硫化鎘薄膜多做為太陽能電池中的緩衝層或是視窗層，本研究使用化學水浴沉積法（CBD）成長硫化鎘薄膜。有別於傳統CBD方法使用ammonia當作錯合劑，本研究採用ammonia-free方法生長硫化鎘薄膜。以sodium citrate當作錯合劑，醋酸鎘提供Cd2+來源，硫脲提供S2-來源，並使用氫氧化鉀KOH調整酸鹼度(pH值)。
本研究改良過去實驗室學長製程，再經由製程參數：溫度、pH值與時間的調整搭配，製作出硫化鎘薄膜，並得出最佳製程參數。
研究結果發現pH值為13時不會有硫化鎘的形成，pH值為11.5的薄膜結晶優選性相對於pH值為10較好，也能形成連續薄膜。製程溫度升高，X光繞射的結晶強度只有稍微的增加，表面形貌無明顯變化，能隙值也無明顯的增加，顯示溫度參數影響很小。此外，隨著沉積時間的增加，硫化鎘膜厚、能隙值都增加，結晶方位慢慢改變、SEM表面形貌 也由圓形逐漸變成長條形。
參照文獻並對照低掠角XRD繞射圖與光譜儀結果計算出的能隙值，推測最佳製程參數pH=11.5、70°C所生成的硫化鎘薄膜為Hexagonal結構。而且沉積時間只需10分鐘就有良好的結晶優選性。EDS元素成分比分析提供在不同的沉積時間之硫化鎘薄膜的反應進行程度資訊。由霍爾量測分析得知製作出的硫化鎘薄膜為n型半導體，載子濃度為1.62×1014 cm-3，電子遷移率為1665 cm2/V．s。經由以上的分析與比較，得知pH=11.5、70°C，沉積時間10分鐘的53 nm厚的硫化鎘薄膜最適合應用於薄膜CIGS太陽能電池做為緩衝層。

Cadmium sulfide (CdS) is an indispensable layer of thin film solar cell such as CIGS and CdTe solar cell, there are many methods to synthesize CdS films. Chemical Bath Deposition (CBD) was used in this study. Ammonia is used as complexing agent in classical CBD, but we use an ammonia-free process to synthesize CdS films. Sodium citrate is substituted for ammonia as complexing agent Cd(Ac)2 dissociates to form Cd2+. Thiourea is applied as S2 source. KOH is used to adjust the pH value.
The process used in our laboratory is improved in this study. The influence of pH value, deposition temperature, and deposition time are studied. We get the most appropriate process parameters through experiment. There is no CdS thin film deposited on substrate when pH=13. CdS films deposited in process pH=11.5 is a continuous film on substrate and has better preferred crystal orientation than pH=10. The CdS films in process pH=10 is a porous and discontinuous film. When process temperature rises, the crystal intensity slightly increases with no obvious influence on the morphology and energy band gap. The pH value has a bigger impact on process than the parameter temperature. Theresults of different deposition time provide information of CdS formation process. As deposition time increase, the film thickness and energy band gap increase. The crystal orientation changes gradually and the SEM surface mophology changes from sphere-like to strip-like.
According to the X ray diffraction pattern, the band gap calculated from results of optical spectrophotometer and a published literature, we could indicate that the CdS film deposited with the best process pH=11.5, 70°C has a hexagonal structure. It needs only 10 min to form CdS crystalline film with preferred orienttation. EDS analysis of elemental composition ratio at different deposition time provides information on the reaction during process. The CdS deposited is an n-type semiconductor. The carrier concentration is 1.64×1010 cm-3 and the mobility is 1714 cm2/Vs by Hall measurement. The CdS film with 53nm thickness prepared with pH=11.5, 70°C, and deposition time 10 min is appropriate to be a buffer layer in CIGS thin film solar cell.

摘要 I
Abstract III
致謝 V
目錄 VI
圖目錄 IX
表目錄 XVI
第一章 序論 1
1.1 前言 1
1.2 硫化鎘材料的基本介紹 5
1.3 含硫化鎘（CdS）的太陽能電池簡介 6
1.3.1碲化鎘（CdTe）太陽能電池 6
1.3.2 硒化銅銦鎵（CIGS）太陽能電池 8
第二章 文獻回顧 10
2.1 太陽能電池原理 10
2.2 太陽光的頻譜照度 13
2.3 太陽能電池的電性量測 15
2.4 緩衝層 16
2.4.1 硫化鎘緩衝層介紹 16
2.4.2 硫化鎘緩衝層相關文獻回顧 18
2.5 化學水浴沉積法 22
2.5.1 化學水浴沉積法介紹 22
2.6 錯合劑氨水與檸檬酸鈉的比較 26
2.7 不同的鎘鹽對硫化鎘薄膜的影響 28
2.8 硫化鎘形成過程與反應機制 33
2.9 二硫化鐵（FeS2）吸收層主要特性 35
Shenqiang Ren團隊[55]有將硫化鎘CdS與二硫化鐵FeS2 pyrite此二種材料做搭配，並製備出太陽能電池，其製備出硫化鎘量子點並與二硫化鐵奈米晶體做混和，並以旋轉塗佈的方式塗佈在ITO基板上，最後製備成太陽能電池，但其光電轉化效率僅1.1%，仍然有進步的空間[55]。2.10 研究動機與實驗目的 36
第三章 實驗步驟 40
3.1實驗所使用之藥品 41
3.2 實驗前處理（清洗基板與燒杯） 42
3.2.1 清洗燒杯 42
3.2.2 清洗基板(康寧玻璃) 42
3.3 化學水浴法合成硫化鎘並鍍製薄膜 43
3.4使用儀器介紹 46
3.4.1加熱攪拌器（hot plate） 46
3.4.2 pH meter 46
3.4.3低掠角X-ray繞射分析儀 46
3.4.4場發射掃描式電子顯微鏡（FESEM） 47
3.4.5光性質量測 47
3.4.6霍爾量測 47
第四章 結果與討論 48
4.1 製程改良與反應機構 48
4.2 製程中不同參數對硫化鎘薄膜性質探討 49
4.3 不同製程參數對於硫化鎘薄膜結晶性質的影響 51
4.4 不同製程參數對於硫化鎘表面形貌與膜厚的影響 58
4.5 硫化鎘薄膜穿透率、反射率、吸收係數與能帶寬 77
4.6 硫化鎘薄膜之元素含量分析 87
4.7 硫化鎘薄膜之電性量測 97
4.8 硫化鎘薄膜之TEM分析 99
第五章 結論 104
參考資料 105

[1]. 莊嘉琛。太陽能工程－太陽電池篇。全華科技圖書股份有限公司。2003。
[2]. 洪永杰。III-V 族半導體太陽能電池專利檢索與分析報告。2005
[3]. X. Wu, J.C. Keane, R.G. Dhere, C. DeHart, A. Duda, T.A.Gessert, S. Asher, D.H. Levi, P. Sheldon, Proc. 17th European Photovoltaic Solar Energy Conf. (Munich, Germany 22–26 October 2001), 2001, p. 995
[4]. G.J. Bauhuis, P. Mulder, E.J. Haverkamp, J.C.C.M. Huijben, J.J. Schermer, Solar Energy Materials & Solar Cells, vol. 93, pp. 1488-1491, 2009
[5]. Repins, M.A. Contreras, B. Egaas, C. DeHart, J. Scharf, C.L. Perkins, B. To, and R.N. Noufi, Prog. Photovolt: Res. Appl., vol. 16, pp. 235-239, 2008.
[6]. O’Regan B, Graetzel M, A low-lost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films, Nature, 1991, 353(6346), pp.737-740.
[7]. Gratzel M,Photoelectrochemical cells, Nature, 2001, 414(6861), 338-344.
[8]. G. Larramona, C. Chone, A. Jacob, D. Sakakura, B. Delatouche, D. Pere, X. Cieren, M. Nagino, R. Bayon, Chem. Mater. 18 (6) (2006) 1688.
[9]. E.-Z. Liang, C.-F. Lin, W.-F. Su, SPIE Proc. 4641 (2002) EI.
[10]. B.S. Moon, J.H. Lee, H. Jung, Thin Solid Films 511 (2006) 299.
[11]. D. Barreca, A. Gasparotto, C. Maragno, E. Tondello, C. Sada, Chem. Vapour Depos. 10 (4) (2004) 229.
[12]. D.R. Acosta, C.R. Magana, A.I. Martinez, A. Maldonado, Solar Energy Mater. Solar Cells 82 (1–2) (2004) 11.
[13]. J.W. Choi, A. Bhupathiraju, M.A. Hasan, J.M. Lannon, J. Crystal Growth 255 (1–2) (2003) 1.
[14]. M.T.S. Nair, P.K. Nair, R.A. Zingaro, E.A. Meyers, J. Appl. Phys. 751994) 1557.
[15]. 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)
[16]. D. Hariskos, M. Powalla, N. Chevaldonnet, D. Lincot, A. Schindler, B. Dimmler, Thin Solid Films 387 (2000) 179.
[17]. [16] D.S. Boyle, A. Bayer, M.R. Heinrich, O. Robbe, P.O. O’Brien, Thin Solid Films 361–362 (2000) 150.
[18]. P. Nemec, I. Nemec, P. Nahalkova, K. Knizek, P. Maly, J. Cryst. Growth 240 (2002) 484.
[19]. P. Nemec, I. Nemec, P. Nahalkova, Y. Nemcova, F. Trojanec, P. Maly, Thin Solid Films 403–404 (2002) 9.
[20]. K.Zweibel, Harnessing solar cell-The photovoltaics challenge. (1990).
[21]. W.G.Adams, and R.E. Day, Proc. R. Soc (1877)113.
[22]. S.O. Kasap, Optoelectronics and Photonics: Principles and Practices,New Jersey, Prentice Hall, 2001.
[23]. Jenny Nelson, The Physics Of Solar Cells, Landon., Imperial College Press, 2003.
[24]. 敖建平,何青,孫國忠,劉芳芳,黃磊,李葳,李風岩,孫雲,薛玉明,Chinese Journal Of Semiconductors Vol.26(2005)
[25]. D.Hariskos,S.Spiering,M.Powalla,ThinSolid Films,pp.99-109,2005
[26]. C Platzer-Bjorkman,J,Kessler, L. Stolt, Processdings, 3rd World Conference of Photovoltaic Energy Conversion, Osaka, Japan,p.461 (2003)
[27]. P.Konagai,Y.Ohtake,T.Okamoto,Mater.Res.Soc.Symp.Proc.426.P.153(1996)
[28]. H.Fukui AO. Ohtaka AT.Suzuki AK Funakoshi, Phys Chem Miner-als,Vol30,PP.511-516,2003
[29]. P.K. Nair, M. T. S. N., V.M. Garcia, O.L. Arenas, Y. Pena,A. Castillo, I.T. Ayala, O. Gomezdaza, A. Sanchez, J. Campos, and R. S. H. Hu, M.E. Rincon (1998). "Semiconductor thin films by chemical bath deposition for solar energy related applications." Solar Energy Materials and Solar Cells 52: 313 - 344.
[30]. QI LIU,GUOBUNG MAO, surface review and letters,Vol.16,NO.3(2009) 469-474
[31]. A. V. Feitosa, M. A. R. Miranda, J. M. Sasaki, and M. A. Ara´ujo-Silva, (2004). "A New Route for Preparing CdS thin Films by Chemical Bath Deposition Using EDTA as Ligand." Brazilian Journal of Physics 34( 2B).
[32]. Paul O'Brien, Tahir Saeed (1996). "Deposition and characterization of cadmium sulfide thin films by chemical bath deposition" Journal of Crystal Growth 158( 4): 497-504
[33]. M.B. Ortun˜o Lo´pez,TJ.J. Valenzuela-J´auregui, M. Sote-lo-Lerma"Highly oriented CdS films deposited by an ammonia-free chemical bath" method Thin Solid Films 429 (2003) 34–39
[34]. F. M. Amanullah, A. S. Al-Shammari, A. M. Al-Dhafiri (2005). "Co-activation effect of chlorine on the physical properties of CdS thin films prepared by CBD technique for photovoltaic applications." physica status solidi (A) 202(13): 2474-2478.
[35]. M. Rami, E. Benamar,M. Fahoume, F.Chraibi and A. Ennaoui, Solid State Sciences 1, pp.179-188, 1999.
[36]. Akintunde, J. A. (2000). "Effects of Deposition Parameters and Conditions on the Physical and Electro-Optical Properties of Buffer Solution Grown CdS Thin Films." physica status solidi (a) 179( 2): 363-371.
[37]. B. Malinowska,M. Rakib, G. Durand (2005). "Analytical characterization of cadmium cyanamide in CdS thin films and bulk precipitates produced from CBD process in pilot plant " Solar Energy Materials and Solar Cells86(3): 399-419
[38]. Y. Hashimoto, N. Kohara, T. Negami, et al., Solar Energy Material and Solar
[39]. Hani Khallaf, Isaiah O. Oladeji, Guangyu Chai, Lee Chow Thin Solid Films 516 (2008) 7306–7312
[40]. D. A. Mazo´n-Montijo, M. Sotelo-Lerma, M. Quevedo-Lo´pez, M. El-Bouanani, H. N. Alshareef, F. J. Espinoza-Beltra´n, R. Ramı´rez-Bon Applied Surface Science 254 (2007) 499–505
[41]. J. E. Macintyre (executive editor), F. M. Daniel, V. M. Stirling (assis-tanteditors), Dictionary of Inorganic Compounds-Chemical Database ,1st Editions, Published by Charpman and Hall(1992).
[42]. H. Moualkia, S. Hariech, M.S. Aida Thin Solid Films 518 (2009) 1259–1262
[43]. K. Ravichandran, P. Philominathan Applied Surface Science 255 (2009) 5736–5741
[44]. M. Becker and H.Y.Fan,J.Phys.Chem.solids23,p.1219(1962)
[45]. T. S. Moss, Optical Properties of Semiconductors (Butterworths, London, 1959)
[46]. J.Tauc, Grigorov. R, and A. Vancu, Phys. Status Solid i. 15, 627 (1966)
[47]. N. F. Mott and E. A. Davis, Electronic Processes in Non-crystalline Materials (Clarendon, Oxford, 1971)
[48]. G. Mustafa, M. R. I. Chowdhury, D. K. Saha, S. Hussain, and O. Islam Dhaka Univ. J. Sci. 60(2): 283-288, 2012 (July)
[49]. C. A. Vincent, Modern Batteries: Edward Arnold, London, (1984), p.182.
[50]. Technology for Energy Efficiency and Solar Energy Conversion ix, p.67(1990)
[51]. Ennaoui. A, Fiechter. S, Goslowsky. H, Tributsch. H, Journal of Electrochemical society, Vol.132(7)(1985), pp.1579-1582
[52]. Peter C. Rieke and Susan B. Bentjen, Chem. Mater. 1993, 5, 43-53
[53]. D. Abou-Ras, G. Kostorz, A. Romeo, D. Rudmann, A.N. Tiwari Thin Solid Films 480–481 (2005) 118– 123
[54]. G.Sivakumar, V. Hariharan and K.Abith Elixir Optical Materials 48 (2012) 9433-9436
[55]. Alec Kirkeminde, Randall Scott and Shenqiang Ren Nanoscale, 2012, 4, 7649-7654
[56]. T. Nakada and A. Kunioka Appl. Phys. Lett. 74, 2444 (1999)
[57]. M. Rusu, Th. Glatzel, A. Neisser, C. A. Kaufmann, S. Sadewasser, and M. Ch. Lux-Steiner Appl. Phys. Lett. 88, 143510 (2006)