臺灣博碩士論文加值系統

本研究在超高真空的背景下，在不同的O2/Ar流量比例（Ar固定5.85 sccm）下利用射頻反應性磁控濺擊金屬鈦（Ti）靶材以生長TiO及TiO2等氧化鈦（泛稱TiOx）薄膜，同時，利用臨場的光釋放能譜術（Optical Emission Spectroscopy; OES）監控電漿物種（即Ti流通量）的變化，以獲得薄膜沉積的金屬�o中毒轉變行為，依“Ti殘餘金屬強度”多寡釐清金屬區、過渡區及中毒區的分野，並採用事後的拉塞福背向散射能譜術（Ti、O組成分析）、掠角X光繞射術（微結構分析）及電阻率與沉積速率數據，清楚地理解每一個區域的TiOx薄膜特性。
其中，金屬區發生在中毒比例達50%，其確實可生長電阻率僅101、499 μΩ-cm的金屬性Ti及TiO1.0（計量比）薄膜；過渡區發生在中毒比例70~80%，其所生長的薄膜為計量比不足的半導體性TiO2薄膜（TiO1.5、TiO1.66）；中毒區發生在中毒比例≧ 95%，其可生長計量比（TiO2.0）及稍過計量比（TiO2.2）薄膜。薄膜的沉積速率會隨著O2流量比例的上升而稍微增加，並於95%~100%的完全中毒情況劇降至1/3~1/4。這種沉積速率的變化狀況與Ti靶材的中毒程度及薄膜的莫耳體積差異有關。最後，掠角X光繞射分析顯示生長於金屬區的TiO1.0薄膜有明顯的複晶結構，而生長於過渡區的氧不足TiO2及中毒區的計量TiO2.0薄膜並沒有良好的結晶狀態，但經過高溫氧氣退火後，前者會轉變為銳鈦曠（A-TiO2）與金紅石（R-TiO2）双相共存，後者則會轉變為A-TiO2。水接觸角量測證實，此兩種薄膜均具有光誘發超親水特性，並以A-TiO2薄膜單相較佳且其親水性在無光線照射時回覆時間較長。

The research grows titanium oxide TiO and TiO2 (generally called TiOx) with ultra high vacuum reactive magnetron sputtering titanium target in different O2/Ar flow ratio, and monitors the difference of plasma type with in-situ optical emission spectroscopy (OES) to get hysteresis effect of deposited metal thin films, and then separates the division of metal zone, transition zone and poisoned zone by “the intensity of remnant titanium”. After that, use Rutherford backscattering spectroscopy (composition analysis of Ti and O), grazing x-ray diffraction (microstructure analysis) and the data of electric resistivity and deposition rate to understand the characteristic of TiOx in each zone clearly.
It is sure that metal Ti and TiO (stoichiometric) thin films with resistivity 101 and 499 μΩ-cm can be grown in 50% poisoned metal zone. The poisoned ratio of the transition zone is 70~80% and there are semi-conductive TiO2 thin films under stoichiometric (TiO1.5, TiO1.66). The poisoned ratio of the poisoned zone is over 95% and there are stoichiometric (TiO2.0) and slightly over stoichiometric thin films (TiO2.2).The thin film deposition rate will increase slightly with oxygen flow ratio rising, and sharply drop to 1/3~1/4 during complete poisoning, about 95%~100%. The change of deposition rate depends on the poisoned degree of titanium target and the difference of molar volume. Finally, grazing x-ray diffraction analysis indicates that TiO1.0 thin films grown in metal zone have apparent poly crystal structure, and oxygen insufficient TiO2 grown in transition zone and stoichiometric TiO2.0 thin film grown in poisoned zone have not great crystalline condition, but the former one will transform to coexisting anatase (A-TiO2) and rutile (R-TiO2) phases, and the latter to A-TiO2 after high temperature annealing in oxygen atmosphere. Water contact angle measurement indicates that the two type of thin films both are photo-induced ultra hydrophilic and the single phase A-TiO2 thin films are better, and their hydrophilic behavior have longer reverse time without light.

中文摘要…………………………………………………………………I
英文摘要………………………………………………………………III
總目錄……………………………………………………………………V
表目錄.................................................VIII
圖目錄..................................................XII
第一章、緒論..............................................1
1.1 研究背景與動機........................................1
1.2 研究目的..............................................4
第二章、文獻回顧..........................................7
2.1 二氧化鈦薄膜特性......................................7
2.2 反應性濺鍍氧化鈦之遲滯行為............................8
2.3 反應性濺鍍氧化鈦之薄膜特性分析........................9
2.4 OES臨場監控反應性濺鍍電漿之製程......................11
2.5 二氧化鈦薄膜的觸媒與親水性...........................13
2.5.1 光催化.............................................13
2.5.2 光誘發超親水性.....................................15
第三章、實驗細節與薄膜分析...............................28
3.1 實驗流程指引.........................................28
3.2 磁控濺鍍系統.........................................30
3.3 光放射能譜術及EmiCon系統.............................31
3.4 反應性磁控濺鍍之薄膜沉積行為.........................32
3.4.1 實驗細節...........................................32
3.4.2 氧化性與真空退火製程...............................34
3.5 薄膜特性檢測與分析...................................35
3.5.1 表面輪廓儀（α-Step）...............................35
3.5.2 四點探針儀（Four-Point Probe）.....................36
3.5.3 掠角X光繞射儀（GIXRD）.............................37
3.5.4 拉塞福背向散射分析儀（RBS）........................39
3.5.5 親水性試驗（Contanct angle）.......................42
第四章、結果與討論.......................................58
4.1 光譜特徵轉變情況.....................................58
4.2 中毒－金屬轉換曲線與氧訊號變化情況...................60
4.3 薄膜組成分析.........................................62
4.4 電阻率與沉積速率.....................................65
4.5 微結構分析...........................................67
4.5.1 剛沉積薄膜.........................................67
4.5.2 真空退火薄膜.......................................69
4.5.3 氧氣退火薄膜.......................................70
4.6 光誘發超親水性試驗...................................71
第五章、結論.............................................93
參考文獻.................................................95

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