臺灣博碩士論文加值系統

在過去的文獻中，半導體化合物通常是以乾式的製程技術來製備，電沉積是一種應用合成半導體化合物的新興方法，特別是用在氧化物或硫化物上。II-VI族化合物是具有寬能隙而且直接能隙的半導體材料，在這裡利用電沉積的方式製備半導體薄膜，透過不同的製備條件，尋求薄膜製程的最佳化條件。
在本實驗中，主要是研究利用電沉積方法製備氧化鋅、硫化鋅和硒化鋅薄膜，藉由不同的電沉積參數，例如電鍍液濃度、沉積電位、沉積溫度等條件，鍍製薄膜。從實驗中可以發現氧化鋅需要在較高溫的環境，避免產生氫氧化鋅，經過實驗後氧化鋅在80℃、-1.3V的條件下能生成較好氧化鋅薄膜。硫化鋅和硒化鋅則是需要透過錯合劑的幫助，才能使其共沉積ITO玻璃上，加入氨水有助於硫化鋅的生成，而不同的檸檬酸鈉的量則是會影響硒化鋅的沉積。在後段的退火過程，如果沒有在真空系統下退火，會造成硫化鋅和硒化鋅的氧化，使得XRD的訊號減弱。

In previous researches, semiconductor thin films were usually prepared by dry methods. Electrodeposition is emerging as a method for the synthesis of semiconductor thin films, especially chalcogenides and oxides. Having direct and wide band gap, II-VI compound semiconductors are potential material for use for photovoltaic devices. We use the way to prepare semiconductor in order to find the optimization by patterns.
In this experiment, we study to prepare zinc oxide, zinc sulfur and zinc selenium by electrodeposition. According to the parameters of electrodeposition, e.g. concentration, deposited potential and deposited temperature else. In this study, we can find zinc oxide which needs to grow in high temperature, and zinc sulfur and zinc selenium need to deposit on ITO glass with complexing agent. In the finial process of annealing, it makes zinc sulfur and zinc selenium oxidized without vacuum system, and the signals of XRD are weaker.
In this study we deposit the ZnO thin films onto the ITO-coated glass substrate by electrochemical deposition from the 0.5 M Zn(NO3)2 electrolyte. Optimized deposition parameters such as electrolyte concentration, electrochemical potential and bath temperature were also discussed. Cyclic voltammetry experiments were performed to determine the reaction potential. Orientation (002) in ZnO thin film of XRD spectrum can be used as indicator

目錄
中文摘要………………………………………...………..I
英文摘要………………………………………………..Ⅱ
誌謝………………...……………………………………..Ⅲ
目錄………………………………………………………IV
表目錄……...……………………………………………..Ⅷ
圖目錄……………………………………………………IX
第一章 緒論………………………………………………1
1-1 前言……………………………………………………………………1
1-2 研究動機………………………………………………………………2
第二章 研究背景與實驗方法……………………………4
2-1 研究背景………………………………………………………………4
2-1-1 氧化鋅介紹…………………………………………………………4
2-1-2 硫化鋅介紹…………………………………………………………6
2-1-3 硒化鋅介紹…………………………………………………………7
2-2 II-VI族半導體薄膜製備方式………………………9
2-2-1 化學氣相沉積法(Chemical Vapor Deposition，CVD) ……………10
2-2-2 濺鍍法(sputtering) ………………………………………………10
2-2-3 脈衝式雷射蒸鍍(Pulsed Laser Deposition，PLD ) ……………11
2-2-4原子層磊晶法(Atomic Layer Deposition，ALD) …………………12
2-2-5 化學浴沉積法(Chemical Bath Deposition，CBD) ……….…………13
2-2-6 電化學沉積法(Electrochemical deposition) ……………...…………14
2-3 電化學原理…………………………………………14
2-3-1循環伏安法(Cyclic Voltammetry) ………………………………15
2-3-2 定電位電解法(Chronoamperometry) ………………………17
2-3-3 定電流電解法(Chronopotentiometry) …………………………17
2-3-4 電化學的優勢與劣勢………………………………………………17
第三章 實驗……………………………………………19
3-1實驗流程及步驟……………………………………19
3-1 實驗流程………………………………………………………………20
3-1-1 實驗藥品……………………………………………………………21
3-1-2 電極系統……………………………………………………………21
3-2 電化學沉積反應機制…………..……………………21
3-2-1 電化學沉積氧化鋅(ZnO)薄膜……………………………………21
3-2-2 電化學沉積硫化鋅(ZnS)薄膜……………………………………22
3-2-3 電化學沉積硒化鋅(ZnSe)薄膜……………………………………23
3-3電化學系統及儀器架設……………………………23
3-4 電沉積方法鍍膜……………………………………24
3-4-1 ITO玻璃前處理………………………………………………………24
3-4-2 氧化鋅薄膜鍍製……………………………………………………25
3-4-3 硫化鋅薄膜鍍製……………………………………………………25
3-4-4 硒化鋅薄膜鍍製……………………………………………………25
3-5 試片分析……………………………………………26
3-5-1 結構材料分析……………………………………………………26
3-5-2 光學分析……………………………………………………………27
第四章 結果與討論……………………………………28
4-1 氧化鋅………………………………………………28
4-1-1 循環伏安法分析……………………………………………………28
4-1-2 沉積電位與溫度分析………………………………………………29
4-1-3 pH值影響……………………………………………………………37
4-1-4 退火溫度的探討……………………………………………………40
4-2 硫化鋅………………………………………………45
4-2-1 循環伏安法分析……………………………………………………45
4-2-2 組成比例與氨水濃度討論…………………………………………49
4-2-3 氧化電位與時間……………………………………………………55
4-2-4 pH值影響……………………………………………………………64
4-2-5 退火溫度的探討……………………………………………………68
4-3 硒化鋅………………………………………………73
4-3-1 循環伏安法分析……………………………………………………73
4-3-2 錯合劑濃度討論……………………………………………………76
4-3-3 沉積電位的探討……………………………………………………81
4-3-4 pH值影響……………………………………………………………85
4-2-5 退火溫度的探討……………………………………………………90
第五章 結論……………………………………………95
參考文獻…………………………………………………96
附錄……………………………………….………………98

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