在電化學之陽極氧化鍍著二氧化鈦之研究中，文獻中陽極使用的皆是純鈦基材，因而限制了電化學法鍍著二氧化鈦薄膜的應用範圍。本研究主要的目的是以電化學法於異質的矽晶片基材上鍍著二氧化鈦薄膜，並與純鈦基材上結果比較，藉由詳細的製程監控與鍍膜分析，期望獲得高品質之二氧化鈦鍍膜。
實驗在室溫下1 M H2SO4鍍液中進行，以掃描電壓與定電壓模式
鍍著二氧化鈦薄膜於鈦箔與鍍鈦矽晶片上，同時並改變掃描電壓速率
及定電壓值，以探討鍍膜的成長與電壓大小的關係。鍍著結果經X光
繞射分析顯示，鈦箔在掃描0-100 V之鍍膜結晶結構為anatase與
rutile，鍍鈦矽晶片在掃描0-100 V之鍍膜結晶結構為anatase。鈦箔上
出現rutile之原因，可能是高電壓之驅動與火花放電產生之高熱，使
anatase部分相轉變為rutile。定電壓60 V以上，鈦箔表面即生成
anatase，鍍鈦矽晶片則在定電壓80 V以上生成anatase，此電壓值範
圍與兩基材在掃描0-100 V實驗中，電流產生振盪之電壓值範圍相
同，電流的振盪可能與陽極上產生介電崩潰有關，因此anatase可能
在電壓達崩潰電壓以上生成，而鍍鈦矽晶片上生成anatase之電壓值
較高可能是因基材之晶粒尺寸差異造成氧化進行所需之電壓不
同。拉曼光譜分析兩基材在掃描電壓與定電壓之鍍著結果，相當一致
顯示鍍膜表面均含有anatase相之結晶。所以兩基材在低於崩潰電壓
鍍著條件下，鍍膜厚度很薄，可能為非晶質結構之鈍態二氧化鈦膜。
高於崩潰電壓時，薄膜產生介電崩潰，陽極繼續反應並開始形成
anatase相之結晶，厚度隨電壓值升高而增加。以掃描式電子顯微鏡觀
察不同模式之鈦箔與鍍鈦矽晶片之鍍著結果，兩基材之鍍膜形貌上明
顯不同，可能由於鍍著過程中表面氧氣生成量的差異所致，造成鈦箔
上鍍膜易被氧氣撐破形成裂紋，而鍍鈦矽晶片上鍍膜則較緻密且無裂
紋產生。

Concerning the anodic oxidation-based electrochemical synthesis of of TiO2 films, the material used for anode should be titanium. The main purpose of this research is to prepare TiO2 films on heterogeneous substrates such as Si instead of pure Ti by electrochemical oxidation and compare to the results on titanium substrates. Through the programmable control of the process and the analyses of the resultant thin films, we expect to obtain the high quality TiO2 thin films on Si substrates.
The deposition has been performed at room temperature in 1 M H2SO4. Scanning voltage mode and constant potentiodynamic mode are used in the deposition of TiO2 thin films both on Ti and Ti/Si substrates. XRD results show that anatase and rutile phases of TiO2 were present on Ti foil whereas only anatase could be found on Ti/Si when both types of specimens were potentiodynamically scanned to 100 V with different scanning rates. When the electrolytic voltage is above 60 V using potentiodynamic mode, the surface of Ti foils exhibits an anatase phase. The anatase was formed on Ti/Si at a higher voltage of 80 V. Raman spectroscopy results also confirms the existence of the anatase phase on these two types of substrates.The resultant morphology of the films on the two types of substrates is also drastically different. The higher electrochemical surface activity and more rapid anodic reactions including the production of oxygen for Ti/Si substrates are the main causes of such differences.

目錄
摘要
Abstract
第一章 緒論
1-1 研究背景………………………………………………..1
1-2 研究動機………………………………………………..2
1-3 研究目的………………………………………………..3
第二章 文獻回顧與理論背景
2-1 文獻回顧………………………………………………..5
2-2 理論背景………………………………………………10
第三章 研究方法
3-1 實驗流程……………………………………………....13
3-2 電化學沈積系統………………………………………13
3-3 基材之準備……………………………………………14
3-4 電化學鍍著……………………………………………16
3-5 分析儀器………………………………………………17
第四章 結果與討論
4-1 鍍著時電解電壓、電流與時間之關係……………..20
4-1-1 掃描電壓模式實驗……………………………….21
4-1-2 定電壓模式實驗………………………………….25
4-2 二氧化鈦鍍膜之外觀觀察與結晶構造之分析……..26
4-2-1 掃描電壓模式之鍍膜外觀分析………………….26
4-2-2 定電壓模式之鍍膜外觀分析…………………….27
4-2-3 掃描電壓模式鍍著之XRD分析………………...29
4-2-4 定電壓模式鍍著之XRD分析…………………...32
4-3 二氧化鈦鍍膜之微結構分析與元素成分分析..……34
4-3-1 掃描式電子顯微鏡分析………………………….34
4-3-2 鍍膜膜厚分析…………………………………….37
4-3-3 元素成分分析…………………………………….38
4-4 鍍膜化學組態分析…………………………………..41
4-5 熱氧化對照實驗結果(對照實驗)…………………...43
4-6 本實驗中氧化機構之探討…………………………..45
第五章 結論…………………………………………………...48
參考文獻……………………………………………………...50

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