本研究探討了通過連續離子層吸附和反應（SILAR）法製備的硫化銀摻雜銦在氧化鋅納米柱之上形成了一種新型的異質結構光陽極的形貌、晶體和光電化學性能。在本實驗中，首先利用一種簡單且低成本的水熱法在FTO基板上合成了氧化鋅奈米柱，再通過SILAR法在氧化鋅奈米柱上沉積不同的圈數的硫化銀摻雜銦。並根據材料分析，確認實驗成功製備出摻雜銦的硫化銀/氧化鋅奈米柱的結構。在此結構中，氧化鋅奈米柱的高表面積作為載體，增加了硫化銀摻雜銦的載子，提高了氫氣產生的效率。得到優化後的光陽極能隙寬度約為1.03 eV，將氧化鋅的吸收邊界拓寬到近紅外光。光電化學轉換研究表明，在0.35 M的硫化鈉和0.5 M的亞硫酸鈉混合溶液中用100 mW/cm2的模擬太陽光照射下，9圈沉積的光電極在-0.6 V（vs Ag/AgCl）下光電流密度為7.7 mA/cm2，此結果是相當有研究潛力的結果。
而第二部分同樣是將硫化鉍透過SILAR法沉積奈米顆粒在性價比高的氧化鋅上，並透過熱退火使結構穩定。硫化鉍/氧化鋅的能隙寬度大約有1.6 eV，可驅使水分解反應，使反應過程中，由光陽極產出氧氣。在光電化學量測中可以看到，在0.5 M的硫酸鈉電解液中施加0.6 V（vs Ag/AgCl）時電壓的光電流密度約有7.6 mA/cm2，且利用溶氧機量測，量測出法拉第效應高達98.32%，通過這一系列實驗，證實了在氧化鋅上沉積硫化物形成新型異質結構能成為相當有前景的光電極材料。

This study investigates a novel heterostructured photoanode consisting of indium-doped silver sulfide deposited on zinc oxide nanorods using the successive ionic layer adsorption and reaction (SILAR) method. In the experiment, zinc oxide nanorods were synthesized on a fluorine-doped tin oxide (FTO) substrate using a simple and low-cost hydrothermal method. Subsequently, different SILAR cycles were employed to deposit indium-doped silver sulfide onto the zinc oxide nanorods. Material analysis confirmed the successful fabrication of the indium-doped silver sulfide/zinc oxide nanorod structure. The high surface area of the zinc oxide nanorods serves as a carrier, enhancing the charge carrier concentration of the indium-doped silver sulfide and improving the efficiency of hydrogen generation. The optimized photoanode exhibits a bandgap width of approximately 1.03 eV, extending the absorption edge of zinc oxide into the near-infrared range. Photovoltaic conversion studies revealed that under simulated solar illumination of 100 mW/cm2 in a mixed solution of 0.35 M sodium sulfide and 0.5 M sodium bisulfite, the photoelectrode with nine SILAR cycles achieved a photocurrent density of 7.7 mA/cm2 at -0.6 V (vs Ag/AgCl). These results demonstrate significant research potential.

The second part of the study involves the SILAR deposition of bismuth sulfide nanoparticles onto cost-effective zinc oxide, followed by thermal annealing to stabilize the structure. The bismuth sulfide/zinc oxide heterostructure exhibits a bandgap width of approximately 1.6 eV, enabling water splitting reactions and the production of oxygen at the photoanode. The photoelectrochemical measurements show that at an applied voltage of 0.6 V (vs Ag/AgCl) in a 0.5 M sulfuric acid electrolyte, the photoelectrode achieves a photocurrent density of approximately 7.6 mA/cm2. Moreover, oxygen evolution was measured using an oxygen meter, yielding a high Faradaic efficiency of 98.32%. Through this series of experiments, it has been confirmed that the deposition of sulfides on zinc oxide to form a novel heterostructure holds great promise as a photoelectrode material.

謝誌 i
摘要 ii
Abstract iii
目錄 v
圖目錄 ix
表目錄 xi
第一章 緒論 1
1-1 前言 1
1-2 太陽能 2
1-3 空氣質量 4
1-4 氫能 5
第二章 理論基礎與文獻回顧 6
2-1 電化學 6
2-1-1 光電化學 6
2-1-2 電化學系統 6
2-1-3 半導體能隙寬度 7
2-1-4 水裂解 8
2-1-5 光電化學產氫 8
2-2 文獻回顧 9
2-2-1 氧化鋅 (ZnO) 9
2-2-2 硫化銀 (Ag2S) 10
2-2-3 摻雜銦 (In doped) 10
2-2-4 硫化鉍 (Bi2S3) 10
2-3 研究動機 11
2-3-1 In-doped Ag2S/ZnO異質結構應用於光電化學產氫 11
2-3-2 Bi2S3/ZnO異質結構應用於光電化學水分解 11
第三章 實驗方法與步驟 12
3-1 氧化鋅奈米柱製備 12
3-1-1 基板清洗 12
3-1-2 放置氧化鋅晶種在FTO基板 13
3-1-3 水熱法-氧化鋅奈米陣列結構 13
3-2 硫化銀摻雜銦/氧化鋅製備 14
3-2-1 連續離子層吸附法-硫化銀摻雜銦 14
3-3 硫化鉍/氧化鋅製備 15
3-3-1 連續離子層吸附法-硫化鉍 15
3-3-2 熱處理-硫化鉍 16
3-4 材料分析 16
3-4-1 場發射掃描式電子顯微鏡 16
3-4-2 穿透穿透式電子顯微鏡 17
3-4-3 X-ray 繞射儀 18
3-4-4 X射線光電子能譜儀 18
3-4-5 紫外線-可見光光譜儀 19
3-5 光電化學分析 20
3-5-1 線性伏安法 20
3-5-2 入射光子-電子轉換效率 21
3-5-3 莫特蕭特基量測 21
3-5-4 電化學交流阻抗頻譜分析 22
3-5-5 氣相層析儀 23
第四章 結果與討論 24
4-1 硫化銀摻雜銦/氧化鋅異質結構應用於光電化學產氫 24
4-1-1 硫化銀摻雜銦/氧化鋅異質結構SEM分析 24
4-1-2 硫化銀摻雜銦/氧化鋅異質結構XRD分析 27
4-1-3 硫化銀摻雜銦/氧化鋅異質結構XPS分析 28
4-1-4 硫化銀摻雜銦/氧化鋅異質結構Abs分析 29
4-1-5 硫化銀摻雜銦/氧化鋅異質結構LSV分析 31
4-1-6 硫化銀摻雜銦/氧化鋅異質結構IPCE分析 33
4-1-7 硫化銀摻雜銦/氧化鋅異質結構EIS分析 34
4-1-8 硫化銀摻雜銦/氧化鋅異質結構Mott-Schottky分析 35
4-1-9 硫化銀摻雜銦/氧化鋅異質結構氫氣產出分析 37
4-1-10 總結 39
4-2 硫化鉍/氧化鋅異質結構應用於光電化學產氫 41
4-2-1 硫化鉍/氧化鋅異質結構SEM分析 41
4-2-2 硫化鉍/氧化鋅異質結構TEM分析 43
4-2-3 硫化鉍/氧化鋅異質結構XRD分析 44
4-2-4 硫化鉍/氧化鋅異質結構XPS分析 45
4-2-5 硫化鉍/氧化鋅異質結構Abs分析 46
4-2-6 硫化鉍/氧化鋅異質結構LSV分析 47
4-2-7 硫化鉍/氧化鋅異質結構IPCE分析 48
4-2-8 硫化鉍/氧化鋅異質結構Mott-Schottky分析 49
4-2-9 硫化鉍/氧化鋅異質結構溶氧量分析 50
4-2-10 在不同濃度的電解液下之分析 52
4-2-11 總結 53
第五章 結論與未來展望 55
第六章 參考資料 56

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