本論文主要是利用電化學分析方法來研究銅銦鎵硒薄膜太陽能電池吸收層的電沈積，藉此研究電沈積的機制來改善製程條件。由於電沈積優異高生產量與低成本，使其很有潛力成為成長金屬與半導體薄膜的方法，由於適合大面積生產以及無真空環境的需求讓可以實現量產，但是要將其應用在先進的薄膜製程上有許多挑戰與困難，如薄膜均勻性的改善、製程的穩定度、薄膜的品質與結晶性。然而電鍍液的組成對此步驟的效率有很大的影響，本文中利用各種電化學分析如循環伏安法、線性掃瞄伏安法作為主要的研究工具來探討電鍍溶液的成分。
而電沈積是沈積複和材質的主要技術，他相對有高真空需求的技術來說有極佳的生產優勢，因此電沈積被應用於發展太陽能光電，二硒化銅鎵銦(CIGS)在薄膜太陽應用上頗受矚目，單步驟電沈積是生產CIGS薄膜很有潛力的技術，但是多元素的電鍍液組成不易控制，電位的影響限制了各成分的濃度比例，線性掃瞄伏安法是用來研究銅銦硒競爭以及添加劑效用的重要方法，在傳統的方式，溶液濃度被相對的電壓控制來達到特定原子比例的CIGS薄膜，而光輔助電沈積提供一種調整CIGS薄膜原子比例的方式且可進一步提升薄膜品質，並且導入以以及加熱溶液等方式來改善CIGS薄膜均勻度與結晶性;後製程更使用了高壓退火方式增加薄膜結晶性，最後使用電化學蝕刻改善CIGS薄膜表面成分，進而產生等有序空位化合物層改善CIGS薄膜太陽能電池光電轉換效率;開路電壓(Voc)可由69 mV提升至374 mV，填充因子可由26.3 %提升至55 %，光電轉換效率可由0.49 %提升至7.12 %;並套用在濺鍍製程之CIGS薄膜太陽能電池上也可提升光電轉換效率，開路電壓(Voc)可由650 mV提升至693 mV，填充因子可由58 %提升至65 %，光電轉換效率可由11.4 %提升至13.8 %

In this thesis, electrochemical analyses were used to investigate the mechanism of electrodeposition process of thin film solar cell of Cu, In, Ga and Se compounds. Electrodeposition is a promising method for forming metal and semiconductor thin films due to its excellent gap-filling capacity and high throughput. Low cost mass production can be achieved because of large area plating under non-vacuum circumstances. However, there are several challenges of crystallinity and smooth films for applying electrodeposition to advanced thin film production. Electrochemical analyses, such as cyclic-voltammetry stripping (CVS) and linear scan voltammetry (LSV), are the major tools to investigate the composition of plating electrolytes.
Electrodeposition is a major technology to deposit complex metallic layers. It is scalable at low cost as compared to technologies requiring high vacuum. Therefore, electrodeposition has been developed for the applications of photovoltaics. CuInGaSe2 (CIGS) has been spotlighted for its applications in thin film solar cells. Single step electrodeposition is the most promising electrochemical technique to produce the CIGS film for solar cell applications. However, the composition of the CIGS film is hard to control in a ternary solution. The variation of electrolyte concentrations is restricted for single potential electrodeposition. LSV is an important method to investigate the influences of additives and the competitions of the Cu/In/Ga/Se. In the conventional deposition, the concentrations of electrolytes are restricted due to the correspondent plating potential of each ion to achieve a specific atomic ratio of the CIGS film. The electrodeposition methods of heating solution and substrate solution and photo-assistedwas used in the CIGS deposition to
improve the film quality and adjust the atomic ratio of the CIGS film, and we applied the pressurized annealed methods to made crystallinity CIGS films; at last electrochemical etching changed the surface atomic ratio of the CIGS film toincreasethe conversion efficiency of CIGS solar cells by made OVC(order vacancy compound) layer. The CIGS solar cells though the improved process by this work, the Voc was improved from 69 mV to 374 mV, the fill factor from 26.3 % to 55 % and the conversion efficiency from 0.49 % to 7.12 %.The solar cell of sputter CIGS films after electrochemical, the Voc was improved from 650 mV to 693 mV, the fill factor from 58 % to 65 % and the conversion efficiency from 11.4 % to 13.8 %.

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