臺灣博碩士論文加值系統

本篇論文主要利用三源共蒸鍍方式，成長 CuInSe2 (簡稱CIS) 主吸收層，並利用鈉玻璃薄膜作為絕緣層，觀察鈉擴散對於CIS的影響，以及於不鏽鋼基板上製作完整可撓式薄膜式太陽電池，元件結構為Al/ZnO:Al/ZnO/CdS/CuInSe2/Mo/SLGTF/Stainless Steel。
本實驗利用基板採用不銹鋼薄片，並鍍上鈉玻璃薄膜(soda lime glass)做為絕緣層及防止擴散層(Diffusion barrier)，並同時作為鈉的擴散來源，並分析CIS在無鈉基板及含鈉基板的微結構與電性差異。並於不銹鋼基板上製作CIS太陽電池。鉬背電極 (Mo)與不鏽鋼基板之間以交流濺鍍方式鍍上鈉玻璃薄膜做為絕緣層；Mo為低應力且低電阻薄膜，採用直流磁控濺鍍方式鍍製；CIS主吸收層在分子束蒸鍍系統(MBE)中採用兩階段共蒸鍍成膜；硫化鎘(CdS)緩衝層(buffer layer)採用化學水浴法來鍍製；氧化鋅(ZnO)與氧化鋅(ZnO:Al)透明導電層(window layer)以交頻磁控濺鍍方式鍍製；再以直流磁控濺鍍鋁(Al)電極完成元件。在同一個製程下以鈉玻璃薄膜取代氧化矽薄膜作為絕緣層，其開路電壓與短路電流密度上的改善：開路電壓提升16.7 %，短路電流密度提高9.8%。

This paper describes an investigation into the fabrication of absorber layer CuInSe2 films by co-evaporation process. And we used the stainless steel substrates to manufacture Al / ZnO:Al / ZnO /CdS / CuInSe2 / Mo / SLGTF / Stainless Steel(SS) flexible thin-film solar cell.
The flexible solar cells were fabricated using soda-lime glass thin layers (SLGTL) as a diffusion barrier layer and an alkali source material deposited on various flexible substrates prior to the Mo backcontact layer deposition. Mo back contact layers were deposited by DC sputtering. The CIS absorber layers were grown by the two-stage process using a molecular beam epitaxy (MBE) apparatus. Then the CdS buffer layer was deposited by the chemical bath, RF sputter deposition of intrinsic ZnO and ZnO:Al (AZO) layer. Under the same process condition, using SLGTF as diffusion barrier layer improved open circuit voltage (Voc) 16.7% and short circuit current density (Jsc) 9.8%.

第一章 簡介 1
1.1前言 1
1.2 CuInSe2太陽電池之研究發展 4
1.3 CuInSe2薄膜性質 5
1.4元件設計分析與探討 9
1.4.1元件結構設計 9
1.4.2 元件轉換效率之基本參數 13
1.4.3基板與各層薄膜之特性 14
1.5 研究目的 25
第二章 薄膜製程系統、實驗步驟與分析儀器 29
2.1 薄膜製程系統 29
2.1.1 三槍磁控濺鍍系統： 29
2.1.2 共焦磁控濺鍍系統： 30
2.1.3 分子束蒸鍍系統 (Molecular Beam Deposition) 31
2.2 元件製造流程與步驟 33
2.2.1 不銹鋼基板之處理 34
2.2.2 鈉玻璃薄膜之鍍製 35
2.2.3 鉬薄膜之鍍製 35
2.2.4 共蒸鍍成長CIS薄膜 36
2.2.5 CdS之鍍製 37
2.2.6 ZnO之鍍製 37
2.2.7 ZnO:Al之鍍製 38
2.2.8 鋁金屬電極成長 38
第三章 薄膜特性分析方法與儀器 39
3.1 X-ray 繞射儀 39
3.2掃描式電子顯微鏡 (SEM) 39
3.3霍爾量測 (Hall measurement) 39
3.4四點探針 (Four-point probe) 40
3.5熱探針量測 (Hot probe) 41
3.6吸收光譜儀 (Spectrophotometer) 42
3.7反射光譜儀 (Spectral reflectance measurement) 42
3.8電流-電壓特性曲線量測 (I-V measurement) 43


第四章 實驗結果與討論 44
4.1 不鏽鋼基板 44
4.2 鈉玻璃之鍍製 44
4.3 Mo金屬背電極 48
4.4 CuInSe2主吸收層 51
4.5 CdS 緩衝層 62
4.6 ZnO透光層 67
4.7 AZO透光層 68
4.8元件之製作與元件量測 70
第五章 結論 74
第六章 參考文獻 76

1.K. Zweibel, Harnessing Solar Power, The Photovoltaics Challenge, Plenum Press, New York (1990)
2.H.J. MŐller, Semiconductor solar cell, Artech House, Boston ∙ London, Ch.2 , (1993)p.41
3.R. Singh, G.W. Thompson, V. Jayaraman, S. Sanagapalli and V. K. Rangari. Solar Cells, Volume 3, Issue 2, March, (1981)p95
4.T. Naakada, M. Mizutani, Y. Hagiwara, A.Kunioka, Solar Energy Material and Solar Cell , Volume 67, Issues 1-4, ( 2001) P 255
5.J. Hedstrom,H. Ohlsen, M.Bodegard, A. Kylner,L. Stolt,D. Hariskos, M. Ruckh , H. Schock, IEEE, ( 1993)p. 364.
6.K. Ramanathan , A. Miguel , Contreras,L. Craig ,Perkins, Sally Asher, S Falah. Hasoon, James Kean. Prog. Photovolt: Res. Appl. 11: (2003) p. 225.
7.A. Shimizu, S. Chaisitsak, T. Sugiyama ,A. Yamada . Thin solid films, 361-362: (2000) p. 193.
8.L.C. Olsen, F.W. Addis, D. Greer, W. Lei, First WCPEC, (1994)p. 194
9.W. Eisele, A. Ennaoui, P. Schubert-Bischoff, M. Giersig, C. Pettenkofer, J. Krauser, M. Lux-Steine , Solar Energy Materials & Solar Cells 75 (2003) 17
10.J.L. Shay and J.H. Wernick, Ternary chalcopyrite semiconductors : Growth, Electronic properties, and applications. (1975)
11.J.Tuttle, D. Albin, J. Goral, C. Kennedy and R. Noufi; Solar Cell, 24, (1988)p67.
12.H. Neumann and R.D. Tomlinson; Solar Cell,301, 28(1990)
13.F. Abou-Elfotouh, D.J. Dunlavy and T.J. Coutts; Solar Cell,237, (1986),p27
14.J.A. Thornton, T.C. Lommasson, H.Talidh and B.H. Tseng, Solar Cell, 24(1988)
15.D. Temjurbar , Thin Solid Films ,65, (1992)215.
16.C. Guillen, J. Herrero , Journal of Applied Physics,71,11,(1992)5479.
17.K. Subbaramaiah and V. Sundara Raja, Thin Solid Films, 28(1992)247.
18.F.J. Garcia and M.S. Tomar, Japan Journal of Applied physics, 22, Suppl.1, (19483)p535.
19.S.P. Grindle, C.W. Smith and S.D. Mittleman, Applied Physics Letters, 35(1) , (1979)24.
20.A. C. Rastogi, K. S. Balakrishnan, R. K. Sharma, Kiran Jain . Thin Solid Films, (1999) p179
21.D. Temjurbar and J.Phirde, Thin Solid Films, (1992) p215
22.N. Kavcar, M.J. Carter and R. Hill, ASolar energy Materials and Solar Cells , (1992)p 13
23.L. L. Kazmerski, M. Hallerdt, P. J. Ireland, R. A. Mickelsen and W. S. Chen, Journal of Vacuum Science Technology. (1983)p395
24.W.N. Shafarman, J.E. Phillips, Proceedings of the 25th IEEE Photovolt. Spec. Conf. IEEE, Washington, D.C., ( 1996)p. 917
25.J.Hedstrom, H. Ohlsen, M. Bodegard, A. Kylner, L.Stolt, D. Hariskos, Proc. 23rd IEEE photovoltaic Specialist Conf., (1993).p.364
26.S.William ,S. Lars . CIGS solar cells ,Handbook of Photovoltaic Science and Engineering. LuqueA, HegedusS (eds). Wiley: Chichester UK,2003; Chap. 13. (2005)p 567
27.T.Satoh, Y.Hashimoto, S.Shimakawa, S.Hayashi, T.Negami, Proceedings of the 12th Int. Phot. Sci. and Eng. Conf., Korea, (2001)p. 93
28.F. Kessler, K. Herz, M. Powalla, M. Hartmann, M. Schmidt, A. Jasanek, H.W. Schock, Proceeding Vol. 668 of the Mat. Res. Soc. Symp., San Francisco, p. H3. (2001)6. 1
29.M. Hartmann, M. Schmidt, A. Jasenek, H.-W. Schock, F. Kessler, K. Herz, M. Powalla, Proceedings of the 28th IEEE Phot. Spec. Conf., Anchorage, (2000)p. 638
30.D Rudmann, AF Da Cunha, M Kaelin, J. Appl. Phys. 84, (2004)1129.
31.A.Goetzberger, Materials & Solar Cells, 74, (2002)p1.
32.K. Ramanathan, G. Teeter, J.C. Keane, R. Nouf. Appl. 11, (2003).p.225
33.A. Miguel, K. Contreras, J. Ramanathan, F. AbuShama, D.L. Hasoon, B. Young, B. Egass and R. Noufi , Prog. Photovolt.: Res. Appl. 13 (2005), p. 209.
34.S.H. Wei, S.B. Zhang, and A. Zunger, J. Appl. Phys. 85, (1999) 7214 .
35.M. Igalson, M. Wimbor, J. Wennerberg, Thin Solid Films , (2001)p.225
36.M. Hartmann, M. Schmidt, A. Jasenek, H.-W. Schock, F. Kessler, K. Herz, M. Powalla,Proceedings of the 28th IEEE Phot. 2000, p. 638.
37.K. Ramanathan, R.N. Bhattacharya, J. Granata. Conference record of the 26th IEEE PVSC, (1997)p. 319
38.W. Eisele, A. Ennaoui, P Schubert. IEEE, (2000)p. 692
39.G. Gordillo, C. Calderon. IEEE, (2001)p. 614
40.T. Naakada, M. Mizutani, Y. Hagiwara, A.Kunioka, Solar Energy Material and Solar Cell ,67, (2001) p.255
41.K. Ellmer, J. Phys. D: Appl. Phys. 34 (2001)3097
42.K. Ellmer, R. Wendt. Surface and Coatings Technology Volume 93, Issue 1,(1997),p 21.
43.J. Yoo, J. Lee, S. Kim, K. Yoon, I.J. Park, S.K. Dhungel. Thin Solid Films. 480-481, (2005) p.213.
44.W.J. Jeong, S.K. Kim, G.C. Park. Thin Solid Films. (2006)p.180.
45.H.J. MŐller , A. House, Boston ∙ London, Ch.2(1993) p.41.
46.Z. Zhu, T. Nomura, M. Miyao and M. Hagino, Journal of crystal growth. 95, (1989) p.529.
47.S. Ishizuka, A. Yamada, P. Fons, and S. Niki. J. Renewable Sustainable Energy 1, 013102 (2008); doi:10.1063/1.3005376
48.S. Ishizuka, H. Hommoto, N. Kido, K. Hashimoto. Applied Physics Express (2008); 1: 092303.
49.K. Ellmer, J. Phys. D: Appl. Phys., 34, (2001)p. 3097
50.A.L. Fahrenbruch and R.H. Bube, Academic Press, New York, (1983)p. 473
51.C. Persson, A. Zunger. Phys. Rev. Lett., vol. 91, (2003) p. 266