臺灣博碩士論文加值系統

異質結構作為增強光電化學反應的方法已被廣泛研究，文獻中製備SrTiO3/TiO2的方法多為水熱法與陽極氧化法，尚未有以水熱-化學電池法搭配還原氣氛退火製程。在本研究中，使用直流非平衡磁控濺鍍製備的導電TiN薄膜作為工作電極，於氫氧化鈉和醋酸鍶電解液中通過簡便的水熱-化學電池法製備SrTiO3/TiN薄膜，在80°C下反應30分鐘，過程中未施加外部電壓或電流，隨後，將薄膜在不同氧分壓的控制氣氛(air、N2、N2/5%H2)中進行退火，以氧化TiN的方式生成SrTiO3/TiO2異質結構薄膜。
根據XRD和FE-SEM結果顯示，立方相SrTiO3以顆粒狀生長於TiN薄膜上，在經過氧分壓較高的air與N2氣氛後退火後，TiN完全氧化為TiO2，因此光電流密度極低，而在經過N2/5%H2的還原氣氛中退火超過700°C後，TiN未完全氧化為TiO2，形成了SrTiO3/TiO2/TiN異質結構薄膜，這些薄膜的峰值光電流密度可以達到7000 μA/cm2以上，顯著高於在高氧分壓下退火和退火前的薄膜，這主要是由於在高溫和低氧分壓下TiN緩慢氧化生成的大晶粒TiO2，除此之外，在這種退火條件下生成的氧空位也可能起到重要作用。由電化學阻抗量測與霍爾分析顯示異質結構薄膜中的載子分離效率得到提高，而光致發光光譜則表明可能存在缺陷，進一步以EPR與XPS分析中證實氧空位的存在，結果明確顯示，SrTiO3/TiO2/TiN異質結構薄膜對光電化學反應的增強有顯著貢獻。機制也得到了闡明。統整實驗結果得知本研究成功製備出SrTiO3/TiO2/TiN 異質結構薄膜，在 N2/5%H2 氣氛900℃退火 3 小時，可得本研究最高的光電流密度7185±438 µA/cm2，而高光電化學電流的原因需要SrTiO3/TiO2異質結構、還原氣氛退火引入氧空位與導電TiN底層的幫助，三種條件缺一不可，並可由此預測高光電化學反應薄膜之製程區間。
關鍵詞: 水熱-化學電池法、退火、異質結構、缺陷、鈦酸鍶、二氧化鈦、氮化鈦、光電化學、還原氣氛

Heterostructures as a method to enhance photoelectrochemical reactions have been widely studied. In the literature, the preparation methods for SrTiO3/TiO2 are mostly hydrothermal and anodization methods. However, there has not yet been a method combining hydrothermal-galvanic couple synthesis and reduction atmosphere annealing. In this study, a conductive TiN film prepared by unbalanced DC magnetron sputtering was used as the working electrode. SrTiO3/TiN films were prepared using a simple hydrothermal-galvanic couple synthesis in a sodium hydroxide and strontium acetate electrolyte at 80°C for 30 minutes without applying any external voltage or current. Subsequently, the films were annealed in controlled atmospheres with different oxygen partial pressures (air, N2, N2/5%H2) to form SrTiO3/TiO2 heterostructure films by oxidizing TiN.
According to XRD and FE-SEM results, cubic phase SrTiO3 grows as particles on the TiN film. After annealing in atmospheres with higher oxygen partial pressures (air and N2), TiN is completely oxidized to TiO2, resulting in very low photocurrent density. However, after annealing in a reducing atmosphere of N2/5%H2 at temperatures above 700°C, TiN is not completely oxidized to TiO2, forming SrTiO3/TiO2/TiN heterostructure films. The peak photocurrent density of these films can reach over 7000 μA/cm², significantly higher than that of films annealed in high oxygen partial pressure or before annealing. This is mainly due to the large-grain TiO2 formed by the slow oxidation of TiN at high temperature and low oxygen partial pressure. Additionally, oxygen vacancies generated under such annealing conditions may also play an important role. Electrochemical impedance measurements and Hall analysis show improved carrier separation efficiency in the heterostructure films, while photoluminescence spectra indicate possible defects, further confirmed by EPR and XPS analyses to reveal the presence of oxygen vacancies. The results clearly demonstrate that the SrTiO3/TiO2/TiN heterostructure films significantly enhance photoelectrochemical reactions, and the mechanism has been elucidated.In summary, this study successfully prepared SrTiO3/TiO2/TiN heterostructure films. Annealing in N2/5%H2 atmosphere at 900°C for 3 hours resulted in the highest photocurrent density of 7185±438 µA/cm2 in this study. The high photoelectrochemical current is attributed to the SrTiO3/TiO2 heterostructure, the introduction of oxygen vacancies through reduction atmosphere annealing, and the conductive TiN substrate. All three conditions are indispensable, and this allows predicting the process range for high photoelectrochemical reaction films.
Keywords: Hydrothermal-galvanic couple synthesis, Annealing, Heterostructure, Defects, Strontium titanate, Titanium dioxide, Titanium nitride, Photoelectrochemisty, Reducing atmosphere

第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
1.3 研究目的 2
1.4支持本研究國科會計畫 2
第二章 理論背景與文獻回顧 3
2.1 理論背景 3
2.1.1 水熱、化學電池與水熱-化學電池法 3
2.1.2 光電化學反應 4
2.1.3 異質結構 6
2.1.4 氧空位缺陷 8
2.1.5 光電流密度與電化學阻抗 9
2.2 文獻回顧 11
2.2.1 本實驗室以水熱-化學電池法製備鈣鈦礦薄膜 11
2.2.2 鈦酸鍶/二氧化鈦異質結構應用於光電化學反應文獻 18
2.2.3 於材料內引入氧空位應用於光電化學反應文獻 20
第三章 研究方法 22
3.1 實驗流程與參數 22
3.1.1 氮化鈦薄膜製程 23
3.1.2 水熱-化學電池法製備鈦酸鍶薄膜 24
3.1.3 不同氣氛下退火鈦酸鍶薄膜 25
3.2 特徵分析 25
3.2.1 四點探針儀 25
3.2.2 X光繞射儀 25
3.2.3 場發射掃描式電子顯微鏡 25
3.2.4 場發射穿透式電子顯微鏡 26
3.2.5 電子能量損失能譜儀 26
3.2.6 X光光電子能譜儀 26
3.2.7 電子順磁共振儀 26
3.2.8 螢光光譜系統 26
3.2.9 電化學分析儀 27
3.2.10 紫外光/可見光/近紅外光光譜儀 27
3.2.11 霍爾效應分析儀 27
第四章 結果 28
4.1 導電TiN薄膜電極分析 28
4.2 以水熱-化學電池法製備鈦酸鍶薄膜 29
4.2.1 電流-時間曲線與薄膜外觀 29
4.2.2 結晶相與顯微結構分析 30
4.2.3 能隙分析 32
4.2.4 光電流密度 33
4.2.5 成分分析 33
4.3 不同氣氛退火鈦酸鍶薄膜以製備鈦酸鍶/二氧化鈦異質結構 36
4.3.1 不同氣氛之氧分壓 36
4.3.2 薄膜外觀 37
4.3.3 結晶相與微結構分析 37
4.3.4 光電流密度 43
4.3.5 電化學分析 48
4.3.6 載子濃度與遷移率 51
第五章 討論 54
5.1 高光電化學電流表現 54
5.1.1 與實驗室過去結果之比較 54
5.1.2 高光電化學電流的製程條件 58
5.2 高光電化學電流提高的原因 63
5.2.1 SrTiO3/TiO2/TiN 異質結構 63
5.2.2 氧空位的引入 66
5.2.3 氮化鈦導電層的幫助 72
5.3 高光電化學電流之機制 76
第六章 結論 78
參考文獻 80

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