37] Hultman L. A. Robertsson, H.T Hentzell G. I.Engstr m, Psaras P.A. Crystallization of amorphoussilicon during thin-film gold reaction, J.Appl.Phys,1987(62):3647-3655
[38] Konno T..Sinclair J.R Metal-contact Induced Crystallization of Semiconductors, Mater.Sci.Eng.A.,Al179/Al180,1994:426-432
[39] Jang J. Oh J.-Y. Kim S.-K. Choi Y.-J..Yoon S.-Y Kim C.-O.Electric-field-enhanced crystallization ofamorphous silicon, Nature,1998(395):481-483
[40] Jinz, Bhat G A, Yeung M, et al. Nickel induced crystallization of amorphous silicon thin films[J].J.Appl. Phys,1998,84(1):194-200
[41] Kishore R. Hotz C. Naseem H.H. et al. Aluminum-Induced Crystallization of AmorphousSilicon(a-Si:H) at150℃[J].Electrochemical and Solid-State Letters,2001,4(2):14-16
[42] J.Schneider, J.Klein, M.Muske, et al. Aluminum-induced crystallization of amorphous silicon:preparation effect on growth kinetics [J]. Journal of Non-crystalline Solids,2004,338-340:127-130
[43] E. pihan, A. Slaoui, P. RocaiCabarrocas et al. Polycrystalline silicon films byaluminum-induced crystallization: growth process vs. silicon deposition method [J]. Thin Solid Films,2004,451-452:328-333
[44] W. Cai, D. Wan. Induced crystallization of amorphous silicon film in contact with aluminum, ThinSolid Films,1992,219:1-3
[45]黄国银.多晶硅薄膜的制备和表征[D].浙江：浙江大学，2006：9-14
[46]张塍.等离子清洗的应用与技术[J].电子工业专用设备，2006，6：21-27
[47] Terrence G. Vargo,Patrick M. Thompson, Louis J. Gerenser,et al．Monolayer Chemical Lithographyand Characterization ofFluoropolymer Films. Langmuir1992,8,:130-134
[48] T. Ochiai, M. Kiboku, Y Iriyama et al. Formation of Methanol by Microwave-Plasma Reduction ofCO2with H2O[J]. Thin Solid Film,1996,287:169
[49] Kang E. T. Tan K. L. Surface Modification and Functionalization of Polytetrafluoroethylene Films[J].Macromolecules,1996,29(21):6872–6879
[50] Momose, Y., Tamura, Y., Ogino, M., et al. Chemical reactivity between Teflon surfaces subjected toargon plasma treatment and atmospheric oxygen[J]. Journal of Vacuum Science&Technology A:Vacuum, Surfaces, and Films,1992,10(1):229-238
[51] Piekoszewki J., Werner Z., Langner J. et al. Modification of the surface properties of materials bypulsed plasma beams[J]. Surface and Coatings Technology,1998,106:228-233