Copper indium gallium diselenide (CIGS), which is cheap and has high efficiency, is one of the potential alternative energy. Moreover, Cd-free materials which are used to replace the CdS buffer layer is expected to solve the problem of environmental safety. In this thesis, we devote the research to replace the toxic material with ZnS buffer layer and to reach the near efficiency devices which use the CdS buffer layer. It is divided into three parts. In the first part, effects of CBD process on ZnS film properties are discussed. In the second part, effects of the precursor NH3 concentration on ZnS film properties and the defects on PN junction are discussed. In the final part, completing the devices with ZnS buffer layer and discussing the effects of light soaking and RTA. In this circumstance, the devices with ZnS buffer layer which almost achieve the efficiency with CdS-based device.

銅銦鎵硒太陽能電池以低成本及高效率的優點成為極具發展潛力的替代再生能源，並且目前希望發展無鎘製程材料取代原本的硫化鎘緩衝層，以解決環境安全問題。本實驗中致力於使用硫化鋅緩衝層取代原本的有毒材料，期望達到相同效率的元件。本論文主要分為三部份：第一部份為探討化學浴沉積法中製程及參數的差異對於薄膜性質的影響；第二部份藉由前趨物氨水濃度的調變，探討薄膜性質於材料特性上的差異以及形成PN二極體時缺陷對於元件的影響；第三部份為硫化鋅緩衝層製作成完整元件，量測其效率，並探討Light soaking及退火對於元件效率的影響，而將硫化鋅緩衝層應用於銅銦鎵硒太陽能電池上，效率已可接近硫化鎘緩衝層所製作的元件。

參考文獻
[1] KRI Report No. 8 Solar cells 2005.
[2] http://ferekide.blog.usf.edu/background-of-cadmium-telluride-cdte-thin-film-photovoltatic-cells/
[3] Archer, M. D., The past and present. In: Clean electricity from photovoltaics. Imperial College Press: London, 2001; p 1-32.
[4] http://www.materialsnet.com.tw/DocPrint.aspx?id=8238
[5] Oregan, B.; Gratzel, M., Nature 1991, 353 (6364), 737-740.
[6] Bach, U.; Lupo, D.; Comte, P.; Moser, J. E.; Weissortel, F.; Salbeck, J.; Spreitzer, H.; Gratzel, M.; Nature 1998, 395 (6702), 583-585.
[7] http://usa.o.gp/
[8] Sze, S. M, Semiconductor Devices Physics and Technology, 2nd Edition, WILEY, 2001.
[9] Zhang, S. B.; Wei, S. H.; Zunger, A.; Katayama-Yoshida, H., Phys. Rev. B 1998, 57 (16), 9642-9656.
[10] Kronik, L.; Cahen, D.; Schock, H. W., Adv. Mater. 1998, 10 (1), 31
[11] Ishizuka, S.; Yamada, A.; Islam, M. M.; Shibata, H.; Fons, P.; Sakurai, T.; Akimoto, K.; Niki, S., J. Appl. Phys. 2009, 106 (3), 6.
[12] Contreras, M. A.; Tuttle, J.; Gabor, A.; Tennant, A.; Ramanathan, K.; Asher, S.; Franz, A.; Keane, J.; Wang, L.; Noufi, R., Sol. Energy Mater. Sol. Cells 1996, 41-2, 231-246.
[13] Schlenker, T.; Laptev, V.; Schock, H. W.; Werner, J. H., Thin Solid Films 2005, 480, 29-32.
[14] Contreras, M. A.; Egaas, B.; King, D.; Swartzlander, A.; Dullweber, T., Thin Solid Films 2000, 361, 167-171.
[15] Contreras, M. A., PROGRESS IN PHOTOVOLTAICS: RESEARCH AND APPLICATIONS 1999, 7, 6.
[16] Park, J. S.; Dong, Z.; Kim, S.; Perepezko, J. H., J. Appl. Phys. 2000, 87 (8), 3683-3690.
[17] Canava, B.; Guillemoles, J. F.; Vigneron, J.; Lincot, D.; Etcheberry, A. In Chemical elaboration of well defined Cu(In,Ga)Se2 surfaces after aqueous oxidation etching, Pergamon-Elsevier Science Ltd: 2003; pp 1791-1796.
[18] Darga, A.; Mencaraglia, D.; Djebbour, Z.; Dubois, A. M.; Guillemoles, J. F.; Connolly, J. P.; Roussel, O.; Lincot, D.; Canava, B.; Etcheberry, A. In Two step wet surface treatment influence on the electronic properties of Cu(In,Ga)Se2 solar cells, Feb 2; Elsevier Science Sa: pp 2550-2553.
[19] Wei, S. H.; Zhang, S. B.; Zunger, A., Appl. Phys. Lett. 1998, 72 (24), 3199-3201.
[20] DS, A., MATER RES SOC S P 1991, 228, 267.
[21] Wei, S. H.; Zunger, A., J. Appl. Phys. 1995, 78 (6), 3846-3856.
[22] D. J. Schroeder, J. L. H., G. D. Berry, and A. A. Rockett In hole concentration increases due to incorporation of Ga, Proceedings of the 11th International Conference on Ternary and Multi- nary Compounds, New York, New York.
[23] W. N. Shafarman, R. K., and B. E. McCandless In efficiency increases when Ga is 0~0.3, Proceedings of the 25th IEEE Photovoltaic Specialists Conference, New York, New York, 1996; p 763.
[24] M. A. Contreras, H. W., D. Niles, K. Ramanathan, R. Matson, J. Tuttle, J. Keane, and R. Nouf In efficiency decreases when Ga > 0.3, Proceedings of the 25th IEEE Photovoltaic Specialists Conference, New York, New York, 1996; p 809.
[25] Contreras, M. A.; Noufi, R. In Chalcopyrite Cu(In,Ga)Se2 and defect-chalcopyrite Cu(In,Ga)3Se5 materials in photovoltaic P-N junctions, Apr; Elsevier Science Bv: pp 283-288.
[26] Anant, H., Proceedings of the 32th IEEE Photovoltaic Specialists Conference 2006, 557.
[27] Rau, U.; Schmidt, M., Thin Solid Films 2001, 387 (1-2), 141-146.
[28] Rothwarf, A. D. a. A., Proceedings of the 23th IEEE Photovoltaic Specialists Conference 1993, 475
[29] Hegedus, S. S.; Shafarman, W. N., Prog. Photovoltaics 2004, 12 (2-3), 155-176.
[30] Akinmasa Yamada, H. T., Koji Matsubara, Shigeru Niki, Keiichiro Sakurai, Shogo Ishizuka, Kakuya Iwata Compound solar cell and process for producing the same. 2005.
[31] Hariskos, D.; Ruckh, M.; Ruhle, U.; Walter, T.; Schock, H. W.; Hedstrom, J.; Stolt, L., Sol. Energy Mater. Sol. Cells 1996, 41-2, 345-353.
[32] T. Negami, T. A., T. Satoh, S. Shimakawa, S. Hayashi, Y. Hashimoto Proceedings 29th IEEE Photovoltaic Specialist Conference, New Orleans, USA, New Orleans, USA, 2002; p 656.
[33] A. Romeo, R. G., S. Buzzi, D. Abou-Ras, D.L. Batzner, D. Rudmann, H. Zogg, A.N. Tiwari Proceedings 14th IEEE Photovoltaic Specialist Conference, Bangkok, Thailand, Bangkok, Thailand, 2004; p 705.
[34] Ohtake, Y.; Kushiya, K.; Ichikawa, M.; Yamada, A.; Konagai, M., Jpn. J. Appl. Phys. Part 1 - Regul. Pap. Short Notes Rev. Pap. 1995, 34 (11), 5949-5955.
[35] C. Platzer-Bjorkman, J. K., L. Stolt In Atomic layer deposition of Zn(O,S) buffer layers for high efficiency Cu(In,Ga)Se-2 solar cells, PROCEEDINGS OF 3RD WORLD CONFERENCE ON PHOTOVOLTAIC ENERGY CONVERSION, Osaka, Japan, Osaka, Japan, 2003; p 461.
[36] Naghavi, N.; Spiering, S.; Powalla, M.; Cavana, B.; Lincot, D., Prog. Photovoltaics 2003, 11 (7), 437-443.
[37] Rusu, M.; Glatzel, T.; Neisser, A.; Kaufmann, C. A.; Sadewasser, S.; Lux-Steiner, M. C., Appl. Phys. Lett. 2006, 88 (14), 3.
[38] Glatzel, T.; Rusu, M.; Sadewasser, S.; Lux-Steiner, M. C., Nanotechnology 2008, 19 (14), 7.
[39] Hariskos, D.; Spiering, S.; Powalla, M., Thin Solid Films 2005, 480, 99-109.
[40] D. Lincot, R. O.-B., J. Vedel, M. Ruckh, J. Kessler, K. O. Velt- haus, D. Hariskos, and H. W. Schock In etching by ammonia, Proceedings of the 11th European Photovoltaic Solar Energy Conference, Montreux (Harwood Acdemic, Chur, Switzerland), Montreux (Harwood Acdemic, Chur, Switzerland), 1992; p 870.
[41] J. Vidal, O. Vigil, O. de Melo, N. Lopez, O. Zelaya-Angel, Materials Chemistry and Physics 61 (1999) 139-142
[42] C. Cruz-Vazquez, F. Rocha-Alonzo, S.E. Burruel-Ibarra, M. Barboza-Flores, R. Bernal, M. Inoue, Appl. Phys. A 79, 1941-1945 (2004)
[43] Jie Cheng, DongBo Fan, Hao Wang, BingWei Liu, YongCai Zhang and Hui Yan, Semicond. Sci. Technol. 18 (2003) 676-679
[44] F. Gode, C. Gumus, M. Zor, Journal of Crystal Growth 299 (2007) 136-141
[45] http://zh.wikipedia.org/wiki/%E7%A1%AB%E5%8C%96%E9%94%8C
[46] Alireza Goudarzi, Ghaffar Motedayen Aval, Reza Sahraei, Hiva Ahmadpoor, Thin Solid Films 516 (2008) 4952-4957
[47] Katsumi Kushyia, Osamu Yamase, Jpn. J. Appl. Phys. Vol. 39 (2000) pp. 2577-2582
[48] Paul O’Brien, John McAleese, J. Mater. Chem., 1998 8(11), 2309-2314
[49] C. Guillen, M.A. Martinez, J Herrero, Thin solid films 339 (1999) 148-153
[50] Reza Sahraei, Ghaffar Motedayen Aval, Alireza Goudarzi, Journal of Alloys and Compounds 466 (2008) 488-492
[51] 劉庭芝, 多樹旺, 張萌, 向軍淮, 張榮發, 胡長員, 朱世峰, 中國有色金屬學報, Vol. 19 N0.9
[52] Qi Liu, Mao Guobing, Ao Jianping, Applied Surface Science 254 (2008) 5711-5714
[53] Y.Zhang, X.Y. Dang, J. Jin, T. Yu, B.Z. Li, Q. He, F.Y. Li, Y. Sun, Applied Surface Science 256 (2010) 6871-7875
[54] Poulomi Roy, Jyoti R. Ota, Suneel Kumar Srivastava, Thin Solid Films 515 (2006) 1912-1917
[55] Schmid, D.; Ruckh, M.; Grunwald, F.; Schock, H. W., J. Appl. Phys. 1993, 73 (6), 2902-2909.
[56] Kylner, A. The Role of CdS Buffer Layer in the Cu(In,Ga)Se2 Thin Film Solar Cell. Uppsala University, 1998.
[57] J. Kessler, M. R., D. Hariskos, U. Ruhle, R. Menner, H.W. Schock In etching by ammonia, Proceedings of the 23th IEEE Photovoltaic Specialists Conference, Louisville, KY, Louisville, KY, 1993; p 447.
[58] Tokio Nakada, Masayuki Mizutani, “Improved Efficiency of Cu(In,Ga)Se2 Thin Film Solar Cells with Chemically Deposited ZnS Buffer Layer by Air-annealing Formation of Homojunction by Solid Phase Diffusion” 2000 IEEE
[59] Sambhu Kundu, Larry C. Olsen, Thin Solid Films 471 (2005) 298-303
[60] Schmid, D.; Ruckh, M.; Schock, H. W., Sol. Energy Mater. Sol. Cells 1996, 41-2, 281-294.
[61] Contreras, M. A.; Wiesner, H.; Tuttle, J.; Ramanathan, K.; Noufi, R., Sol. Energy Mater. Sol. Cells 1997, 49 (1-4), 239-247.
[62] Romero, M. J.; Jones, K. M.; AbuShama, J.; Yan, Y.; Al-Jassim, M. M.; Noufi, R., Appl. Phys. Lett. 2003, 83 (23), 4731-4733.
[63] Kijima, S.; Nakada, T., Appl. Phys. Express 2008, 1 (7), 3.
[64] R.N. Bhattacharya, K. Ramanathan, Solar Energy 77 (2004) 679-683
[65] D. Hariskos, S. Spiering, M. Powalla, Thin Solid Film 480-481 (2005) 99-109
[66] A.O. Pudov, J.R. Sites, M.A. Contreras, T. Nadaka, H.W. Schock, Thin Solid Films 480-481 (2005) 273-278
[67] M. Bar, A. Ennaoui, J. Kiaer, T.Kropp, R. Saez-Araoz, N. Allsop, I. Lauermann, H.W. Schock, M.C. Lux-Steiner, Journal of Applied Physics 99, 123503 (2006)
[68] B.C. Lin, P. Shen, S.Y. Chen, J. Phys. Chem. C 2011, 115, 5003-5010