臺灣博碩士論文加值系統

因應環保問題與能源危機，氫能源被視為重要的解決方法之一，有效利用太陽能藉由光觸媒分解水產氫，便是此研究的終極目標。目前實驗室所製備出的AgInZn7S9光觸媒粉體之產氫速率，可達0.791 mA/cm2，本論文說明報導使用化學水浴法、熱蒸鍍法和電泳沉積法互相搭配，以兩階段方式製備四成份的(Ag-In-Zn)S固態溶液之可見光光觸媒薄膜，期望有良好的光反應活性，應用於氫氣之生產。
首先，我們先以熱蒸鍍法成長一層ZnS薄膜，再使用化學水浴法成長AgInS2薄膜。經過高溫燒結後，分析其組成、結晶結構與表面型態，發現薄膜試片在800 °C高溫燒結後仍為混相結構，由SEM表面型態分析判斷此四成分化合物半導體並不均勻。
第二種薄膜製備方式是先使用化學水浴法製備出(Ag-In-Zn)S粉體，以丙酮為溶劑，超音波震盪器使顆粒懸浮，將基材浸泡於懸浮溶液中，(Ag-In-Zn)S粉體在溶劑揮發後會附著在基材上，最後以高溫燒結方式將粉體固定在基板上。所獲得之樣品具有單一相結晶結構，亦具有階梯狀之表面型態，顯示以化學水浴法製備粉體搭配懸浮液浸泡方式，可以成功製備出(Ag-In-Zn)S固態溶液之薄膜試片。
為了解決薄膜試片的裸露問題，先以熱蒸鍍法所成長之ZnS薄膜取代矽晶圓基材。雖然薄膜試片較為緻密，但仍為混相結構之(Ag-In-Zn)S薄膜。也許將粉體的鋅含量降低，或者是調整熱處理環境，便可以將此兩階段製備的多成分硫化物在高溫下形成單一相之(Ag-In-Zn)S固態溶液。
由於化學水浴法所製備的(Ag-In-Zn)S粉體顆粒較小，可以電泳沉積法製備(Ag-In-Zn)S薄膜。初步的研究結果顯示，使用相同之四成分硫化物粉體，電泳沉積法較溶劑蒸乾法容易製備出緻密薄膜，亦具有單一相(Ag-In-Zn)S結晶結構。然而在光電化學研究方面，給予偏壓1V vs. SCE，在犧牲試劑電解質環境，照光強度100 mA/cm2，光電流值僅為0.0294 mA/cm2。綜合上述研究結果，目前我們已經解決多成分硫化物薄膜相分離的問題，使用溶劑蒸乾法或者是電泳沉積法皆可以得到單一相固態溶液，然而光電化學性質並未如預期。更多薄膜性質的研究，尤其是電子遷移機制的探討，將會是薄膜製程與光電化學反應系統往後努力的方向。

Hydrogen energy is considered to be an important renewable energy sources because of environmental protection and energetic crisis, and hydrogen production from water splitting is via photocatalyst. Visible light is a majority in the solar spectrum. The rate of hydrogen production of AgInZn7S9 powder which was made in tour lab is 0.791 mA/cm2. In the research, (Ag-In-Zn)S solid solution film was prepared by two steps which is composed of chemical bath deposition, thermal evaporation and electrodeposition. We hope that the value of photocurrent density of the film is large and the film could be applied in hydrogen production.
First, ZnS film was prepared by thermal evaporation, and then AgInS2 film was prepared by chemical bath deposition above ZnS film. The product was finally thermally treated. Base on the analytical tools of X-ray diffractometer and field emission scanning electron microscopy, the (Ag-In-Zn)S thin film was characterized in terms of the crystal structures, surface morphologies and thickness. The results showed that the product still belongs to a mixed-phase structure.
Second, (Ag-In-Zn)S powder was prepared by chemical bath deposition, and then acetone was added as a solvent. The particles were suspended by an ultrasonicator. The substrate was immersed in the suspended solution. After acetone was evaporated, (Ag-In-Zn)S particles adhered on the substrate which was thermally treated. Base on the analytical tools of X-ray diffractometer and field emission scanning electron microscopy, the (Ag-In-Zn)S thin film was characterized in terms of the crystal structures, surface morphologies and thickness. The results showed that the product had a single phase structure and an stair-shaped appearance. The thin film of (Ag-In-Zn)S solid solution was manufactured by the method.
To solve the vacant space in the films, the silicon wafer was instead of ZnS film. Base on the analytical tools of X-ray diffractometer and field emission scanning electron microscopy, the (Ag-In-Zn)S thin film was characterized in terms of the crystal structures, surface morphologies and thickness. The results showed the thin film had a more compact structure and a mixed-phase crystal structure. We expected that (Ag-In-Zn)S thin film of solid solution was fabricated by decreasing the component of Zinc.
The size of particles which were prepared by using chemical bath deposition was small. Therefore, we used electrodeposition to manufacture more compact thin film. With an applied potential of 1 V vs. SCE, (Ag-In-Zn)S thin film which was prepared by electrodeposition had a current density of 0.0294 mA/cm2.The above results indicated that the current density of the thin film was improved by thermally treating and deposition times.

目錄
中文摘要……………………………………………………….……….....i
英文摘要………………………………………………………...……….iii
目錄……………………………………………………………….………v
圖目錄……………………..……………………………………….……viii
表目錄……………………………………………………………….......xiv
第一章 緒論…………………………………………………..…………..1
1.1 研究背景………………………………………….…..………….1
1.2 研究動機………………………………………….….…….…….6
第二章 文獻回顧……………………………………………….….……..9
2.1 光觸媒分解水產氫原理………………………..………..………9
2.2 Ag-In-S半導體無機薄膜簡介………………………….………10
2.2.1 Ag-In-S薄膜製備技術………………………….………..12
2.2.1.1 噴霧熱裂解法(Spray Pyrolysis, SP)……………..12
2.2.1.2 硫化法(Sulphurization)………………………........13
2.2.1.3 連續式離子層吸收和反應法(Successive Ionic
Layer Adsorption and Reaction)….………....……13
2.2.1.4 熱蒸鍍法(Thermal Evaporation)…………….……14
2.2.1.5 化學水浴沉積法(Chemical Bath Deposition, CBD)
.……………………………………………………..14
2.3 (Ag-In-Zn)S半導體薄膜簡介…………………….…..…...……15
第三章 研究方法與步驟………………………………….…….....……17
3.1實驗藥品………………………………………….…….....…….17
3.2實驗儀器……………………………………………………..….18
3.3實驗檢測儀器……………………………………………..…….18
3.4實驗方法…………………………………………………...…....20
3.4.1 ZnS薄膜(熱蒸鍍法)+AgInS2薄膜(化學水浴法)…..……20
3.4.2以化學水浴法製備(Ag-In-Zn)S粉體再長成薄膜…..…..23
3.4.3 ZnS薄膜(熱蒸鍍法)+(Ag-In-Zn)S懸浮溶液(化學水浴法)
………………………………………………………..…...25
3.4.4以熱蒸鍍法(Thermal Evaporation)製備(Ag-In-Zn)S薄膜
……………………………………….………………….…25
3.4.5以電泳沉積法製備(Ag-In-Zn)S薄膜…………………....26
第四章 結果與討論……………………………………………………..27
4.1 ZnS薄膜(熱蒸鍍法)+AgInS2薄膜(化學水浴法)……..………27
4.1.1 晶型結構與表面型態分析………………………..……..27
4.2 以化學水浴法製備(Ag-In-Zn)S粉體再長成薄膜……….…....39
4.2.1 粉體機制探討………………………………………..…..39
4.2.2 (Ag-In-Zn)S粉體產氫速率之量測……………………..41
4.2.3 晶型結構與表面型態分析……………………………..42
4.2.3.1 在固定燒結溫度下，不同燒結時間對薄膜成長之
影響………………………………………………43
4.2.3.2在固定燒結溫度和時間下，不同鍍膜次數對薄膜成
長之影響…………………………………………50
4.2.4 UV-Vis圖譜分析……………………………………….57
4.3 ZnS薄膜(熱蒸鍍法)+(Ag-In-Zn)S懸浮溶液(化學水浴法)…59
4.3.1 晶型結構與表面型態分析……………………………..59
4.4 以電泳沉積法製備(Ag-In-Zn)S薄膜………………………...64
4.4.1 晶型結構與表面型態分析……………………………..64
4.4.2 光電化學測量…………………………………………..74
4.4.2.1 光電極薄膜製備………………………………….74
4.4.2.2 光電化學分析…………………………………….75
第五章 結論與未來展望………………………………………………79
參考文獻………………………………………………………………..80
 
圖目錄
圖1-1 利用太陽能產氫可能的路徑圖[6] 4
圖1-2 Honda-Fujishima effect：1. TiO2電極 2. Pt電極 3.隔膜 4. 外部負載 5.伏特計 5
圖1-3 AgInS2/ZnS相圖(1：單相合金；2：兩相合金)：(1)液相，(2)液相+α，(3)液相+ξ，(4)α，(5)液相+ξ+α，(6)液相+ξ+γ，(7) ξ+γ，(8)γ， 8
(9)γ+α，(10)γ+γ’，(11)γ’，(12)γ’+α，(13)α+β，(14)β。[16] 8
圖2-1 半導體光觸媒水分解之原理示意圖[17] 9
圖2-2 犧牲試劑之添加有助於光催化產生水產氫氣和氧氣 10
圖2-3 (a)與(b)分別為AgInS2之tetragonal和orthorhombic兩種結構，(c)為AgIn5S8 cubic結構[21]。 11
圖3-2 薄膜燒結900 °C之溫控曲線 21
圖3-3 使用化學水浴法鍍膜之實驗裝置圖 22
圖3-4 AgInS2薄膜製備流程圖 23
圖3-5 以化學水浴法製備(Ag-In-Zn)S粉體之實驗示意圖 24
圖3-6 以熱蒸鍍法製備(Ag-In-Zn)S薄膜之實驗示意圖 25
圖3-7 以電泳沉積法成長(Ag-In-Zn)S薄膜示意圖 26
圖4-1 熱蒸鍍法所製備出ZnS薄膜之XRD圖 28
圖4-2 以熱蒸鍍法所製備之ZnS薄膜之SEM圖。(a)放大倍率1K，(b)側視圖：放大倍率1K 29
圖4-3 實驗參數A、B、C、D，薄膜試片於700 °C分別燒結1小時、2小時、3小時、4小時之XRD圖 31
圖4-4 實驗參數E1、E2，薄膜試片於800 °C燒結30分鐘之XRD圖 31
圖4-5 實驗參數F1、F2，薄膜試片於800 °C燒結10分鐘之XRD圖 32
圖4-6 實驗參數G1、G2，薄膜試片於850 °C燒結10分鐘之XRD圖 32
圖4-7 實驗參數A，薄膜試片於700 °C燒結1小時之SEM圖。(a)放大倍率5K，(b)放大倍率1K 33
圖4-8 實驗參數B，薄膜試片於700 °C燒結2小時之SEM圖。(a)放大倍率5K，(b)放大倍率1K 34
圖4-9 實驗參數D，薄膜試片於700 °C燒結4小時之SEM圖。(a)放大倍率5K，(b)放大倍率1K 35
圖4-10 實驗參數E2，薄膜試片於800 °C燒結30分鐘之SEM圖。(a)放大倍率10K，(b)放大倍率2K 36
圖4-11 實驗參數F2，薄膜試片於800 °C燒結10分鐘之SEM圖。(a)放大倍率5K，(b)放大倍率1K 37
圖4-12 實驗參數G2，薄膜試片於850 °C燒結10分鐘之SEM圖。(a)放大倍率4.01K，(b)放大倍率1.5K 38
圖4-13 (Ag-In-Zn)S粉體之產氫速率(於300 W氙燈照射和反應溫度25 °C，在犧牲試劑下反應8小時) 42
圖4-14 薄膜試片於燒結溫度800 °C，不同燒結時間之照片 43
圖4-15 實驗參數A、B3、C，薄膜試片於燒結溫度800 °C，分別燒結30分鐘、10分鐘、5分鐘之XRD圖 45
圖4-16 實驗參數A，薄膜試片於燒結溫度800°C，燒結30分鐘之SEM圖。(a)放大倍率100K，(b)放大倍率50K，(c)側視圖：放大倍率10K 46
圖4-17 實驗參數B3，薄膜試片於燒結溫度800 °C，燒結10分鐘之SEM圖。(a)放大倍率100K，(b)側視圖：放大倍率10K，(c)側視圖：放大倍率2K 47
圖4-18 實驗參數C，薄膜試片於燒結溫度800 °C，燒結5分鐘之SEM圖。(a)放大倍率100K，(b)放大倍率50K，(c)放大倍率25K，(d)放大倍率10K，(e)放大倍率600，(f)側視圖：放大倍率10K，(g)側視圖：放大倍率2K 50
圖4-19 實驗參數D1、D2、D3，薄膜試片於燒結溫度800 °C，燒結時間5分鐘，分別鍍膜1、2、3次之XRD圖 51
圖4-20 實驗參數D1，薄膜試片於燒結溫度800 °C，燒結時間5分鐘，鍍膜1次之SEM圖。(a)放大倍率200K，(b)放大倍率100K，(c)放大倍率50K，(d)側視圖：放大倍率13K，(e)側視圖：放大倍率1.3K 54
圖4-21 實驗參數D2，薄膜試片於燒結溫度800 °C，燒結時間5分鐘，鍍膜2次之SEM圖。 (a)放大倍率100K，(b)放大倍率50K，(c)側視圖：放大倍率5K 55
圖4-22 實驗參數D3，薄膜試片於燒結溫度800 °C，燒結時間5分鐘，鍍膜3次之SEM圖。(a)放大倍率100K，(b)放大倍率50K，(c)放大倍率25K，(d)側視圖：放大倍率3K 57
圖4-23 不同鋅含量(Ag-In-Zn)S薄膜之反射式吸收光譜圖 58
圖4-24 實驗參數A、B、C，薄膜試片於燒結時間5分鐘，不同燒結溫度(800 °C和850 °C)和鍍膜次數(1次和2次)之XRD圖 60
圖4-25 實驗參數A，薄膜試片於燒結溫度800 °C，燒結時間5分鐘，鍍膜1次之SEM圖。(a)放大倍率70K，(b)側視圖：放大倍率10K 61
圖4-26 實驗參數B，薄膜試片於燒結溫度800 °C，燒結時間5分鐘，鍍膜2次之SEM圖。(a)放大倍率15K，(b)放大倍率1K，(c)側視圖：放大倍率5K 62
圖4-27 實驗參數C，薄膜試片於燒結溫度850 °C，燒結時間5分鐘，鍍膜1次之SEM圖。(a)放大倍率50K，(b)放大倍率1K，(c)側視圖：放大倍率1K 63
圖4-28 電泳沉積法所製備之(Ag-In-Zn)S薄膜試片 64
圖4-29 實驗參數A2、B2，薄膜試片於燒結溫度800 °C，燒結時間5分鐘，分別以一般高溫燒結爐和快速升溫燒結爐燒結之XRD圖 66
圖4-30 實驗參數A2，薄膜試片於一般高溫燒結爐中，以800 °C高溫燒結時間5分鐘，鍍膜1次之SEM圖。(a)放大倍率100K，(b)放大倍率50K，(c)放大倍率25K，(d)放大倍率1K，(e)放大倍率100 68
圖4-31 實驗參數B2，薄膜試片於一般高溫燒結爐中，以800 °C高溫燒結時間5分鐘，鍍膜1次之SEM圖。(a)放大倍率100K，(b)放大倍率50K，(c)放大倍率25K，(d)放大倍率1K，(e)放大倍率100 70
圖4-32 實驗參數C1，薄膜試片於一般高溫燒結爐中，以800 °C高溫燒結時間5分鐘，鍍膜1次之SEM圖。(a)放大倍率100K，(b)放大倍率50K，(c)放大倍率25K，(d)放大倍率1K，(e)放大倍率100 72
圖4-33 實驗參數D2，薄膜試片於一般高溫燒結爐中，以800 °C高溫燒結時間5分鐘，鍍膜2次之SEM圖。(a)放大倍率100K，(b)放大倍率50K，(c)放大倍率25K，(d)放大倍率1K，(e)放大倍率100 74
圖4-34 光電極之製備 75
圖4-35 實驗參數A2，薄膜試片於一般高溫燒結爐中，以800 °C高溫燒結時間5分鐘，鍍膜1次之光電流圖譜 77
圖4-36 實驗參數B1，薄膜試片於快速升溫燒結爐中，以800 °C高溫燒結時間5分鐘，鍍膜1次之光電流圖譜 77
圖4-37 實驗參數C1，薄膜試片於一般高溫燒結爐中，以800 °C高溫燒結時間5分鐘，鍍膜1次之光電流圖譜 78
圖4-38 實驗參數D2，薄膜試片於一般高溫燒結爐中，以800 °C高溫燒結時間5分鐘，鍍膜2次之光電流圖譜 78
 
表目錄
表1-1 各類碳氫化合物重組之單位產氫成本與能量效率比較[5] 4
表4-1 薄膜試片於不同燒結溫度和燒結時間之實驗參數彙整表 30
表4-2 實驗參數A試片之元素組成比例表 39
表4-3 薄膜試片於800 °C燒結，不同燒結時間之實驗參數彙整表 45
表4-4 薄膜試片於燒結溫度800 °C，燒結時間5分鐘，不同鍍膜次數之實驗參數彙整表 51
表4-5 具有不同鋅含量之試片實驗彙整表 58
表4-6 薄膜試片於燒結時間5分鐘，不同燒結溫度和鍍膜次數之實驗參數彙整表 60
表4-7 薄膜試片於燒結溫度800 °C，燒結時間5分鐘，使用不同粉體重量、不同燒結方式和鍍膜次數之實驗參數彙整表 65

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