本實驗是以分層電鍍銅，銦，硒三種元素在鉬基板上來作為研究。首先本實驗發現電鍍銦在銅薄膜上時，會產生銅銦相與銦相共存，並且銦有聚集的現象。所以此時本實驗的研究目標分成了兩個部份來探討CIS不同反應機構的研究，第一個部份則是阻止銅銦相的生成，本實驗嘗試在銅薄膜上電鍍上硒後再電鍍銦，並且研究最佳的電鍍硒秒數能夠成功阻擋銅銦相的產生，並且探討一階段式熱處理與二階段式熱處理對於合成CIS薄膜的影響。第二個部份為走CIS反應機制的Type-III，先合成出穩定的Cu11In9化合物，再此化合物上電鍍一層硒。實驗研究不同的RTA熱處理溫度與持溫時間對CIS薄膜的影響，利用FE-SEM來觀察CIS薄膜表面的微結構變化，XRD來分析CIS的結晶性，並用拉曼來做輔助有無雜相的存在。
實驗結果顯示以Cu11In9為初始相的CIS薄膜，其CIS的晶粒是比較大的，大約是在3μm~4μm之間。然而實驗結果也發現走這個路徑必須要用較高的RTA溫度，這樣所合成出的薄膜空洞與雜相會比較少。而本實驗也成功找出了電鍍硒的參數能夠成功阻擋銅銦相的產生。實驗發現利用兩階段式熱處理對於此路徑所合成出的CIS結構有很大的變化。實驗最後嘗試把整個元件製作出來，並且利用IV curve的測量，來研究元件中各層的鍍膜對於整個元件PN接面的影響。

In the research, we found the existence of Cu-In phase while electrodepositing indium onto copper layer. Therefore, our experiment separated into two routes. The first route was to prevent the formation of Cu-In phase by electrodepositing a selenium thin film between the Cu and In layer. The effect of two steps thermal treatment was also took into discussion in route two. The second route was to form steady Cu11In9 compound following an electrodeposition of selenium layer, and through RTA process we obtained a stiochiometric CuInSe2 compound. Furthermore, we study the effect of RTA temperature on the microstructure of CuInSe2 thin films. The crystal structure of the thin films was identified by powder x-ray diffraction (XRD). Raman spectroscopy was applied for analysis of second phases. The microstructure was observed by scanning electron microscope (SEM).
The SEM image of Cu11In9 thin films showed that the grain size was about 3μm~4μm. And we also found that higher temperature was need in route one to form CuInSe2 thin films of good quality. In route two, electrodeposited selenium with enough thickness could prevent the formation of Cu-In phase, and the film quality became better through two steps thermal treatment. By IV curve measurement we understood the characteristic of PN junction in the cell.

[1] D. Lidgate, Engineering Science and Education Journal, 1,221-227, (1922).
[2] 楊宏澤,”太陽能發電系統與工程上課講義”,2008
[3] 邱秋燕,廖曰淳,楊慕震,黃渼雯,羅一玲,銅銦鎵硒太陽電池-非真空製程技術發展簡介,工業材料雜誌,264, (2008)
[4] Yang, J., et al., Recent progress in amorphous silicon alloy leading to 13% stable cell efficiency. 26 PVSC, 563-568, (1997)
[5] Mitchell, K.W., et al., CuInSe2 cells and modules, IEEE transaction on electron devices, 37, 410-417, (1990).
[6] Dimmler, B., M. Powalla, and H.W. Schock, CIS-based thin film photovoltaic modules: Potential and prospects. Prog. Photovolt: Res. Appl., 10, 149-157, (2002).
[7] Chu, N. and D. Honeman, Solar cells, 31, 197(1991)
[8] S. Jost, F. Hergert, R. Hock, J. Schulze, A. Kirbs, T. VoX and M. Purwins, The formation of CuInSe2 thin film solar cell absorbers from electroplated precursors with varying selenium content, Solar Energy Materials & Solar Cells, 91, 1669–1675 (2007)
[9] M. Gossla, H. Metzner, and H.-E. Mahnke, Coevaporated Cu–In films as precursors for solar cells, Journal of Applied Physics, 86, 3624-3632 (1999)
[10] K.T. Ramakrishna Reddy, I. Forbes, R.W. Miles, M.J. Carter and P.K. Dutta, Materials Letters, 37, 57–62 (1998)
[11] L. L. Kerr. S. Kim, S. Kincal. M. Ider, S. Yoon, and T. J. Anderson, IEEE, 0-7803-7471-1/02, 676-679 (2002)
[12] 陳譽升, “以分層電鍍銅銦硒薄膜製備二硒化銅銦太陽能電池之研究”, 成功大學 (2009)
[13] G. Sasikala, S. Moorthy Babu and R. Dhanasekaran, Electrocrystallization and characterization of CuInSe, thin films, Mater. Chem. Phys., 42, 210 (1995)
[14] M. Paunovic, M. Schlesinger, Fundamentals of electrochemical deposition, 2nd ed. (Wiley, New Jersey, 2006)
[15] 胡啟章, 電化學原理與方法, 1st ed. (五南圖書出版, 台北, 2002)
[16] S. Beyhan, S. Suzer, F. Kadırgana, Complexing agent effect on the stoichiometric ratio of the electrochemically prepared CuInSe2 thin films, Solar Energy Materials & Solar Cells, 91, 1922 (2007)
[17] Mitchell, K.W., et al., CuInSe2 cells and modules, IEEE transaction on electron devices, 37(2), 410-417, 1990.
[18] Adolf Goetzberger, Christopher Hebling, Photovoltaic materials, past, present, future, Solar Energy Materials & Solar Cells, 62, 1(2000)
[19] L. Kaupmees, M. Altosaar, O. olubujeva, E. Mellikov, Study of composition reproducibility of electrochemically co-deposited CuInSe2 films onto ITO, Thin Solid Films, 515,5891 (2007)
[20] R. Klenk, J. Klaer, R. Scheer, M.Ch. Lux-Steiner, I. Luck, N. Meyer, U. Rqhle, Solar cells based on CuInS2—an overview, Thin Solid Films, 509, 480–481(2005)
[21] 林明獻, 太陽電池入門技術, 2nd ed. (全華圖書股份有限公司, 台北, 2008)
[22] J. S. Park, Z. Dong, Sungtae Kim, and J. H. Perepezko, CuInSe2 phase formation during Cu2Se/In2Se3 interdiffusion reaction, Journal of Applied Physics, 87, 3683 (2000)
[23] N.B. Chaure, J. Young, A.P. Samantilleke and I.M. Dharmadasa, Electrodeposition of p–i–n type CuInSe2 multilayers for photovoltaic applications, Sol. Energy Mater. Sol. Cells, 81, 125 (2004)
[24] N.B. Chaure, A.P. Samantilleke, R.P. Burton, J. Young and I.M. Dharmadasa, Electrodeposition of p+, p, i, n and n+-type copper indium gallium diselenide for development of multilayer thin film solar cells, Thin Solid Films , 472, 212 (2005)
[25] F.O. Adurodija, J. Song, S.D. Kim, S.H. Kwon, S.K. Kim, S.H. Yoon and B.T. Ahn, Growth of CuInSe2 thin film by high vapour Se treatment of co-sputtered Cu-In alloy in a graphite container, Thin Solid Films, 338, 13-19 (1999)
[26] O. Volobujeva, M. Altosaar, J. Raudoja, E. Mellikov, M. Grossberg, L. Kaupmees and P. Barvinschi, SEM analysis and selenization of Cu–In alloy films produced by co-sputtering of metals, Solar Energy Materials & Solar Cells 93,11–14 (2009)
[27] T. L. Chu and Shirley S. Chu, Large Grain Copper Indium Diselenide Films, Solid-State Science and Technology, 131, 2182 (1984)
[28] Frederick Adurodija, Jinsoo Song, Seok Ki Kim, Ki Hwan Kang and Kyung Hoon Yoon, CuInSe2 Thin Films Prepared from High-Vapor Selenization of Co-sputtered Cu-In Precursor Layers, Journal of the Korean Physical Society, 32, 87-92 (1998)
[29] Sang Deok Kim and Hyeong Joon Kim, Characteristics of CuInSe2 Thin Films Grown by the Selenization Method, Journal of the Korean Physical Society, 35, 403-405 (1999)
[30] D. Braunger, D. Hariskos, G. Bilger, U. Rau and H.W. Schock, Influence of sodium on the growth of polycrystalline Cu(In,Ga)Se2 thin films, Thin Solid Films, 361, 161(2000)
[31] O. Roussel, O. Ramdani, E. Chassaing, P.P. Grand, M. Lamirand, A. Etcheberry, O. Kerrec, J.F. Guillemoles, and D. Lincota, First Stages of CuInSe2 Electrodeposition from Cu(II)-In(III)-Se(IV) Acidic Solutions on Polycrystalline Mo Films, Journal of The Electrochemical Society, 155, D141 (2008)
[32] T. P. Gujar, V. R. Shinde, Jong-Won Park, Hyun Kyung Lee, Kwang-Deog Jung and Oh-Shim Joo, Characterization of Electrochemically Grown Crystalline CuInSe2 Thin Films, Journal of The Electrochemical Society, 156, E8 (2009)
[33] A. Romeo, M.Terheggen, D.Abou-Ras, D.L.Batzner, F.-J.Haug, M.Kalin, D.Rudmann and A. N. Tiwari, Prog. Photovolt: Res. Appl., 12, 97 (2004)
[34] Capasso, F. and G. Maragaritondo, Heterojunction band, discontinuities: Physics and device application. Elsevier science (1987)
[35] 汪建民,材料分析,1st ed.(中國材料科學學會,新竹,1998)
[36] 林麗娟, X光繞射原理及其運用, 工業材料, 86, 101(1994)
[37] N.B. Chaure, A.P. Samantilleke, R.P. Burton, J. Young and I.M. Dharmadasa, Electrodeposition of p+, p, i, n and n+-type copper indium gallium diselenide for development of multilayer thin film solar cells, Thin Solid Films , 472, 212 (2005)
[38] A. D. L. Humphris, M. J. Miles, and J. K. Hobbs, A mechanical microscope, High-speed atomic force microscopy, Applied Physic Letters, 86, 034106 (2005)
[39] D.L.Simth, Chap10 Film Analysis, Thin Film Deposition, (McGraw-Hill, New York, USA, 1995)
[40] J. Łaz ˙ewski, H. Neumann, K. Parlinski, G. Lippold, B. J. Stanbery, Lattice dynamics of CuAu-ordered CuInSe2, Physical Review, 68, 144108 (2003)
[41] J. Parkes, R.D. Tomlinson, and M.J. Hampshire, J. Appl. Crystal-logr. 6, 414, (1973)
[42] H.W. Spiess, V. Haeberlen, G. Brandt, A. Ra ¨uber, and J.Schneider, Phys. Status Solidi B , 62, 183 (1974)
[43] J. M. Merino, J.L. Martin de Vidales, S. Mahanty, R. Diaz and F.Rueda, J. Appl. Phys., 80, 5610 (1996)
[44]O. A.Balitskii, V. P. Savchyn and V. O. Yukhymchuk, Semicond. Sci. Technol., 17, 1-4 (2002)
[45] Víctor Izquierdo-Roca1, Edgardo Saucedo, Phys. Status Solidi, 206, 1001 –1004 (2009)