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研究生： 陳仲緯
Jun-wei Chen
論文名稱： 二段陽極處理法應用於鈦薄膜成長之研究
The application of 2-step anodization in Ti thin film growth
指導教授： 陳志臣
Jyh-chen Chen
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 能源工程研究所
Graduate Institute of Energy Engineering
畢業學年度： 99
語文別： 中文
論文頁數： 67
中文關鍵詞： 陽極處理 、薄膜 、二氧化鈦奈米管
外文關鍵詞： anodization, TiO2 nanotube, film
相關次數： 點閱：10  下載：0 
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    • 二氧化鈦奈米管陣列具有較大比表面積、穩定物理與化學性質，可應用在光電化學產氫、染料敏化太陽能電池與光觸媒等領域。薄膜製程可依照不同用途，將金屬鍍在不同基板製備出微小元件使應用範圍更函寬廣。本實驗採用射頻濺鍍系統，將鈦薄膜濺鍍於FTO導電玻璃上，放置含有0.25 wt.%氟化銨、3 vol.%水與乙二醇之油性電解液中，固定陽極處理時間改變不同電壓與固定電壓改變不同陽極處理時間，觀察超音波震盪後圖案層(pattern)表面形態變化；而不同超音波震盪頻率對試片會產生不同破壞，導致試片內部殘留應力使試片產生應力腐蝕，應力腐蝕會使二氧化鈦奈米管表面產生裂痕，降低光吸收，導致光電流下降。本研究將超音波震盪頻率提升至110KHz以上，以陽極處理製備出結晶性較佳二氧化鈦奈米管陣列。

    The TiO2 nanotube arrays have large surface area, high chemical and physical stability, which are important for many applications such as photo-electrochemical hydrogen generation, dye-sensitized solar cell and catalyst field. According to the different applications, Ti metal will be deposited on different substrates to fabricate micro device to extend application potential of thin film. In this study, we used Radio Frequency (RF) magnetic sputter system to deposit Ti thin film on Fluorine-doped tin oxide (FTO) glass and then anodized in 0.25 wt.%NH4F, 3 vol.%water and ethylene glycol ( EG ) electrolyte solution. We can observe the pattern morphologies due to change of different anodization voltage and anodization time. Different ultrasonic frequency destroyed sample, inducing residual stress to make Stress Corrosion Cracking ( SCC ) begin, which causing absorption and photocurrent of TiO2 nanotube arrays decrease. When the ultrasonic frequency increase above 110KHz, the result showed that the better crystallinity TiO2 nanotube structure have been grown.

    目錄 摘要......................................................i Abstract ................................................ii 致謝....................................................iii 目錄.....................................................iv 圖目錄. .................................................vi 表目錄. .................................................ix 符號說明 .................................................x 第一章 緒論 ..............................................1 1-1 研究背景 .............................................1 1-2 文獻回顧 .............................................3 1-2-1 二氧化鈦基本結構性質 ...............................3 1-2-2 二氧化鈦製備方法 ...................................4 1-2-3 陽極處理法 .........................................5 1-3 研究目的 ............................................10 第二章 實驗方法與內容 ...................................20 2-1 實驗方法 ............................................20 2-2 實驗流程 ............................................20 2-2-1 基材準備 ..........................................20 2-2-2 鈦薄膜沉積 ....................................... 21 2-2-3 陽極處理 ..........................................22 2-2-4 退火處理 ..........................................23 2-2-5 光電極之封裝及光電流檢測 ..........................23 2-3 實驗檢測 ............................................24 2-3-1 原子力顯微鏡 ......................................24 2-3-2 場發式掃描電子顯微鏡 ..............................24 2-3-3 X-ray繞射儀 .......................................24 2-3-4 紫外光-可見光光譜儀 ...............................25 2-3-5 恆電位儀 ..........................................25 第三章 結果與討論 .......................................30 3-1 不同參數對鈦薄膜上pattern影響 .......................30 3-1-1 不同電壓對pattern表面影響 .........................30 3-1-2 不同時間對pattern表面影響 .........................31 3-2 二段陽極處理之二氧化鈦奈米管形成 ....................31 3-3 不同震盪頻率對二段陽極處理造成差異 ..................34 3-3-1 不同震盪頻率對pattern影響 .........................34 3-3-2 不同震盪頻率試片陽極處理後差異 ....................35 3-3-3 光穿透與光吸收量測 ................................36 3-3-4 光電流量測 ........................................37 第四章 結論 .............................................62 參考文獻 ................................................63 圖目錄 圖1.1 染料敏化太陽能電池示意圖...........................11 圖1.2 太陽光電化學分解水之氧化還原示意圖.................11 圖1.3 太陽光電化學產氫示意圖.............................12 圖1.4 二氧化鈦相圖.......................................13 圖1.5 二氧化鈦晶體結構(Rutile) ..........................14 圖1.6 二氧化鈦晶體結構(Anatase) .........................14 圖1.7 陽極處理電流密度曲線圖.............................15 圖1.8 二氧化鈦奈米管成長示意圖...........................15 圖2.1 (a)實驗流程圖(b)實驗流程示意圖 ....................26 圖2.2 磁控濺鍍原理示意圖.................................27 圖2.3 濺鍍腔體...........................................27 圖2.4 二氧化鈦薄膜之退火曲線圖...........................28 圖3.1 不同電壓電流密度-時間曲線圖 .......................39 圖3.2 相同時間不同陽極處理電壓(a) 20V(b) 30V(c) 40V(d) 50V 殘留pattern之AFM圖.......................................40 圖3.3 相同電壓不同陽極處理時間(a) 15min(b) 45min(c) 60min殘留 pattern之AFM圖 .......................................41 圖3.4 不同薄膜厚度一段陽極處理與二段陽極處理(a)電流密度-時間(b)以log轉換曲線圖.....................................42 圖3.5 不同薄膜厚度一段陽極處理 (a)電流密度-時間(b)以log轉換曲線圖 .... .............................................43 圖3.6 相同薄膜厚度一段與兩段陽極處理(a)電流密度-時間(b)以log轉換曲線圖........................................... 44 圖3.7 二段陽極處理前試片表面之SEM圖......................45 圖3.8 二段陽極處理50秒試片表面之SEM圖....................46 圖3.9 二段陽極處理50秒試片橫截面之SEM圖..................46 圖3.10 二段陽極處理200秒試片表面之SEM圖..................47 圖3.11 二段陽極處理200秒試片橫截面之SEM圖................47 圖3.12 二段陽極處理600秒試片表面之SEM圖..................48 圖3.13 二段陽極處理600秒試片橫截面之SEM圖................48 圖3.14 二段陽極處理1200秒試片表面之SEM圖.................49 圖3.15 二段陽極處理1200秒試片橫截面之SEM圖...............49 圖3.16 一段陽極處理試片表面之SEM圖.......................50 圖3.17 一段陽極處理試片橫截面之SEM圖.....................50 圖3.18 不同超音波震盪頻率之XRD繞射圖.....................51 圖3.19 40KHz震盪後pattern表面之SEM圖.....................52 圖3.20 70KHz震盪後pattern表面之SEM圖.....................52 圖3.21 70KHz震盪後pattern表面放大之SEM圖 ................53 圖3.22 110KHz震盪後pattern表面之SEM圖....................53 圖3.23 120KHz震盪後pattern表面之SEM圖....................54 圖3.24 133KHz震盪後pattern表面之SEM圖....................54 圖3.25 陽極處理完(40KHz)表面之SEM圖......................55 圖3.26 陽極處理完(40KHz)表面放大之SEM圖..................55 圖3.27 陽極處理完(70KHz)表面之SEM圖......................56 圖3.28 陽極處理完(70KHz)表面放大之SEM圖..................56 圖3.29 陽極處理完(110KHz)表面之SEM圖.....................57 圖3.30 陽極處理完(110KHz)表面放大之SEM圖.................57 圖3.31 陽極處理完(120KHz)表面之SEM圖.....................58 圖3.32 陽極處理完(120KHz)表面放大之SEM圖.................58 圖3.33 陽極處理完(133KHz)表面之SEM圖.....................59 圖3.34 陽極處理完(133KHz)表面放大之SEM圖.................59 圖3.35 退火前與不同震盪頻率退火後之XRD繞射圖.............60 圖3.36 不同震盪頻率之穿透光譜圖..........................60 圖3.37 不同震盪頻率之吸收光譜圖..........................61 圖3.38 不同震盪頻率之光電流變化曲線圖....................61 表目錄 表1.1 二氧化鈦奈米結構各製程優缺點比較...................16 表1.2 陽極處理相關文獻...................................17 表1.3陽極處理相關文獻(2).................................18 表1.4陽極處理相關文獻(3).................................19 表2.1藥品、濺鍍靶材與玻璃基板名稱....................... 29

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