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研究生： 鄭亨
Heng Jheng
論文名稱： 以化學水浴法製備AgInS2可見光光電極及其摻雜銅之研究
production of undoped and Cu-doped visible-light photoelectrode by chemical bath deposition
指導教授： 洪勵吾
Lih-Wu Hourng
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 能源工程研究所
Graduate Institute of Energy Engineering
畢業學年度： 97
語文別： 中文
論文頁數： 82
中文關鍵詞： 半體體薄膜 、光電極 、化學水浴法
外文關鍵詞： semiconductor thin film, photoelectrode, chemical bath deposition
相關次數： 點閱：21  下載：0 
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    • 摘要
    　　光電極產氫，為一種結合太陽能與氫能此兩種極具潛力且被視為未來兩顆新星之替代能源的新研究方向，利用光觸媒與電化學原理，將光電極置於水溶液中吸收太陽能，並利用此吸收的能源將水解離變成氫氣與氧氣，之後再將解離之氫氣收集起來，應用於氫能發電，此即為光電極產氫之基本概念。
    本實驗利用化學水浴法－此為一種設備簡單、製作便宜、產生廢料少且易於處理、具備大面積製備、極具經濟效益的化學製程，製備AgInS2可見光光電極薄膜，研究其材料特性，並應用於光電解水產氫。
    　　研究結果顯示AgInS2半導體光電極在無施加偏壓下照光可得到接近 4 mA/cm2的光電流密度，而在摻雜銅之後光電流在同樣條件下，可提升至5.5 mA/cm2之電流密度。
    　　因此，本研究應用化學水浴法此簡單製程所製備的AgInS2半導體光電極，為相當具成本優勢且光電轉換效率良好之極具潛力的材料之ㄧ。

    Abstract
    Hydrogen energy is regarded as prosperous alternative energy in the future. Among the hydrogen production methods, photoelectrochemical method is a promising technology. Based on photocatalytic and electrochemical principles, the photoelectrode absorbs solar energy and electrolyzes water into oxygen and hydrogen ions. The hydrogen ions move in the solution to the counter electrode and recover as hydrogen gas.
    In our experiment, the chemical bath deposition (CBD) method is adopted to produce AgInS2 visible-light photoelectrode film. CBD is simple, cheap, easier in handling waste, and large in area deposition. The influences of working parameters, such as: electrolytic concentration, heat treating, film thickness on the performance of hydrogen production are investigated in details.
    Experiments show that AgInS2 photoelectrode has almost 4 mA/cm2 photocurrent density at 0 bias. After doping Cu into AgInS2 at the same conditions, photocurrent density increases to 5.5 mA/cm2. Therefore, producing hydrogen with AgInS2 photoelectrode by chemical bath deposition is proved to have low-cost, yet efficient in the photo-electron conversion.

    總目錄 摘要 I Abstract II 總目錄 III 表目錄 VI 圖目錄 VII 符號說明 XII 第一章　緒論 1 1.1 前言 1 1.2 光電極發展 3 1.3 化學水浴法(CBD, Chemical Bath Deposition) 5 1.4 AgInS2可見光光電極薄膜 7 1.5 文獻探討 8 1.5.1 光觸媒文獻回顧 8 1.5.2 化學水浴法製備薄膜文獻回顧 9 1.5.3 Ag-In-S化合物半導體薄膜文獻回顧 11 1.5.4 摻雜金屬元素後光觸媒效能提升之文獻回顧 14 1.6 研究目的 14 第二章 化學水浴法原理 15 2.1 離子濃度積與溶解度積 15 2.2 成長機制 17 第三章 實驗步驟與方法 20 3.1 實驗參數設定 20 3.2 實驗藥品與實驗裝置 20 3.2.1 實驗藥品 20 3.2.1.1反應鍍液(Ag+、In3+、S2-)使用藥品 20 3.2.1.2銅(Cu)離子摻雜溶液之使用藥品 21 3.2.1.3 薄膜電性分析時配製電解質溶液之使用藥品 22 3.2.2 實驗基材 23 3.2.3 實驗設備 23 3.3 實驗步驟 24 3.3.1 基材清洗 24 3.3.2 鍍液配製 25 3.3.3 反應鍍液配製方法 26 3.3.4 半導體光觸媒薄膜之後處理 27 3.4 薄膜物性量測分析 27 3.4.1 XRD(X-ray Diffraction, X光粉末繞射儀) 27 3.4.2 SEM(Scanning electron microscope, 掃描式電子顯微鏡) 28 3.4.3 EDS(Energy Dispersive Spectrometer, 能量散射光譜儀) 29 3.4.4 UV-visible(紫外/可見光光譜儀) 29 3.4.5 電化學(光電流)量測分析 29 第四章 結果與討論 32 4.1 AgInS2半導體光觸媒薄膜製備 32 4.1.1 反應物濃度比例( [Ag+]/[In3+] )對薄膜的影響 32 4.1.2 pH值(HNO3含量)對薄膜的影響 33 4.1.3 鍍膜層數對薄膜的影響 37 4.1.4 磁石轉速對薄膜的影響 38 4.1.5 燒結溫度對薄膜的影響 39 4.2 銅摻雜之AgInS2半導體光觸媒薄膜製備 40 第五章 結論與未來展望 43 5.1結論 43 5.2未來展望 44 參考文獻 45 表目錄 表一 反應溶液參數表..........................................................................51 表二 銅離子摻雜溶液參數表..............................................................51 表三 量測電性分析所需配製之溶液參數表......................................52 表四　實驗變因與參數設定..................................................................52 表五 薄膜物性檢測儀器表..................................................................53 表六　EDS化學元素分析 [Ag+]/[In3+]=4, 500rpm, 燒結400℃ 一小時下鍍一層..........................................................................53 表七 EDS化學元素分析 [Ag+]/[In3+]=4, 500rpm, 燒結400℃ 一小時下鍍二層..........................................................................54表八 EDS化學元素分析 [Ag+]/[In3+]=4, 500rpm, 燒結400℃ 一小時下鍍三層..........................................................................54表九 EDS化學元素分析 [Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃ 一小時下摻雜銅2%....................................................................55 表十 EDS化學元素分析 [Ag+]/[In3+]=3, HNO3=15ml, 燒結300℃ 一小時下摻雜銅4%....................................................................55 表十一 EDS化學元素分析 [Ag+]/[In3+]=4, HNO3=15ml, 燒結　　 　　　　300℃一小時下摻雜6%..........................................................56 圖目錄 圖1-1　本多-藤島效應系統圖...............................................................57 圖1-2　光電極原理示意圖....................................................................57 圖1-3　太陽能量光譜圖........................................................................58 圖1-4 氧化物光觸媒於犧牲試劑下之產氫與產氧活性....................58 圖1-5 硫化物光觸媒於犧牲試劑下之產氫活性................................59 圖1-6 光觸媒摻雜金屬後之能隙圖....................................................59 圖2-1 化學水浴法成長機制................................................................60 圖2-2 化學水浴法薄膜成長階段示意圖............................................60 圖3-1 清洗基材流程圖........................................................................61 圖3-2 ITO基材封裝後之試片組........................................................61 圖3-3 金屬陽離子溶液調配流程........................................................62 圖3-4　用於摻雜之金屬銅離子溶液配製流程....................................62 圖3-5 化學水浴法流程示意圖............................................................63 圖3-6 化學水浴法實驗設置圖............................................................63 圖3-7　布拉格繞射示意圖....................................................................64 圖3-8 半導體光觸媒薄膜電極封裝示意圖........................................64 圖4-1 HNO3=15ml, 500rpm, 燒結400℃一小時下, 不同反應物濃度 比之光電極薄婆XRD圖譜.......................................................65 圖4-2 [Ag+]/[In3+]=3, 1000rpm, 燒結400℃一小時下, 不同HNO3量 之光電極薄膜XRD圖譜...........................................................65 圖4-3 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時下, 不同HNO3量之 光電極薄膜XRD圖譜..............................................................66 圖4-4 反應時間與薄膜生長厚度關係................................................66 圖4-5 pH值與薄膜厚度的關係..........................................................67 圖4-6 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時下, HNO3=9ml條 件下之光電極薄膜光電流量測結果........................................67 圖4-7 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時下, HNO3=15ml 條件下之光電極薄膜光電流量測結果....................................68 圖4-8 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時下, HNO3=21ml 條件下之光電極薄膜光電流量測結果....................................68 圖4-9 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時下, 不同HNO3量 之光電極薄膜XRD圖譜..........................................................69 圖4-10 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時下不同HNO3量 之光電極薄膜紫外/可見光光譜圖.........................................69 圖4-11 穿透定律示意圖......................................................................70 圖4-12 [Ag+]/[In3+]=4、500rpm、燒結400℃一小時下, 不同HNO3 量之光電極薄膜之能隙..........................................................70 圖4-13 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時下, 鍍膜層數不同 之光電極薄膜XRD圖譜........................................................71 圖4-14 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時, 鍍一層條件下之 光電極薄膜掃描式電子顯微鏡圖..........................................71 圖4-15 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時, 鍍二層條件下之 光電極薄膜掃描式電子顯微鏡圖..........................................72 圖4-16 [Ag+]/[In3+]=4, 500rpm, 燒結400℃一小時, 鍍三層條件下之 光電極薄膜掃描式電子顯微鏡圖..........................................72 圖4-17 [Ag+]/[In3+]=3, HNO3=15ml, 燒結400℃, 一小時下磁石轉速 不同之光電極薄膜XRD圖譜................................................73 圖4-18 [Ag+]/[In3+]=3, HNO3=15ml, 燒結400℃一小時下, 磁石轉速 不同之光電極薄膜紫外/可見光光譜圖.................................73 圖4-19 [Ag+]/[In3+]=3, HNO3=15ml, 燒結400℃一小時, 磁石轉速 500rpm條件下之光電極薄膜光電流量測結果....................74 圖4-20 [Ag+]/[In3+]=3, HNO3=15ml, 燒結400℃一小時, 磁石轉速 750rpm條件下之光電極薄膜光電流量測結果....................74 圖4-21 [Ag+]/[In3+]=3, HNO3=15ml, 燒結400℃一小時, 磁石轉速 1000rpm條件下之光電極薄膜光電流量測結果..................75 圖4-22 [Ag+]/[In3+]=4, HNO3=15ml, 磁石轉速500rpm下, 於不同燒 結溫度之光電極薄膜XRD圖譜............................................75 圖4-23 [Ag+]/[In3+]=4, HNO3=15ml, 磁石轉速500rpm下, 於不同燒 結溫度之光電極薄膜紫外/可見光光譜圖.............................76 圖4-24 [Ag+]/[In3+]=4, HNO3=15ml, 磁石轉速500rpm, 300℃燒結一 小時條件下之光電極薄膜光電流量測結果..........................76 圖4-25 [Ag+]/[In3+]=4, HNO3=15ml, 磁石轉速500rpm, 350℃燒結一 小時條件下之光電極薄膜光電流量測結果..........................77 圖4-26 [Ag+]/[In3+]=4, HNO3=15ml, 磁石轉速500rpm, 400℃燒結一 小時條件下光電極薄膜光電流量測結果..............................77 圖4-27 [Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時下不同摻雜 濃度之光電極薄膜XRD圖譜................................................78 圖4-28 [Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時, 摻雜銅2% 條件下之光電極薄膜掃描式電子顯微鏡圖..........................78 圖4-29 [Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時, 摻雜銅4% 條件下之光電極薄膜掃描式電子顯微鏡圖..........................79 圖4-30 [Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時, 摻雜銅6% 條件下之光電極薄膜掃描式電子顯微鏡圖..........................79 圖4-31 [Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時, 摻雜銅2% 條件下之光電極薄膜光電流量測結果..................................80 圖4-32 [Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時, 摻雜銅4% 條件下之光電極薄膜光電流量測結果..................................80 圖4-33 [Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時, 摻雜銅6% 條件下之光電極薄膜光電流量測結果..................................81 圖4-34　[Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時, 摻雜銅4%　 　　　　條件下之光電極薄膜紫外/可見光光譜圖.............................81 圖4-35　[Ag+]/[In3+]=4, HNO3=15ml, 燒結300℃一小時, 摻雜銅4% 條件下之能隙值......................................................................82

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