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  • 學位論文

太陽能用三元 Ag-In-Se 材料相平衡與 In/Ag2Se 之界面反應

Phase equilibria of ternary Ag-In-Se solar material system and the In/Ag2Se interfacial reactions

指導教授 : 陳信文

摘要


太陽能的應用是當今重要之課題。其中Ag-In-Se材料系統之三元化合物AgInSe2為具有良好光電效益的太陽電池材料,更吸引了相當多之研究探討。而Ag-In-Se相平衡及In/Ag2Se界面反應對相關太陽能材料開發及製備相當重要。首先主要部分為三元系統相平衡以及界面反應探討。由純銀、純銦及純硒製備不同組成之三元合金,於450oC經長時間熱處理(3個月)以達平衡。除了平衡相之分析外,意外發現靠近富銀端時之部分合金,於熱處理後長出銀鬚經過3天以上於450oC的熱處理後會在合金表面析出銀鬚。析出的銀鬚觀察表面,具有一定的結晶性,以XRD及TEM等方式分析其結構,推測生成原因與錫鬚類似均為應力累積所造成。第二項主要部分為Ag2Se與In之固/液界面反應。以純銀與硒製備Ag2Se基材。並與純銦置於450oC及300oC爐中反應。在450oC反應初期,於界面可以見到一層反應層生成。經過三分鐘以上的反應時間, In/Ag2Se界面間會生成兩層結構明顯相異的反應層,從型態可略分為縱向成長及橫向擴散的兩層反應層。兩種不同型態的反應層均為涵蓋了二種以上生成相。依據生成相組成,此二種生成相為Liquid 與In4Se3。而在300℃界面反應之部分,初期生成一反應層,內部涵蓋的生成相依總組成判斷為Liquid+In4Se3。到了120分鐘後,基材端生成一縱向,與450℃反應類似結構之反應層,但其中所涵蓋之生成相與先前不同,為Ag2In+In4Se3。而其中並出現另一塊狀生成相AgInSe2,對生成之反應層進行X光繞射分析,可觀察出具有相對應化合物之繞射峰,而生成Ag2In而非AgIn2的現象,有文獻提到隨著時間增加而產生相變,由原來之AgIn2轉變為Ag2In,判斷其結構為反應形成。

並列摘要


Abstract Solar energy devices and their applications are among the most important research nowadays. Ternary Ag-In-Se and their related materials, especially the AgInSe2 ternary compound, have very good photo-galvanic properties, and have been intensively investigated. The knowledge of Ag-In-Se phase equilibria and In/Ag2Se interfacial reaction is crucial to the development and preparation of Ag-In-Se solar energy materials. However, very limited literatures are available. This study thus plans to work on the phase equilibria and interfacial reactions. The first part is about phase equilibria. Ternary Ag-In-Se alloys were prepared with pure Ag, In and Se. The alloys were equilibrated at 450oC, and the equilibrium phases were determined. Surprisingly, Ag whisker was found in the Ag-rich alloys after annealing in 450oC, It was also observed that these whiskers’ growth were with preferred growth direction and plane. With XRD and TEM analysis, a preferred orientation is determined. And the Ag whisker formation is a result of stress release from the solidified alloys. The second part is about In/Ag2Se interfacial reactions. The Ag2Se substrate was prepared with pure Ag and Se, and was reacted with pure indium. At the initial stage of reaction in 450oC, a reaction layer was formed at the interface. Two reaction layers were observed after reactions for 3 minutes. The two layers were with different vertical and horizontal morphologies, but were both liquid and In4Se3 phase. In the investigation at 300oC, a reaction layer was observed in initial stage. And the composition was liquid and In4Se3 phase. After 120 minutes reaction, another reaction layer was observed and had a vertical morphology. Composition of this layer was Ag2In and In4Se3 phase. AgInSe2 phase was also observed in this layer.

參考文獻


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