臺灣博碩士論文加值系統

本研究分別利用鈦片與二氧化鈦奈米粉末(nanopowder)等含鈦起始物置於氫氧化鈉溶液中，經水熱法形成鈉鈦酸鹽奈米線，接著再利用酸處理將鈉鈦酸鹽奈米線置換成氫鈦酸鹽奈米線，最後經由高溫鍛燒將氫鈦酸鹽奈米線相轉移成二氧化鈦奈米線。研究結果得知藉由調變反應時間、反應溫度、氫氧化鈉濃度可控制鈉鈦酸鹽奈米線均勻性與直徑大小，而在最佳反應條件下所成長之奈米線直徑分佈範圍主要在20~30nm，且經由酸處理與升溫相轉移後，奈米線之形貌與直徑變化不大。進一步利用Raman與TEM之材料分析結果可知相轉移後之奈米線確為Anatase相態，且具單晶結構。另外以此單晶奈米線應用於色素增感太陽能電池所得之效率並沒有預期來的高，此可能與奈米線平鋪於導電玻璃而無法發揮其單晶之效用有關。

Sodium titanate nanowires were synthesized by hydrothermal process using Ti foil or P25 in NaOH solution. Sodium titanate nanowires were immersed in HCl for ion exchange to hydrogen titanate nanowires. Hydrogen titanate nanowires were further thermal converted to TiO2 nanowires. Formation parameters, such as NaOH concentrations, reaction temperatures and reaction times during hydrothermal process, are varied to search for suitable reactions for the formation of uniform nanowires. The diameter of the sodium titanate nanowires were in the range of 20 to 30 nm. The morphology and diameter of nanowires would not be changed significantly during ion exchange and thermal conversion. After thermal conversion, anatase TiO2 nanowires were formed , which were confirmed by Raman and TEM analyses. Anatase nanowires were employed to be the anode of the N719 dye-sensitized solar cells(DSSC). The best efficiency obtained in this study is 3.5％, which is much smaller than that of nanoparticle-film DSSC. It is suggested to be ascribed to the lower surface areas of the nanowire DSSC.

第一章 緒論……………………………………………………………………1
1.1 前言…………………………………………………………………………1
1.2 一維奈米材料………………………………………………………………4
1.3 二氧化鈦…………………………………………………………………………7
1.4 研究動機…………………………………………………………………………9

第二章 理論基礎………………………………………………………………………10
2.1 成長一維奈米結構之方法……………………………………………………10
2.1.1 非等方向性奈米晶體之成長………………………………………………10
2.1.2 模具輔助法(Template assisted)……………………………………12
2.1.2.1 使用具有一維奈米結構之模具……………………………………12
2.1.2.2 以適當的界面活性劑來控制不同面向具有不同的成長速度……12
2.1.3 以VLS方法成長………………………………………………………………14
2.1.4 以Solution-Liquid-Solid & Solid-Liquid-Solid 方法成長…………15
2.1.5 螺旋差排導致一維成長(Screw dislocation growth)……………………16

2.1.6 氧化物促進一維奈米線成長 ………………………………………………17
2.2 水熱法…………………………………………………………………………18
2.2.1 水熱法原理 ………………………………………………………18
2.2.2 水熱法優點……………………………………………………………19
2.2.3 水熱法應用………………………………………………………………19
2.3 色素增感太陽能電池理論………………………………………………………20

第三章 實驗步驟與研究方法………………………………………………21
3.1 實驗流程………………………………………………………………………21
3.2 系統設計…………………………………………………………………22
3.2.1 Autoclave反應器……………………………………………………22
3.2.2 UF-D3FS經濟型高溫爐……………………………………………22
3.3 實驗材料…………………………………………………………………………24
3.3.1 反應物……………………………………………………………………24
3.4 實驗操作步驟………………………………………………………………24
3.4.1 鈉鈦酸鹽成長………………………………………………………………24
3.4.2 置換成氫鈦酸鹽……………………………………………………………25
3.4.3 升溫相轉移……………………………………………………………………25
3.5 分析與鑑定……………………………………………………………………25
3.5.1 掃描式電子顯微鏡分析………………………………………………………25
3.5.2 拉曼光譜分析…………………………………………………………………26
3.5.3 穿透式電子顯微鏡……………………………………………………28
3.5.4 紫外線-可見光吸收光譜儀…………………………………………………28

第四章 利用水熱法成長TiO2一維奈米結構…………………………31
4.1 以鈦片為起始物成長鈉鈦酸鹽奈米線………………………………………………31
4.1.1 反應時間之效應………………………………………………………………32
4.1.2 反應溫度之效應………………………………………35
4.1.3 氫氧化鈉濃度之效應………………………………………37
4.2 二氧化鈦奈米線之製備…………………………………………39
4.2.1 酸處理與相轉移處理…………………………………………39
4.2.2 結構分析…………………………………………………………41
4.2.2.1 拉曼光譜分析………………………………………41
4.2.2.2 TEM分析…………………………………………41
4.3 結論…………………………………………………………………………………43
4.4 以P25為起始物成長鈉鈦酸鹽奈米線………………………………………44
4.4.1 氫氧化鈉濃度之效應…………………………………………44
4.4.2 反應溫度之效應………………………………………46
4.5 二氧化鈦奈米線之製備…………………………………………48
4.5.1 酸處理與相轉移處理…………………………………………48
4.5.2 結構分析…………………………………………………………50
4.5.2.1 拉曼光譜分析…………………………………………………50
4.5.2.2 TEM分析……………………………………………………………50
4.6 TiO2奈米線在色素增感太陽能電池方面的應用…………………………………53
4.6.1 TiO2奈米線之塗佈於基板………………………………………………53
4.6.1.1 氫鈦酸鹽奈米線之分散………………………………………53
4.6.1.2 基板之前處理…………………………………………………53
4.6.1.3 升溫相轉移處理…………………………………………………54
4.6.2 不同相態奈米線之UV光譜分析………………………………………………56
4.6.3 不同厚度之Anatase奈米線薄膜於色素增感太陽能電池之效率比較………57
4.7 結論…………………………………………………………………………………60
4.8 未來展望……………………………………………………………………………61

第五章 總結………………………………………………62

第六章 參考文獻…………………………………………64

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