中文摘要
本研究是因應國內能源科技，研究發展製造低成本、大面積、高轉換效率太陽電池的新材料CuInSe2。近幾年來，由於Ⅰ-Ⅲ-Ⅵ2族三元黃銅礦（Chalcopyrite）半導體; CuMX2（M=In，Ga; X=Se，S）在非線性光學及光伏元件的應用上有很大的潛力，尤其是當做太陽電池的材料。針對大面積均勻性的需求，將使用電化學原子磊晶方法達成，而組成調變，是使用分子束磊晶達成變化之目的。分子束磊晶方法除具有低製造成本外，技術上配合電化學原子磊晶方法，可成長大面積磊晶層和具有可控制薄膜之組成之優點。由薄膜組成之控制，進而控制其電性及光學特性，使太陽電池達到高轉換效率之目的。
對大面積CuInSe2基板的研究，我們首先使用電沉積方法在ITO上沉積一層CuInSe2薄膜，再經由超高真空背景下之物理氣相沉積（PVD）進行熱退火處理。最後，再磊晶一層CuInSe2單晶層，完成Epi-ready的大面積CuInSe2基板的製作。再者，在固定銦分子束流量及過量硒分子的條件下，藉由變化銅分子束流量的強度來調變Cu/In比，以得到化學計量組成（stoichiometric）和In-rich或Cu-rich的晶膜。且能夠進一步控制其電導型式。並且經由MBE磊晶成長CuInSe2薄膜可達到成長晶膜的高重製性目的。
最後，希望能夠應用到大面積太陽電池製作，達到高轉換效率的目標。

Abstract
The objective of this proposed study is to develop the new material CuInSe2 for larger area, low cost and high efficiency commercial CuInSe2 based solar cell for the solar resource in Taiwan. Recently, TheⅠ-Ⅲ-Ⅵ2 ternary chalcopyrite semiconductors, CuMX2(M=In, Ga; X=Se, S) have received considerable potential for nonlinear optics and photovoltaic applications such as a promising material for solar cell. For the request of large area homogeneousness, the electrochemical atomic layer epitaxy (ECALE) and molecular beam epitaxy (MBE) are used to deposit and adjust the composition. The combination of the advantages of MBE and ECALE could produce the large area epitaxial layer and get the precise compositions of CuInSe2 films to obtain a high conversion efficiency for commercial solar cell applications.
For the study of large area CuInSe2 substrate, first, the electrochemical atomic layer epitaxy (ECALE) was applied to deposit a layer of CuInSe2 thin film on ITO substrate, and then the physical vapor deposition was applied for the annealing process to adjust the composition wanted. At last, a CuInSe2 epitaxial film was grown on the top of substrate under the MBE process. In addition, under the conditions of fixed In molecular beam flux and excess Se molecular beam flux, we can control the Cu/In composition ratio by changing Cu molecular beam flux to get stoichiometric and In-rich or Cu-rich epitaxial films, and predict the type of conductivity. It could be possible to obtain the high reproducibility and stability of the composition and properties of epilayers by controlling the growth parameters carefully.
Finally, We hope it can be used in the manufacture of solar cell and get large area high conversion efficiency.

目 錄
附表目錄……………...……………………………………….I
附圖目錄……………………………………………………...II
第一章 簡介………………………………...………………...1
1-1 前言……………………………………..………………...1
1-1-1 發展太陽電池的目的…………………..……………………1
1-1-2 太陽電池其種類與應用………………..……………………2
1-1-3 太陽電池之原理……………………….…………………….3
1-1-4 太陽電池之設計考量………………….…………………….7
1-2 高效率和穩定性的CuInSe2晶體結構與材料特性……...8
1-3 成長CuInSe2技術……………………………………….10
1-4 以PVD成長CuInSe2薄膜……………………………...18
1-5 研究目的與前置步驟…………………………………...20
第二章 實驗與原理…………………………………….…...22
2-1 實驗原理與理論………………………………….…..….22
2-1-1 一步驟電沉積原理…………………………………….…..22
2-1-2 物理氣相沉積成長理論………………………………..….23
2-2實驗設備………………………………………….…..….23
2-2-1 電沉積之裝置與儀器…………………………………...…23
2-2-2 PVD成長設備……………………………………….…...24
2-3 實驗步驟……………………………………………..….26
2-3-1 電沉積實驗步驟……………………………………….…..26
2-3-2 PVD實驗步驟…………………………………………....27
2-4 X-Ray繞射分析…………...……………………….…….29
第三章 理論模型模擬之結果與討論…………….…………...32
3-1 以PVD成長CuInSe2反應模型………………….……...32
3-1-1 基本關係式…………………………………..……………..32
3-1-2 將模型應用在CuInSe2……………………….…………….35
3-2 組成控制討論………………………………..……….....38
3-3 成長參數對晶膜組成討論……………………………...42
3-4 結晶特性分析………………………………..………….45
3-5 表面型態……………………………………..………….46
第四章 結 論………………………………………………..47
參考文獻……………………………………………………..97

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