本論文利用電鍍製程在室溫下製備Cu(In,Ga)Se2薄膜，主要目的為提供Cu-In-Ga-Se四元電化學系統的基礎特性分析，並藉由共電鍍的方式沉積出接近理想化學組成之Cu(In,Ga)Se2薄膜。
本實驗由電化學特性分析開始，在傳統的三電極電鍍槽當中，於鉬基板(Mo substrate)上針對含有Cu、In、Ga、Se等四種離子的溶液，從單元素至四元素的溶液系統進行循環伏安法分析，並輔以SEM、EDS、XRD等薄膜分析來判斷各種離子在溶液當中的反應機制。為了建立較完整的電化學資料庫與比較不同基板造成的反應機制差異，我們也進行了使用銅做為基板的電化學分析實驗。實驗結果發現Ga於Cu或Se存在時，有明顯的欠電位沉積效應，透過此種效應，不必施以符合Ga元素還原電位的電壓也可以得到含Ga的Cu(In,Ga)Se2薄膜。接著我們為了確認共電鍍Cu-In-Ga-Se溶液之可行性，將共電鍍所得之初鍍膜與共電鍍的CuInSe2薄膜做比較，利用EDS、XRD等分析來確認其為四元黃銅礦結構化合物Cu(In,Ga)Se2。最後我們討論了各種製程參數對共電鍍Cu(In,Ga)Se2之影響，諸如溶液中In、Ga離子之濃度、電鍍時間、熱退火處理、以及加入檸檬酸鈉(Na-citrate)為錯合劑等等因素。實驗的結果藉由SEM、EDS、XRD、Raman spectroscopy等分析方法，幫助我們分析觀察Cu(In,Ga)Se2薄膜之晶體結構、表面形貌、化學組成等變化，並探討Cu(In,Ga)Se2薄膜產生變化的原因。實驗結果顯示，加入適量的檸檬酸鈉錯合劑可以提升薄膜中的[In]+[Ga]比例。而含有高Ga3+濃度溶液所製備的薄膜經過熱處理後Ga含量有明顯的上升，其原因可能為Cu(In,Ga)Se2薄膜底部的Ga元素擴散所致。

This thesis focus on the co-electrodeposition of stoichimetric Cu(In,Ga)Se2 thin films, and the electrochemical study of the Cu-In-Ga-Se system has been presented. Cyclic voltammegram was adopted to help clarify the electrochemical characteristics of acid solution containing Cu2+, In3+, Ga3+ and H2SeO3 on Mo substrate. Electrochemical behavior from unitary Cu, In, Ga and Se system to quaternary Cu-In-Ga-Se system were fully investigated, and the insertion of Ga into the solid phase was found to be carried out through an induced co-deposition mechanism. For better insight of the mechanism, a cyclic voltammetric study were also performed on Cu substrates. Based on this mechanism, Cu(In,Ga)Se2 thin films were able to be formed on Mo substrate by co-electrodeposition. XRD was used to identify the as-deposited film as the quaternary chalcopyrite compound while composition and morphology were characterized by EDS and SEM, respectively. In order to achieve a higher level of gallium insertion, influence of solution concentration, deposition time, complexing agent and annealing was examined. Results show that the use of complexing agent allowed an stable increase in [In]+[Ga] content by limiting Cu-Se compound formation. Changing in Ga3+ concentration seems no immediate effect on Ga insertion, yet an increasing gallium atomic percentage from 1. 9% to 3.7% was obtained from the annealed Cu(In,Ga)Se2 film with higher Ga3+ concentration, indicating the diffusion of Ga from the underlying Ga-rich Cu(In,Ga)Se2 film after annealing.

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