臺灣博碩士論文加值系統

黃銅礦基太陽能電池有銅銦硒系列CuInSe2[CIS]和銅銦鎵硒系列Cu(In1-XGaX)(Se1-YSY)[CIGS]等兩大種類的化合物太陽能電池。在高光電效率和低材料成本的好處下，銅銦鎵硒太陽能電池值得繼續研究開發。本實驗採用三種不同的前驅物，製備CIS和CIGS粉體，利用XRD、SEM、EDS以及TEM等儀器鑑定其結晶相，成份比及粒子大小、表面型態。
選用CuCl2 ，InCl3， 和SeCl4三種鹽類製備CIS粉體的優點是可以調整成份比，使用[Cu4{Se2P(OiPr)2}4] 、[In{Se2P(OiPr)2}3]二種前驅物製備粉體的優點則為單一相產物。
利用銅銦鎵硒四元素粉體水熱方式製備CIGS，由於粉體無法完全溶解於溶劑，而CuCl2 ，InCl3， GaCl3 和SeCl4四種鹽類和[Cu4{Se2P(OiPr)2}4] 、[In{Se2P(OiPr)2}3]和GaCl3無機化合物可以溶於溶劑中，可以製備出單一相的CIGS粉體，選用鹽類的好處可以控制CIGS粉體成份比，無機化合物製備出的CIGS粉體較無其他雜相生成。

Solar cells with chalocopyrite structure have two major types: copper indium selenium series, CuInSe2[CIS], and copper indium gallium selenium series, Cu(In1-xGax)(Se1-ySy)[CIGS]. Due to the advantages of high photoelectric efficiency and low materials cost, it is worth to keep studying these two material systems. In this experiment, three kinds of different precursors were used to synthesize CIS and CIGS powder. XRD, SEM, EDS, and TEM were then used to analyze crystallization, composition, particle size, and morphology of powder products.

The composition of the product can be adjusted when salts of CuCl2, InCl3, and SeCl4 were used to synthesize the CIS powder. The product can be single phase if precursors of [Cu4{Se2P(O’Pr) 2}4] and [In{Se2P(O’Pr) 2}3] were used.

It is hard to synthesize CIGS powder by using Cu, In, Ga, and Se powder directly, because all these powder can not be completely dissolved into the solvent used in this experiment. The composition of the product can be adjusted when salts of CuCl2, InCl3, GaCl3 and SeCl4 were used to synthesize the CIGS powder. The product can be almost single phase if precursors of [Cu4{Se2P(O’Pr) 2}4], [In{Se2P(O’Pr) 2}3], and GaCl3 were used.

中文摘要 I
Abstract II
謝誌 III
目錄 IV
圖目錄 IX
表目錄 XIV
第一章 緒論 1
1.1 前言 1
1.2 銅銦硒或銅銦鎵硒太陽能電池的發展和演進 3
1.3 研究動機 6
第二章 理論基礎與文獻回顧 8
2.1太陽能電池元件運作原理 8
2.1.1決定太陽能電池的效能的因素 9
2.1.2太陽能電池實際製作考量 11
2.2 三元系的銅銦硒基太陽能電池 13
2.3 四元系的銅銦鎵硒基太陽能電池 16
2.3.1 背面電極(Back Electrode) 18
2.3.2 銅銦鎵硒吸收薄膜層 18
2.3.3 緩衝薄膜層 19
2.3.4氧化鋅薄膜複合層 20
2.4 銅銦硒太陽能電池的製程技術 20
2.5 銅銦鎵硒太陽能電池的製作技術 22
2.5.1電沉積(Electrodeposition)製備CIGS 薄膜 24
2.5.2 真空共蒸著法(Coevaporation) 製備CIGS 薄膜 25
2.5.3 網版印刷製備CIGS 薄膜 27
2.6 合成奈米粒子的方法 29
2.6.1水熱法 ( Hydrothermal method ) 31
2.6.2微波水熱法 ( Microwave Hydrothermal method ) 33
第三章 實驗步驟 35
3.1實驗藥品 35
3.2實驗儀器 39
3.2.1一般儀器 39
3.2.2 dry box.手套箱 40
3.2.3 CEM /Discover聚焦式微波合成反應系統 40
3.2.4廣角X-Ray繞射儀 (Wide-angle XRD) 42
3.2.5掃描式電子顯微鏡 ( Scanning Electron Microscopy，SEM ) 42
3.2.6穿透式電子顯微鏡 ( Transmission Electron Microscopy，TEM ) 43
3.3 實驗部份 43
3.3.1製備CIGS水熱溶液 43
3.3.1.2微波水熱製備CIGS粉體 43
3.3.1.3傳統水熱製備CIGS粉體 44
3.3. 2.1製備CIS前驅液 44
3.3. 2.2微波水熱製備CIS粉體 44
3.3. 2. 3傳統水熱製備CIS粉體 45
3.3. 2. 4製備CIGS前驅液 45
3.3. 2. 5微波水熱製備CIGS粉體 46
3.3. 2. 6傳統水熱製備CIGS粉體 46
3.3. 3.1製備CIS前驅液 47
3.3.3.2微波水熱製備CIS粉體 47
3.3.3.3傳統水熱製備CIS粉體 48
3.3.3.4製備CIGS前驅液 48
3.3.3.5微波水熱製備CIGS粉體 48
3.3.3.6傳統水熱製備CIGS粉體 49
3.4 儀器鑑定 49
3.4.1廣角X-Ray繞射儀 ( Wide-angle XRD ) 鑑定 49
3.4.2掃描式電子顯微鏡 ( SEM ) 49
3.4.3穿透式電子顯微鏡 ( TEM ) 50
第四章 結果與討論 52
4.1利用Cu, In, Ga, Se 四種元素粉末製備銅銦鎵硒粉體 52
4.1.1 微波水熱法製備CIGS粉體 52
4.1. 2傳統水熱法製備CIGS粉體 53
4.1.2.1 傳統水熱法製備前驅液處理 53
4.1.2.2 傳統水熱法製備CIGS粉體 54
4.1.2.3傳統水熱法改變條件製備CIGS粉體 58
4.2. 利用CuCl2 ，InCl3， GaCl3 和SeCl4四種鹽類來製備CIS和CIGS粉體 61
4.2.1.1微波水熱法製備CIS粉體 61
4.2.1.2傳統水熱法製備CIS粉體 62
4.2.2.1微波水熱法製備CIGS粉體 64
4.2.2.2傳統水熱法製備CIGS粉體 67
4.3利用無機化合物[Cu4{Se2P(OiPr)2}4] 和[In{Se2P(OiPr)2}3] 來製備CIS和CIGS粉體 73
4.3.1.1 微波水熱法製備CIS粉體 73
4.3.1.2 傳統水熱法製備CIS粉體 77
4.3.1.3 比較微波水熱和傳統水熱製備CIS粉體 80
4.3. 2.1 微波水熱法製備CIGS粉體 82
4.3.2.2 傳統水熱法製備CIGS粉體 86
4.3.2.3 比較微波水熱和傳統水熱製備CIGS粉體 89
第五章 結論 91
5.1利用Cu, In, Ga, Se 四種元素粉末製備銅銦鎵硒粉體 91
5.2利用CuCl2 ，InCl3， GaCl3 和SeCl4四種鹽類來製備CIS和CIGS粉體 91
5.3利用無機化合物[Cu4{Se2P(OiPr)2}4] 和[In{Se2P(OiPr)2}3] 來製備CIS和CIGS粉體 92
5.4兩種前驅物製備CIS粉體比較 92
5.5 三種前驅物製備CIGS粉體比較 92
第六章 未來改進方向 93
6.1利用Cu, In, Ga, Se 四種元素粉末製備銅銦鎵硒粉體 93
6.2 利用CuCl2 ，InCl3， GaCl3 和SeCl4四種鹽類來製備CIS和CIGS粉體 93
6.3利用無機化合物[Cu4{Se2P(OiPr)2}4] 和[In{Se2P(OiPr)2}3] 來製備CIS和CIGS粉體 93
參考文獻 94

圖目錄
圖 1 - 1矽晶片太陽能電池工作原理 2
圖 1 - 2各種太陽電池材料的光吸收特性比較圖[33] 5

圖 2 - 1 太陽能電池將光能轉換成電能原理示意圖。在中性區的載子仰賴擴散機制制空乏區邊緣。在空乏區內載子移動則仰賴空乏電場作用的漂移行為。另外，蒐集再子的效率和表現複合效應的參數「擴散長度」緊密相關。 8
圖 2 - 2典型太陽能電池元件照光情況下電流密度與電壓的關係 11
圖 2 - 3載子躍遷至導帶之後，多於能量散逸成熱能示意圖。當入射光子的能量大於能隙寬值時，此機制就會發生 12
圖 2 - 4多能隙寬電池的概念(a)光譜分割的方法(b)串疊式電池方法 13
圖 2 - 5黃銅礦的代表性結晶結構 14
圖 2 - 6閃鋅礦的代表性結晶結構[10] 14
圖 2 - 7銅銦硒系化合物太陽能電池元件的基本結構 15
圖 2 - 8銅銦鎵硒系化合物太陽能電池元件的基本結構 16
圖 2 - 9銅銦鎵硒基太陽能電池之吸收係數與光子能量的關係圖 17
圖 2 - 10硒化法的簡單示意圖 21
圖 2 - 11銅銦鎵硒化物型太陽能電池的製作流程 23
圖 2 - 12 電化學沉積製備CIGS 薄膜之設備示意圖[38] 25
圖 2 - 13 II-VI族化合物薄膜太陽能電池的製作方法種類 27
圖 2 - 14 II-VI族化合物薄膜太陽能電池的製作方法種類 27
圖 2 - 15合成奈米粉體製程技術圖[42] 31
圖 2 - 16密閉容器內水的填充度與溫度和壓力關係圖 33

圖 3 - 1為[Cu4{Se2P(OC3H7)2}4]結構圖 36
圖 3 - 2為[In{Se2P(OR)2}3]結構圖 36
圖 3 - 3 Discover外觀正面 39
圖 4 - 1 微波水熱溫度180℃，時間分別(a)30mins.；(b)1hr.；(c)2hrs.；(d)3hrs. 的X-ray圖譜。 52
圖 4 - 2 傳統水熱溫度140℃，時間12小時在反應前幫助粉末溶解溫度分別為 (a)25℃；(b)35℃；(c)45℃；(d)55℃的X-ray圖譜。 53
圖 4 - 3 傳統水熱反應12小時，溫度分別為(a)140℃；(b)180℃；(c)200℃ 55
圖 4 - 4 傳統水熱反應12小時，溫度分別(a)140℃；(b)180℃；(c)200℃的SEM影像。 56
圖 4 - 5 傳統水熱反應12小時，溫度140℃的EDS能譜。 57
圖 4 - 6 傳統水熱反應12小時，溫度180℃的EDS能譜。 57
圖 4 - 7 傳統水熱反應12小時，溫度200℃的EDS能譜。 57
圖 4 - 8 傳統水熱溫度230℃，時間分別為(a)36hrs；(b)48hrs的X-ray圖譜。 59
圖 4 - 9 傳統水熱溫度230℃，時間分別為(a)36hrs；(b)48hrs的SEM圖譜。 59
圖 4 - 10 傳統水熱溫度230℃，時間36hrs的EDS能譜。 60
圖 4 - 11 傳統水熱溫度230℃，時間48hrs的EDS能譜。 60
圖4 - 12 微波水熱反應時間2小時，溫度分別為(a)180℃；(b)190℃的X-ray圖譜。 61
圖 4 - 13 傳統水熱反應溶劑為甲醇，時間24小時，溫度分別為 63
圖 4 - 14 傳統水熱反應溶劑為乙醇，溫度200℃，時間分別為 63
圖 4 - 15 微波水熱反應溶劑為乙醇，時間2hrs，溫度190℃的X-ray圖譜。 65
圖 4 - 16 微波水熱反應溶劑為乙醇，添加terpineol 0.1ml，時間2小時， 66
圖 4 - 17 微波水熱反應溶劑為乙醇，時間2小時，溫度180℃ 66
圖 4 - 18 傳統水熱反應溶劑為甲醇，時間24小時，溫度分別為 69
圖 4 - 19傳統水熱反應溶劑為乙醇，時間24小時，溫度分別為 69
圖 4 - 20 傳統水熱反應溶劑為乙醇，溫度200℃，時間分別為 70
圖 4 - 21 傳統水熱反應溶劑為乙醇，溫度200℃，時間 71
圖 4 - 22 是圖4-21(a)的EDS分析圖 。 71
圖 4 - 23 是圖4-21(b)的EDS分析圖。 71
圖 4 - 24是圖4-21(c)的EDS分析圖。 72
圖 4 - 25是圖4-21(d)的EDS分析圖。 72
圖 4 - 26 微波水熱反應時間30分鐘，溫度分別為 74
圖 4 - 27 微波水熱反應時間30分鐘，溫度分別為 75
圖 4 - 28 微波水熱反應時間30分鐘，溫度140℃的TEM影像和選區繞射圖案。 76
圖 4 - 29 微波水熱反應時間30分鐘，溫度140℃的EDS分析圖。 76
圖 4 - 30 傳統水熱反應時間12小時，溫度分別為 78
圖 4 - 31傳統水熱反應時間12小時，溫度分別為(a)200℃；(b)220℃的SEM圖譜。 79
圖 4 - 32 傳統水熱反應時間12小時，溫度200℃的TEM影像。 79
圖 4 - 33 傳統水熱反應時間12小時，溫度200℃的EDS能譜。 80
圖 4 - 34 微波水熱時間30分鐘，溫度分別(a)100℃；(b)120℃；(c)140℃；(d)160℃；(e)180℃的X-ray圖譜。 83
圖 4 - 35微波水熱時間30分鐘，溫度分別為(a)120℃；(b)140℃；(c)160℃；(d)180℃的SEM圖譜。 84
圖 4 - 36微波水熱溫度為140℃的TEM影像。 85
圖 4 - 37微波水熱溫度140℃的EDS能譜。 85
圖 4 - 38傳統水熱溫度分別為(a)180℃；(b)200℃；(c)220℃的X-ray圖譜。 87
圖 4 - 39傳統水熱溫度分別為(a)180℃；(b)200℃；(c)220℃的SEM圖譜。 88
圖 4 - 40傳統水熱溫度為220℃的TEM影像。 88
圖 4 - 41傳統水熱溫度220℃的EDS能譜。 89


表目錄
表 2 - 1薄帶成形中常用之黏結劑及增塑劑(塑化劑) 27
表 2 - 2 物理法製作奈米粒子方法和其優點 28

表 3 - 1為利用元素微波水熱製備CIGS 41
表 3 - 2為利用元素傳統水熱製備CIGS 42
表 3 - 3為利用鹽類微波水熱製備CIS 43
表 3 - 4為利用鹽類傳統水熱製備CIS 44
表 3 - 5為利用無機化合物微波水熱製備CIGS 45
表 3 - 6為利用無機化合物微波水熱製備CIGS 45
表 3 - 7為利用無機化合物傳統水熱製備CIGS 46
表 3 - 8為利用無機化合物微波水熱製備CIS 47
表 3 - 9為利用無機化合物傳統水熱製備CIS 47
表 3 - 10為利用無機化合物微波水熱製備CIGS 48
表 3 - 11為利用無機化合物傳統水熱製備CIGS 49

表 4 - 1 表列傳統水熱反應12小時不同溫度的EDS分析結果。 58
表 4 - 2 表列傳統水熱溫度230℃，36小時和48小時的EDS分析結果。 60
表 4 - 3 表列傳統水熱溫度200℃，圖4-21(a)(b)(c)(d)的EDS分析結果。 72
表 4 - 4 表列微波水熱反應時間30分鐘，溫度140℃的EDS分析結果。 76
表 4 - 5傳統水熱反應時間12小時，溫度200℃的EDS分析結果。 80
表 4 - 6 為比較傳統水熱和微波水熱各成份比。 81
表 4 - 7 是微波水熱溫度140℃的EDS分析結果。 85
表 4 - 8 傳統水熱溫度220℃的EDS分析結果。 89
表 4 - 9 比較微波水熱和傳統水熱所製備出的CIGS粉體成份比。 90

[1] Miguel A. Contreras , Manuel J. Romero, R. Noufi，“Characterization of Cu(In,Ga)Se2 materials used in record performance solar cells”，Thin Solid Films 511 – 512 (2006) 51 – 54
[2] Philip Jackson, Roland Wurz, Uwe Rau, Julian Mattheis, Matthias Kurth, Thomas Schlotzer, Gerhard Bilger and Jurgen H. Werner，“High Quality Baseline for High
Efficiency, Cu(In1-x,Gax)Se2 Solar Cells”，Prog. Photovolt. Res. Appl. 2007; 15:507–519
[3] A.S. Kindyak , V.V. Kindyak, V.F. Gremenok，“Energy-gap variations in thin laser-deposited Cut In, Ga) Se, films”Materials Letters 28 (1996) 273-275
[4] Arturo Morales-Acevedo，“Effective absorption coefficient for graded band-gap semiconductors and the expected photocurrent density in solar cells”，Solar Energy Materials & Solar Cells 93 (2009) 41– 44
[5]和田隆博,”化合物薄膜太陽電池的最新技術”,材料世界網整理,2007.12
[6] Ingrid Repins, Miguel A. Contreras, Brian Egaas, Clay DeHart, John Scharf, Craig L. Perkins, Bobby To and Rommel Noufi，“19.9%-efficient ZnO/CdS/CuInGaSe2 Solar Cell with 81.2% Fill Factor”，Progress in Photovoltaics: Research and Applications，Appl. 2008; 16:235–239
[7] Y. Hagiwara, T. Nakada, A. Kunioka, “Improved Jsc in CIGS thin film solar cells using a transparent conducting ZnO:B window layer”，Solar Energy Materials & Solar Cells 67 (2001) 267-271
[8]S.M. Sze, Semiconductor Devices physics and technology, Wiley.New York(1985)
[9]A. Luque, Ed., Physical Limitation to Photovoltaic Energy Conversion,IOP Press,Philadelphia(1990)
[10]顧鴻濤，“太陽能電池元件導論”，97.6.20
[11] ParagS.Vasekar , NeelkanthG.Dhere，“Effect of sodium addition on Cu-deficient CuIn1-xGaxS2 thin film solar cells”，Solar Energy Materials & Solar Cells 93 (2009) 69– 73
[12] Jae Ho Yun , Ki Hwan Kim , Min Sik Kim , Byung Tae Ahn , Se Jin Ahn , Jeong Chul Lee , Kyung Hoon Yoon ，“Fabrication of CIGS solar cells with a Na-doped Mo layer on a Na-free substrate”，Thin Solid Films 515 (2007) 5876–5879
[13] Gordillo, G.; Mesa, F.; Calderon, C. ，“Electrical and morphological properties of low resistivity Mo thin films prepared by magnetron sputtering.”，Brazilian Journal of Physics (2006), 36(3B), 982-985.
[14] Yoon, Kyung Hoon; Kim, Seok Ki; Chalapathy, R. B. V.; Yun, Jae Ho; Lee, Jeong Chul; Song, Jinsoo; Ahn, Byung Tae.，“Characterization of a molybdenum electrode deposited by sputtering and its effect on Cu(In,Ga)Se2 solar cells.”，Journal of the Korean Physical Society (2004), 45(4), 1114-1118.
[15] John H. Scofield, A. Duda, D. Albin, B.L. Ballard, P.K. Predecki，“Sputtered molybdenum bilayer back contact for copper indium diselenide-based polycrystalline thin-film solar cells”，Thin Solid Films 260 ( 1995) 26-31
[16] Abou-Ras, Daniel; Mukherji, Debashis; Kostorz, Gernot; Bremaud, David; Kalin, Marc; Rudmann, Dominik; Dobeli, Max; Tiwari, Ayodhya N.，“Dependence of the MoSe2 formation on the Mo orientation and the Na concentration for Cu(In,Ga)Se2 thin-film solar cells.”， Materials Research Society Symposium Proceedings (2005), 865(Thin-Film Compound Semiconductor Photovoltaics), 287-292.
[17]O.Lundberg,M.Edoff,L. Stolt，“The effect of Ga-grading in CIGS thin film solar cells”，Thin Solid Films 480-481(2005)520-525
[18] Neelkanth G. Dhere，“Present status and future prospects of CIGSS thin film solar cells”，Solar Energy Materials & Solar Cells 90 (2006) 2181–2190
[19] H. Komaki, A. Yamada, K. Sakurai, S. Ishizuka, Y. Kamikawa-Shimizu, K. Matsubara, H. Shibata, and S. Niki，“CIGS solar cell with CdS buffer layer deposited by ammonia-free process”，Phys. Status Solidi A 206, No. 5, 1072–1075 (2009)
[20] Sho Shirakata, Katsuhiko Ohkubo, Yasuyuki Ishii and Tokio Nakada，“Effects of CdS buffer layers on photoluminescence properties of Cu(In,Ga)Se2 solar cells”，Solar Energy Materials and Solar Cells，Volume 93, Issues 6-7, June 2009, Pages 988-992
[21] Akira Ichiboshi, Masashi Hongo, Takuya Akamine ,Tsukasa Dobashi and Tokio Nakada，“Ultrasonic chemical bath deposition of ZnS(O,OH) buffer layers and its application to”，Solar Energy Materials and Solar Cells，Volume 90, Issues 18-19, 23 November 2006, Pages 3130-3135
[22] Byung Tae Ahn, Liudmila Larina, Ki Hwan Kim and Soong Ji Ahn，“Development of new buffer layers for Cu(In,Ga)Se2 solar cells”，Pure Appl. Chem., 2008, Vol. 80, No. 10, pp. 2091-2102
[23] Pai-feng Luo, Guo-shun Jiang and Chang-fei Zhu，“Pulsed Laser Deposition ZnS Buffer Layers for CIGS Solar Cells”，Chinese Journal of Chemical Physics (2009), 22, (1), 97-101
[24] Alexei PUDOV, James SITES and Tokio NAKADA，“Performance and Loss Analyses of High-Efficiency Chemical Bath Deposition (CBD)-ZnS/Cu(In1−xGax)Se2 Thin-Film Solar Cells”， Jpn. J. Appl. Phys. Vol. 41 (2002) pp. L 672–L 674
[25] T. Nakada, M. Mizutani, Y. Hagiwara, A. Kunioka，“ High-efficiency Cu(In,Ga)Se2 thin-film solar cells with a CBD-ZnS buffer layer”， Solar Energy Materials & Solar Cells 67 (2001) 255}260
[26] Delahoy, A. E.; Ruppert, A.; Contreras, M.，“Charging and discharging of defect states in CIGS / ZnO junctions，Thin Solid Films (2000), 361-362 140-144.
[27] L. Kronik , B. Mishori , E. Fefer , Y. Shapira , W. Riedl ，“Quality control and characterization of Cu(In,Ga)Se2-based thin-film solar cells by surface photovoltage spectroscopy”， Solar Energy Materials and Solar Cells 51 (1998) 21-34
[28] Rostan, P. J.; Mattheis, J.; Bilger, G.; Rau, U.; Werner, J. H.，“Formation of transparent and ohmic ZnO : Al /MoSe2 contacts for bifacial Cu(In,Ga)Se2 solar cells and tandem structures.” Thin Solid Films (2005), 480-481 67-70
[29] Kessler, J.; Norling, J.; Lundberg, O.; Wennerberg, J.; Stolt, L. ， “Optimization of RF-sputtered ZnO / ZnO : Al for Cu(In,Ga)Se2 based devices.” ，European Photovoltaic Solar Energy Conference, Proceedings of the International Conference, 16th, Glasgow, United Kingdom, May 1-5, 2000 (2000), 1 775-778.
[30] Cooray, Nawalage F.; Kushiya, Katsumi; Fujimaki, Atsushi; Okumura, Daisuke; Sato, Masao; Ooshita, Mineo; Yamase, Osamu.，“Optimization of Al -doped ZnO window layers for large-area Cu(In,Ga)Se2-based modules by RF/DC/DC multiple magnetron sputtering.”，Japanese Journal of Applied Physics, Part 1: Regular Papers, Short Notes & Review Papers (1999), 38(11), 6213-6218
[31] S. Agilana, D. Mangalarajb, Sa.K. Narayandassb, S. Velumanic,Alex Ignatiev，“Structural and optical characterization of CuInSe2 films deposited by hot wall vacuum evaporation method”，Vacuum 81 (2007) 813–818
[32] By Reiner Klenk, Thornus Wulter, Hans- Werner Schock, and David Cuhen，“A Model for the Successful Growth of Polycrystalline Films of CuInSe, by Multisource Physical Vacuum Evaporation”，A h . M ule,. 1993, 5, No. 2
[33] Ahn, Byeong Tae; Lee, Du Yeol; Song, Jin Su; Yoon, Gyeong Hun.，“Manufacturing of CuInSe2 thin films for solar cells by vacuum evaporation.”，Repub. Korean Kongkae Taeho Kongbo (2002),
[34] J. A ´ lvarez-Garcı´a, A. Pe´rez-Rodrı´guez, A. Romano-Rodrı´guez, and J. R. Morante，“Microstructure and secondary phases in coevaporated CuInS2 films: Dependence on growth temperature and chemical composition”， J. Vac. Sci. Technol. A Volume 19, Issue 1, pp. 232-239
[35] Brian E. McCandless and Robert W. Birkmire，“Control of Deposition and Surface Properties of CuInSe2 Thin Films for Solar Cells”， 20th IEEE Photovoltaic Specialists Conference, Vol. 2 (1988), p. 1510
[36] Yoon, J. T.; Yang, H.; Chang, B -H.，“Structural and electrical characteristics of CuInSe2 thin films grown by three-source coevaporation.”， Journal of the Korean Physical Society (1995), 28(3), 354-7.
[37] G.P. Vassilev , P. Docheva , N. Nancheva , B. Arnaudov , I. Dermendjiev ，“Technology and properties of magnetron sputtered CuInSe2 layers”，Materials Chemistry and Physics 82 (2003) 905–910
[38] Huang, Shiyong; Qu, Fengqin; Dai, Zhenhong; Miao, Ye; Zhong, Yurong; Wang, Zhongxun.，“Influence of substrates and sputtering parameters on CuInSe2 quantum dots.”，Guti Dianzixue Yanjiu Yu Jinzhan (2004), 24(2), 249-252, 263.
[39] He, Y. B.; Kriegseis, W.; Meyer, B. K.; Polity, A.; Serafin, M.，“Heteroepitaxial growth of CuInS2 thin films on sapphire by radio frequency reactive sputtering.”，Applied Physics Letters (2003), 83(9), 1743-1745
[40] O. Volobujeva , J. Kois, R. Traksmaa, K. Muska, S. Bereznev, M. Grossberg, E. Mellikov，“Influence of annealing conditions on the structural quality of CuInSe2 thin films”，Thin Solid Films 516 (2008) 7105–7109
[41] F. Kang, J.P. Ao, G.Z. Sun, Q. He, Y. Sun，“Growth and characterization of CuInSe2 thin films via one-step electrodeposition from a lactic acid/sodium lactate buffer system”，Materials Chemistry and Physics，Volume 115, Issues 2-3, 15 June 2009, Pages 516-520
[42] Jean Franpis. Guillemoles, Pierre Cowache, Sylvie Massaccesi, Laurent Thouin, Sylvie Sanchez, Daniel Lincot, and Jacques Vedel,“Solar Cells with Improved Efficiency Based on Electrodeposited Copper Indium Diselenide Thin Films”， Adv. Mater. 6 (5) (1994), p. 379
[43] O. Ramdani, E. Chassaing, B. Canava, P.-P. Grand, O. Roussel, M. Lamirand, E. Rzepka, A. Etcheberry, J.-F. Guillemoles, D. Lincot and O. Kerrec，“Electrochemical Cementation Phenomena on Polycrystalline Molybdenum Thin Films from Cu(II)–In(III)–Se(IV)Acidic Solutions”， J. Electrochem. Soc.
[44] X. Charles Li, Istvan Soltesz, Mindy Wu, Frank Ziobro, Roger Amidon, and Zoltan Kiss，“A nanoparticle ink printing process for all printed thin film copper-indium-selenide (CIS) solar cells”，Proc. SPIE, Vol. 7047, 70470E (2008)
[45] Vervaet, A.; Burgelman, M.; Clemminck, I.; Casteleyn, M.，“Screen printing of CIS films for CIS-cadmium sulfide solar cells.”，E. C. Photovoltaic Sol. Energy Conf., Proc. Int. Conf., 10th (1991), 900-3.
[46] C.R. Abernathy, C.W. Bates Jr., A. Anani, B. Haba and G. Smestad，“Production of single phase chalcopyrite CuInSe2 by spray pyrolysis”， Appl. Phys. Lett. 45 (8) (1984), p. 890
[47] Tomoaki Terasakoa, Seiki Inouea, Tetsuya Kariyab, Sho Shirakata，“Three-stage growth of Cu–In–Se polycrystalline thin films by chemical spray pyrolysis”， Solar Energy Materials & Solar Cells 91 (2007) 1152–1159
[48] Clayton W. Bates Jr.，“Preparation of metal-semiconductor composite films by chemical spray pyrolysis”，Materials Letters 30 (1997) 87-91
[49] Seung Soo Lee, Kook Won Seo, Jong Pil Park, Sin Kyu Kim, and Il-Wun Shim, Inorganic Chemistry,“Deposition of CuInS2 Thin Films Using Copper- and Indium/Sulfide-Containing Precursors through a Two-Stage MOCVD Method”， Vol. 46, No. 3, 2007 1013
[50] M.C. Artaud , F. Ouchen , L. Martin , S. Duchemin, “CuInSe thin films grown by MOCVD: characterization, first devices”，Thin Solid Films 324(1998)115–123
[51] J. Eberhardt , J. Cieslak , H. Metzner , Th. Hahn , R. Goldhahn , F. Hudert , J. Kräußlich , U. Kaiser , A. Chuvilin , U. Reislöhner , W. Witthuhn ，“Epitaxial and polycrystalline CuInS2 layers: Structural metastability and its influence on the photoluminescence”，Thin Solid Films 517 (2009) 2248–2251
[52] Kenji Yoshino,Hirosumi Yokoyama, Kouji Maeda, and Tetsuo Ikari，“Optical characterizations of CuInSe2 epitaxial layers grown by molecular beam epitaxy”，Journal of Applied Physics; 10/15/99, Vol. 86 Issue 8, p4354-4359
[53] S. Niki, A. Yamada, R. Hunger, P.J. Fons, K. Iwata, K. Matsubara, A. Nishio and H. Nakanishi,“Molecular beam epitaxial growth and characterization of CuInSe2 and CuGaSe2 for device applications”， J. Cryst. Growth 237–239 (2002), p. 1993
[54] M. Kaelin , D. Rudmann, A.N. Tiwari，“Low cost processing of CIGS thin film solar cells”，Solar Energy ，77 (2004) 749–756
[55] Li, Ai-min; Qin, Juan; Shi, Wei-min; Wei, Guang-pu.，“Fabrication and properties study of Cu(In1-xGax)Se2 films by vacuum evaporation.”，Proceedings of SPIE (2008), 6984(Sixth International Conference on Thin Film Physics and Applications, 2008),
[56] Inoue, Hironobu; Kitani, Takahiko; Kimura, Tadashi. ，“Continuous vacuum evaporation deposition method of compound semiconductor film.”，Jpn. Kokai Tokkyo Koho (2005), 9 pp.
[57] Delahoy, Alan; Bruns, Juergen; Chen, Liangfan; Akhtar, Masud; Kiss, Zoltan; Contreras, Miguel.，“Advances in large area CIGS technology.”，Conference Record of the IEEE Photovoltaic Specialists Conference (2000), 28th 1437-1440.
[58] Kapil Mukati and Babatunde A. Ogunnaike，“Scaleup of Cu(InGa)Se2 Thin-Film Coevaporative Physical Vapor Deposition Process, 2. Evaporation Source Design”，Industrial & Engineering Chemistry Research (2008), 48(13), 5992-5999.
[59] Bodeg Ard, M.; Granath, K.; Stolt, L.，“Growth of Cu(In,Ga)Se2 thin films by coevaporation using alkaline precursors.”，Thin Solid Films (2000), 361-362 9-16
[60] Kohara, Naoki; Negami, Takayuki; Nishitani, Mikihiko; Wada, Takahiro. ，“Preparation of device-quality Cu(In,Ga)Se2 thin films deposited by coevaporation with composition monitor.” ， Japanese Journal of Applied Physics, Part 2: Letters (1995), 34(9A), L1141-L1144.
[61] M.M. Islam , T.Sakurai , S.Ishizuka, A.Yamada, H.Shibata, K.Sakurai, K. Matsubara, S.Niki, K.Akimoto,“Effect of Se/(Ga+In) ratio on MBE grown Cu(In,Ga)Se2 thin film solar cell”， Journal of Crystal Growth 311 (2009) 2212–2214
[62] M.M. Islam , S.Ishizuka , A.Yamada , K.Sakurai , S.Niki , T.Sakurai , K.Akimoto ，“CIGS solar cell with MBE-grown ZnS buffer layer”， Solar Energy Materials & Solar Cells 93 (2009) 970–972
[63] Ishizuka, Shogo; Yamada, Akimasa; Shibata, Hajime; Sakurai, Keiichiro; Fons, Paul; Matsubara, Koji; Niki, Shigeru.，“Preparation of Cu(In1-xGax)Se2 thin films for solar cells using a Se-radical beam source.”，Materials Research Society Symposium Proceedings (2007),1012(Thin-Film Compound Semiconductor Photovoltaics--2007)
[64] Yoon, Kyung Hoon; Kim, Seok Ki; Chalapathy, R. B. V.; Yun, Jae Ho; Lee, Jeong Chul; Song, Jinsoo; Ahn, Byung Tae.，“Characterization of a molybdenum electrode deposited by sputtering and its effect on Cu(In,Ga)Se2 solar cells.”，Journal of the Korean Physical Society (2004), 45(4), 1114-1118.
[65] Jiao, Fei; Liao, Cheng; Zhou, Zhen; Han, Jun-fei; Xie, Hua-mu; Zhao, Kui.，“Application of sputtering -based laminating selenylation process to preparation of CIGS thin films.”，Zhenkong (2008), 45(4), 66-69.
[66] A. J. Hall, D. Hebert, C. Lei, A. Rockett and S. Siebentritt，“Epitaxial growth of very large grain bicrystalline Cu(In,Ga)Se2 thin films by a hybrid sputtering method”，Journal of Applied Physics 103, 083540 (2008)
[67] Douglas L. Schulz, Calvin J. Curtis, Rebecca A. Flitton, Holm Wiesner, James Keane, Richard J. Matson, Kim M. Jones, Philip A. Parilla, Rommel Noufi, and David S. Ginley，“Cu-In-Ga-Se Nanoparticle Colloids as Spray Deposition Precursors for Cu(In,Ga)Se2 Solar Cell Materials”，Journal of Electronic Materials, Vol. 27, No. 5, 1998
[68] Shirakata, Sho; Kannaka, Yoshiaki; Hasegawa, Harufumi; Kariya, Tetsuya; Isomura, Shigehiro. ，“Properties of Cu(In,Ga)Se2 thin films prepared by chemical spray pyrolysis.”，Japanese Journal of Applied Physics, Part 1: Regular Papers, Short Notes & Review Papers (1999), 38(9A), 4997-5002
[69] Reddy, K. T. Ramakrishna; Chalapathy, R. B. V.，“Spray pyrolysis of CuGaxIn1-xSe2 thin films - electrical and optical properties.”，Institute of Physics Conference Series (1998), 152(Ternary and Multinary Compounds), 317-320.
[70] Wei Li , Yun Sun, Wei Liu, Lin Zhou，“Fabrication of Cu(In,Ga)Se2 thin films solar cell by selenization process with Se vapor”， Solar Energy 80 (2006) 191–195
[71] Wei Liu, Jian-Guo Tian, Zu-Bin Li, Qing He, Feng-Yan Li, Chang-Jian Li and Yun Sun，“Novel in situ resistance measurement for the investigation of CIGS growth in a selenization process”，Semiconductor Science and Technology (2009), 24(3), 035019/1-035019/4.
[72] Han, Donglin; Zhang, Gong; Zhuang, Daming; Yuan, Jinshi; Song, Jun.，“Se vapor selenization method parameters for deposition of CIGS films (I) Influences of Ar flux on microstructure and morphologies of CIGS films.”，Taiyangneng Xuebao (2009), 30(4), 426-429.
[73] J. Kois , M. Ganchev , M. Kaelin , S. Bereznev , E. Tzvetkova , O. Volobujeva , N. Stratieva , A.N. Tiwari，“Electrodeposition of Cu–In–Ga thin metal films for Cu(In, Ga)Se2 based solar cells”，Thin Solid Films 516 (2008) 5948–5952
[74] Xia, Dong-lin; Xu, Man; Li, Jian-zhuang; Zhao, Xiu-jian，“Study of Cu(In,Ga)Se2 thin films by the electrodeposition.”，Rengong Jingti Xuebao (2006),35(5), 1146-1150.
[75] K. Bouabid, A. Ihlal, A. Manar, A. Outzourhit, E.L. Ameziane，“Effect of deposition and annealing parameters on the properties of electrodeposited CuIn1-xGaxSe2 thin films”，Thin Solid Films 488 (2005) 62 – 67
[76] Raghu N. Bhattacharya, Arturo M. Fernandez，“CuIn1-xGaxSe2-based photovoltaic cells from electrodeposited precursor films”，Solar Energy Materials & Solar Cells 76 (2003) 331–337
[77] R. Friedfeld, R.P. Raffaelle, J.G. Mantovani，“Electrodeposition of CuInxGa1-xSe2 thin films”，Solar Energy Materials & Solar Cells 58 (1999) 375}385
[78] I.H. Choi , D.H. Lee，“Preparation of CuIn1-xGaxSe2 films by metalorganic chemical vapor deposition using three precursors”，Thin Solid Films 515 (2007) 4778–4782
[79] S. Spiering , L. Bürkert , D. Hariskos , M. Powalla , B. Dimmler , C. Giesen , M. Heuken，“MOCVD indium sulphide for application as a buffer layer in CIGS solar cells”，Thin Solid Films 517 (2009) 2328–2331
[80] M. Kaelina,, D. Rudmanna, F. Kurdesaua, H. Zogga, T. Meyerb, A.N. Tiwari ，“Low-cost CIGS solar cells by paste coating and selenization”，Thin Solid Films 480–481 (2005) 486–490
[81] T. Wada, Y. Matsuo, S. Nomura, Y. Nakamura, A. Miyamura, Y. Chiba, A. Yamada, and M. Konagai，“Fabrication of Cu(In,Ga)Se2 thin films by a combination of mechanochemical and screen-printing/sintering processes”，phys. stat. sol. (a) 203, No. 11, 2593– 2597 (2006)
[82] D.D. Shivagan , P.J. Dale, A.P. Samantilleke, L.M. Peter，“Electrodeposition of chalcopyrite films from ionic liquid electrolytes”，Thin Solid Films 515 (2007) 5899–5903
[83] D. Lincot , J.F. Guillemoles , S. Taunier , D. Guimard , J. Sicx-Kurdi , A. Chaumont,O. Roussel , O. Ramdani , C. Hubert , J.P. Fauvarque, N. Bodereau, L. Parissi, P. Panheleux, P. Fanouillere, N. Naghavi, P.P. Grand, M. Benfarah, P. Mogensen,O. Kerrec，“Chalcopyrite thin film solar cells by electrodeposition”，Solar Energy 77 (2004) 725–737
[84] Xia, Dong-lin; Zhao, Xiu-jian; Li, Jian-zhuang.，“Influence of Na citrate concentration on Cu(In,Ga)Se2 thin films by electrodeposition.”，Rengong Jingti Xuebao (2005), 34(4), 704-708.
[85] 葉文進 游政家 葉翳民,“電沉積理想化學計量比CIGS 薄膜”，2007材料年會，(NSC95-2221-E-274-019)
[86] R. Caballero, C. Guille´n，“Structural and morphological properties of Cu(In, Ga)Se2 thin films on Mo substrate”，Applied Surface Science 238 (2004) 180–183
[87] Basol, Bulent M.，“Method and apparatus for modifying surface composition of copper-indium-gallium-selenide ( CIGS ) absorbers formed by two-stage process.”，U.S. Pat. Appl. Publ. (2009), 9pp., Cont.-in-part of U.S. Ser. No. 740,248.
[88] Ki Hwan Kim,Kyung Hoon Yoon, Jae Ho Yun and Byung Tae Ahn,Electrochemical and Solid-State Letters，“Effects of Se Flux on the Microstructure of Cu(In,Ga)Se2 Thin Film Deposited by a Three-Stage Co-evaporation Process”，9 (8) A382-A385 (2006)
[89] Doo Youl Lee, Byung Tae Ahn,Kyung Hoon Yoon and Jin Soo Song，“Effect of first-stage temperature on Cu(In,Ga)Se2 solar cells using the evaporation of binary selenide compounds”，Solar Energy Materials and Solar Cells，Volume 75, Issues 1-2, January 2003, Pages 73-79
[90] Jae Ho Yun , Ki Hwan Kim, Byung Tae Ahn and Kyung Hoon Yoon，“Effect of Se beam flux rate on photovoltaic properties of CIGS cells fabricated by three-stage co-evaporation process”， phys. stat. sol. (c) 3, No. 8, 2547– 2550 (2006)
[91] V.K. Kapur, A. Bansal, P. Le, O. Asensio, N. Shigeoka, Proceedings of the 3rd World Conference on Photovoltaic Energy Conversion, Osaka, Japan, May 11–18, 2003, p. 465.
[92] 馬振基,”奈米材料科技原理與應用”,全華,民92
[93] W. J. Dawson, “ Hydrothermal synthesis of advanced ceramic powders. ”,A. Ceram. Bolletin , 67, (1988)1673-1678.
[94] P. Pinceloup; C. Courtois; A. Leriche; B. Thierry,“Hydrothermal synthesis of nanometer-sized barium titanate powders: control of barium/titanium ratio, sintering, and dielectric properties.” ,J. Am. Ceram. Soc, 82 , (1999) , 3049-3056.
[95] S. Komarneni; R. Roy; Q.H. Li,“Microwave-hydrothermal synthesis of ceramic powders. ”,Mater. Res. Bull, 27,(1992) ,1393-1405.
[96] S. Komarneni;R.K. Rajha;H. Katsuki, “Microwave-hydrothermal processing of titanium dioxide.”,Mater. Chem. Phys, 61, (1999) ,50-54,.
[97] Yung-Jung Hsu,Chiu-Ming Hung, Yi-Feng Lin,Ben-Jie Liaw,Tarlok S. Lobana, Shih-Yuan Lu, and C. W. Liu，“[Cu4Se2P(OiPr)24]: A Novel Precursor Enabling Preparation of Nonstoichiometric Copper Selenide (Cu2-xSe) Nanowires”，Chem. Mater. 2006, 18, 3323-3329
[98] Jem-Min Chen, Bidyut K. Santra, C.W. Liu ，“Intermolecular Se‧‧‧Se interactions observed in indium compounds containing dialkyl diselenophosphate ligands: syntheses, structure, and solution studies of [In{Se2P(OR)2}3]”，Inorganic Chemistry Communications 7 (2004) 1103–1105
[99] Y.-G. Chuna, K.-H. Kimb, K.-H. Yoona ，“Synthesis of CuInGaSe2 nanoparticles by solvothermal route”，Thin Solid Films 480–481 (2005) 46–49
[100] Jong WonPark , YoungWooChoi , EunjooLee , OhShimJoo , SunghoYoon , ByoungKounMin，“Synthesis of CIGS absorber layers via a paste coating”，Journal of Crystal Growth 311 (2009) 2621–2625