臺灣博碩士論文加值系統

本研究在超高真空的背景下，以固定的總壓（PO/Ar = 3）下共濺鍍沉積Ti-W複合氧化物（Ti-W-O）薄膜，利用沉積速率與濺鍍功率曲線，控制薄膜組成，以分別康寧玻璃為基材，沉積具有光誘發親水性、防霧、自潔效果之Ti-W複合氧化物薄膜。
第一部份，建立三靶源磁控濺鍍機台設計、裝配以導入本實驗室目前已知的靶材配置、鍍層結構/組成調節與電漿表面改質及鍍層臨場結晶等技術，以利於製造高度耐候且高親水、持久性的防霧自潔TiO2鍍層。
第二部份，使用無鹼的康寧玻璃（型號：7059）基板，以共濺鍍（co-sputter）沉積Ti-W複合氧化物（Ti-W-O）薄膜，利用濺鍍功率調控經過熱處理得到各種組成之Ti-W-O薄膜，並採用國家同步幅射研究中心光源束線（Beam Lines）17B1做X光繞射分析與光束線16A1、、17C1及20A1等設施等分析方法以探討微結構的變化。

In this research, Ti-W composite oxide（Ti-W-O） thin-films were fabricated through a co-sputter deposition in a ultra-high vacuum system under a constant total pressure (PO2/Ar = 3.0). Utilizing the relative curves of deposition rates and sputtering power, we could control the compositions of the thin-films. Using the corning glasses (7075) as substrates, we deposited Ti-W composite oxide thin films with characteristics of photo-induced hydrophility, anti-fogging, and self-cleaning effects.
In the first part, we established a three target magnetron co-sputtering machine and inducted previous set-up methodology in our laboratory, including target disposition, construction and composition regulation of films, plasma surface modification and in-situ film growth technique etc..., to derive a highly tolerance of climate change and persistence of anti-fogging effect titanium dioxide film.
In the second part, we utilized co-sputtering on the base-free Corning glass to growth Ti-W （Ti-W-O）composite oxide thin films .Via altering the sputtering output power and sequence thermal treatment to obtain different compositions of Ti-W-O thin films. Using the beam line 17B1 for XRD and the 16A1, 17C1 beam line for microstructure analysis in the National Synchrotron Radiation Research Center (NSRRC).

總目錄
中文摘要..................................................................................................I
英文摘要.................................................................................................II
總目錄....................................................................................................III
表目錄...................................................................................................VI
圖目錄................................................................................................. VII
第一章、緒論........................................................................................1
1.1 前言................................................................................................1
1.2 研究動機與目的.....................................................................4
第二章、理論基礎與前人研究....................................................6
2.1 三氧化鎢的基本結構與特性...........................................6
2.2 金屬半導體氧化物之自潔防霧機制...........................................7
2.2.1 光觸媒材料簡介.................................................................7
2.2.2 光誘發觸媒機制.............................................................8
2.2.3二氧化鈦的基本結構與特性...............................................10
2.3 WO3-TiO2複合薄膜之自潔防霧..................................12
2.4 同步幅射光譜與二氧化鈦薄膜吸收光譜特徵..........................15
2.4.1同步幅射吸收光譜（SR-XAS）.........................................15
2.4.2二氧化鈦薄膜吸收光譜特徵.........................................17
2.5 光觸媒及超親水性TiO2薄膜之應用..........................19
第三章、實驗方法與步驟.......................................................................34
3.1 實驗流程（Procedures）指引.........................................................34
3.2 濺鍍系統設備…………………..................................................35
3.3 薄膜製備與薄膜沉積原理說明...............................................37
3.4 薄膜特性檢測分析....................................................40
第四章、高濺鍍實驗專用機台設計、裝配與測試....................51
4.1 待改裝感應耦合電漿離子束濺鍍系統......................51
4.2 三靶源磁控濺鍍實驗專用機台改裝…………................55
4.2.1真空腔體改裝目的...............................................................55
4.2.2改裝PERT計畫評核的網狀.............................................56
4.2.3三靶源磁控濺鍍機台主要重點修改及設計考量............58
4.3 三靶源磁控濺鍍機台系統改裝…………..................... 64
4.4 三靶源磁控濺鍍機台系統性能測試………………….........65
第五章、薄膜生長行為與親水特性............................87
5.1組成分析......................................................88
5.1.1沉積速率之影響……………………............88
5.1.2RBS組成分析……………………............90

5.2 XRD繞射分析及相分布探討.............................................93
5.3 XAS分析.......................................................................................97
第六章、結論………..............................................................................118
參考文獻.................................................................................................120
附錄A JCPDS, Card No.21-1272, 21-1276, 27-1452, 53-0678.....127
附錄B TiO2（與Ti）的X光吸收近緣結構......................................128


表目錄
表2.1 WO3薄膜多形態同素異形體及其穩定相之存在溫度範圍……22
表2.2 A-TiO2及R-TiO2多形態結構之相關物性比較...............................23
表2.3光觸媒材料之特殊應用.........................................................................24
表2.4 光觸媒材料應用與產品.........................................................................25
表4.1 TriScrollTM 300 乾式渦卷幫浦之詳細規格一覽表..............................67
表4.2 ANSI GA-12A冷凍幫浦之詳細規格一覽表..................................68
表5.1依據RBS組成分析所得到的各種功率比之薄膜試片的組成分佈....102

圖目錄
圖 2.1 WO3晶體結構示意圖…………………………..…………...…….26
圖2.2典型ReO3結構………………………………………………….26
圖2.3光催化反應示意圖……………………………………………......27
圖2.4二氧化鈦的親水性與疏水性機制………………………...……..28
圖2.5銳鈦礦型與金紅石型二氧化鈦的晶體結構…………………...29
圖2.6光觸媒自潔機制……………..……………...………………….30
圖2.7 TiO2與WO3之多層膜（a）為SEM影像，（b）為能帶關係圖形，TiO2與WO3電子電荷傳遞情況..................................................31
圖2.8 同步幅射光與鄉關光線/能量、物體大小之對照圖……………....32
圖2.9（a）入射與反射光電子波的干涉現像示意圖及（b）Ti的K吸收限之X光吸收光譜……………………………………………..………..33
圖3.1 本研究之實驗流程圖...................................................................44
圖3.2 本研究所使用之超高真空多靶源磁控濺鍍系統實體照片...........45
圖3.3本研究所使用之超高真空多靶源磁控濺鍍系統示意圖….…..46
圖3.4 熱傳導型真空計與電容式真空計之壓力對應曲………..…...…..47
圖3.5 TiO2薄膜使用(a)DC直流和（b）RF射頻磁控濺鍍之光學顯微鏡平面圖…………………………………………..……………..…..48
圖3.6掠角X光繞射（GIXRD）量測示意圖........................................49
圖3.7(a)為國家同步幅射光束線17C，(b)和(c)為光束線16A...50
圖 4.1 TriScrollTM 300 乾式渦卷幫浦之外觀.......................……69
圖 4.2 冷凍幫浦配備簡圖….........................................………….70
圖 4.3冷凍幫浦之內部構造……………………..………..……………71
圖4.4 ANSI GA-12A冷凍幫浦外觀……………………………………71
圖 4.5氣體分子進入多孔性材料的特性……………………………….....72
圖4.6改裝前實驗機台…………………………………………………….73
圖 4.7所改建之TiO2鍍層製備實驗機台...........................................73
圖 4.8 改建之TiO2鍍層製備機台PERT圖................................................74
圖4.9 離子束鍍膜機台改裝前六面圖.........................................................75
圖4.10 （a）改裝前上視圖、（b）預計改裝之上板.................................76
圖4.11上板濺鍍系統加工組裝設計圖（a）為上板加工正視圖、（b）為上視示意圖、（c）為側視圖、（d）為組裝完成實品圖.....................…77
圖4.12側板後視圖........................................................................................78
圖4.13側板轉接頭示意圖............................................................................79
圖4.14修改基座使其具有旋轉及偏壓等多樣性的調整特色....................80
圖4.15 (a) 旋轉加熱基座完成上視圖、（b）加熱器放置圖、（c）加熱器設計圖、（d）組裝完成側視圖. .............................................81
圖4.16真空系統氣體配置.........................................................................82
圖4.17修改前之PLC面板狀態................................................................83
圖4.18修改後之PLC面板狀態................................................................83
圖4.19系統組裝重建過程圖示............................................................84
圖4.20系統組裝完成示意圖........................................................85
圖4.21加熱基座升溫時間對照表..................................................86
圖5.1 WO3薄膜之沉積速率對應直流濺鍍功率（Wdc）的變化曲線.....103
圖5.2 TiO2薄膜之沉積速率對應直流濺鍍功率（Wrf）的變化曲線......103
圖5.3 由WO3（a）及TiO2（450 Wrf）單獨生長之沉積速率（0.7 nm/min）數據所預測之Ti-W-O薄膜沉積速率曲線（b）及實際共生濺鍍之曲線（c）。................................................................104
圖5.4 不同功率比例所生長在石英玻璃之薄膜退火前的RBS組成分佈實驗與模擬能譜圖，其（B）、（D）、（F）、（G）依照Ti含量由低至高的順序排列，且化學式列於圖內.....................105
圖5.5不同功率比例所生長在石英玻璃之薄膜空氣退火550℃後的RBS組成分佈實驗與模擬能譜圖，其（B）、（D）、（F）、（G）依照Ti含量由低至高的順序排列，且化學式列於圖內......................106
圖5.6不同功率比例所生長在純石墨之薄膜退火前的RBS組成分佈實驗與模擬能譜圖，其（B）、（D）、（F）、（G）依照Ti含量由低至高的順序排列，且化學式列於圖內...........................107
圖5.7不同功率比例所生長在純石墨之薄膜空氣退火550℃後的RBS組成分佈實驗與模擬能譜圖，其（B）、（D）、（F）、（G）依照Ti含量由低至高的順序排列，且化學式列於圖內.............................108
圖5.8 剛沉積於康寧玻璃的(A)WO3、(B) Ti1.2W24.1O74.7、(C) Ti2.3W23.0O73.6、(D) Ti9.7W17.7O72.6、(E) Ti21.2W9.05O69.7、(F) Ti22.5W7.75O68.2、(G) Ti27.7W4.3O68、(H)TiO2薄膜試片的XRD圖....109
圖5.9沉積於康寧玻璃（7059），經550℃空氣熱處理30分鐘以後的(A)WO3、(C) Ti2.3W23.0O73.6、(D) Ti9.7W17.7O72.6、(E) Ti21.2W9.05O69.7、(F) Ti22.5W7.75O68.2、(G) Ti27.7W4.3O68、(H)TiO2薄膜試片的XRD圖(入射角1°)。其中，（a1）WO3之波峰繞射資料見圖4.10....................................................................…110
圖5.10 （a）WO3（c）Ti2.3W23.0O73.6薄膜沉積於康寧玻璃經550℃之空氣退火30分鐘後之XRD圖繞射圖.........………………………..111
圖5.11（E）、（F）、（G）、（H）500℃之空氣退火30分鐘XRD繞射圖..112
圖5.12兩組JCPDS資料庫局部數據（05-0388及83-0950）................…113
圖5.13 經過空氣（550℃/1h）退火處理以後的(A)WO3、(C) Ti2.3W23.0O73.6、(D) Ti9.7W17.7O72.6、(E) Ti21.2W9.05O69.7、(F) Ti22.5W7.75O68.2、(G) Ti27.7W4.3O68、(H)TiO2；（I）標準A相（J）標準R相代表性Ti K-edge吸收光譜（NSRRC 16A光束線）...............................…114
圖5.14經過空氣（550℃/30min）退火處理以後的(A)WO3、(C) Ti2.3W23.0O73.6、(D) Ti9.7W17.7O72.6、(E) Ti21.2W9.05O69.7、(F) Ti22.5W7.75O68.2、(G) Ti27.7W4.3O68、(H)TiO2Ti K-edge近緣吸收光譜（NSRRC 16A光束線）...........................................................…115
圖5.15經過空氣（550℃/30 min）退火處理以後的(A)WO3、(C) Ti2.3W23.0O73.6、(D) Ti9.7W17.7O72.6、(E) Ti21.2W9.05O69.7、(F) Ti22.5W7.75O68.2、(G) Ti27.7W4.3O68、(H)TiO2；（I）標準A相（J）標準R相代表性Ti L2,3-edge吸收光譜（NSRRC 20A光束線）....................…………………………………………………...116
圖5.16 經過空氣（550℃/30min）退火處理以後的(A)WO3、(C) Ti2.3W23.0O73.6、(D) Ti9.7W17.7O72.6、(E) Ti21.2W9.05O69.7、(F) Ti22.5W7.75O68.2、(G) Ti27.7W4.3O68、(H)TiO2；（I）標準A相（J）標準R相代表性Ti K-edge吸收光譜（NSRRC 16A光束線）............................………………………………………117

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