臺灣博碩士論文加值系統

三元黃銅礦二硒銅銦(CIS)吸收層有高光學吸收係數(~105 cm-1)、可調能隙大小及長期穩定度等優點 [1]，是個大有可為的薄膜太陽能電池材料。CIS可利用化學組成、缺陷結構與製程條件形成N型或P型材料。目前多元共蒸鍍二硒銅銦鎵(CIGS)和二硒銅銦鋁(CIAS)最高效率分別可達19.9% [2]和16.9% [3]。像其它薄膜一樣，CIS也可以使用硒化 [4]、油墨噴印 [5]和電鍍 [6]等製程形成。太陽能電池的運行與效率極受薄膜形貌的影響。此研究利用濺鍍硒化製程形成幾種銅/(銦+鋁)的CI(A)S薄膜形貌。
使用硒化堆疊金屬先驅物形成富銦(鋁)、富銅及接近標準比例的CI(A)S薄膜，並探討薄膜成份對形貌的影響。結果指出相對於富銦(鋁)的薄膜而言，富銅和接近標準比例的CI(A)S薄膜有較大的晶粒和較平坦的表面，意味著銦含量(或厚度)會影響薄膜結晶和形貌。薄膜硒化在石墨盒或鋁盒沒有發現明顯的不同。在此研究中，所有樣品均以CI(A)S (112)為優選晶相。

The ternary chalcopyrite CuInSe2-like absorber is a promising material for the fabrication of thin-film solar cells due to its high optical absorption coefficient (~105 cm-1), adjustable band gap, and potential for long-term stability [1]. CIS films can be n- or p-type depending on its chemical composition, defect structures and preparation conditions. The highest efficiencies of 19.9% [2] and 16.9% [3] for thin-film Cu(In,Ga)Se2 (CIGS) and Cu(In,Al)Se2 (CIAS) solar cells have been realized by the multi-source elemental co-evaporation process, respectively. Like other thin films, they can also be fabricated by a variety of processes such as selenization [4], ink printing [5], electrodeposition [6], and so on. Film morphology could significantly impact on down stream solar cell processing and efficiency.
This thesis studied film morphology of CI(A)S thin film formed by selenizatoin of various ratio of Cu to In(Al) precursors prepared by sputtering. The composition effects on morphologies of (In,Al)-rich, Cu-rich, and near stoichiometric CI(A)S thin films were studied using selenization of stacked elements precursors. The results show that Cu-rich and near-stoichiometric CI(A)S films had larger grains and smoother surface than (In,Al)-rich film, indicating that In composition (or thickness) can influence on film crystallization as well as morphology. No obvious differences were found for film selenization in graphite box or aluminum box. CI(A)S (112) was the preferred orientation for all studied samples.

Chapter 1 Introduction
1.1 Importance of photovoltaic solar cells...............12
1.2 Brief History of CIS-like Solar Cells................15
1.3 Solar Cell Fundamentals..............................17
1.3.1 Air Mass and Solar Spectrum................19
1.3.2 Solar Cell I-V Characteristics.............22
1.3.3 Other Parameters...........................25
Chapter 2 Introduction to CIS-like solar cells
2.1 The properties of chalcopyrite-based materials...30
2.2 Development of CIS&CIGS thin film solar cells....35
2.3 Compositional analysis...........................42
Chapter 3 Experimental Scheme
3.1 Experimental motivation..........................43
3.2 Experiment procedures............................44
3.3 Process equipments...............................45
3.3.1 Sputter system.............................45
3.3.2 Annealing system...........................47
3.4 Analysis equipments..............................49
3.4.1 X-ray diffraction (XRD)....................49
3.4.2 Scanning Electron Microscope (SEM).........50
3.4.3 X-ray energy dispersive (EDS)..............52
Chapter 4 Results and Discussion
4.1 Selenium deficiency..............................53
4.2 Overflowing selenium problem.....................56
4.3 Extremely In-rich CIS film.......................57
4.4 Extremely Cu-rich CIS film.......................58
4.5 Particles on the surface.........................62
4.6 Negative effects of CIS films deposited on bare soda-lime glass...............................................63
4.7 CIAS film morphology modulation......................66
Chapter 5 Conclusions and Future works
5.1 Conclusions......................................72
5.2 Future works.....................................73

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