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研究生:梁嘉文
研究生(外文):Chia-Wen Liang
論文名稱:化學氣相沉積氧化鈦晶體及其拉曼光譜分析
論文名稱(外文):Chemical Vapor Deposition And Raman Analysis Of TiO2 Nanocrystals
指導教授:蔡大翔
指導教授(外文):Dah-Shyang Tsai
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:化學工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:中文
論文頁數:90
中文關鍵詞:二氧化鈦化學氣相沉積拉曼散射光激發螢光
外文關鍵詞:Titanium oxidechemical vapor depositionRaman scatteringPhotoluminescence
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本論文藉由四異丙基鈦前驅物進行化學氣相沉積,研究二氧化鈦奈米桿成長於二氧化錫摻雜氟(FTO)的導電玻璃及SA(100)基板上。藉由控制不同的化學氣相沉積成長條件,可得到金紅石結構、銳鈦礦結構與兩結構共存的二氧化鈦奈米桿。使用SEM來觀察其形貌、XRD判斷二氧化鈦的晶體結構,利用Raman散射來鑑別二氧化鈦之晶相。
金紅石結構的二氧化鈦在FTO上的成長,受到SnO2薄膜的同屬金紅石(301)優選方向的影響,具有(301)的優選方向;在SA(100)基板上,只顯示(002)單一繞射峰訊號,表示桿狀晶體都朝[001]方向成長。而銳鈦礦結構的二氧化鈦,在FTO上的成長並沒有優選方向;但成長於SA(100)上,具有(220)的優選方向。
由MSC model評估金紅石結構之二氧化鈦奈米桿表面片狀晶體的尺寸,所得到的結果與在FE-SEM電鏡圖觀察到的片狀晶體之尺寸吻合。實驗所成長的二氧化鈦奈米桿,其A1g mode的拉曼散射譜線有譜線變寬的情形,且隨著奈米晶體尺寸的變小而漸寬,而殘留應力及奈米晶體內聲子限制效應的影響,造成A1g mode的拉曼散射譜線有紅位移現象。
由光激發螢光光譜分析的結果,成長於FTO上的金紅石結構、銳鈦礦結構及兩結構共存的二氧化鈦,本身晶格的UV放光顯得較微弱,因為受到二氧化鈦奈米桿表面氧缺陷的影響,分別在503nm、515nm、511nm的波長位置會有很強的綠光放光訊號。
In this thesis, TiO2 nanorods have been grown on the substrates of F-doped tin oxide (FTO) conducting glass and sapphire (SA) (100) using chemical vapor deposition (CVD). Through adjusting the growth parameters of CVD, we may obtain nanorods of rutile, anatase, and mixed phases, which are further examined using scanning electron microscopy (SEM), X-ray diffraction (XRD), raman scattering, and photoluminescence (PL).
TiO2 nanorods of rutile structure grown on FTO are influenced by the preferred orientation of underlying tin oxide, which is also of rutile structure. They both exhibit the preferential crystal plane (301). TiO2 nanorods of rutile structure grown on SA(100) display single (002) diffraction peak, indicating the crystals grow in [001] direction. TiO2 nanorods of anatase structure grown on FTO display no preferred orientation, while a preferential crystal plane of (220) on SA(100).
Fitting the raman scattering signal of rutile TiO2 with modified spatial correlation (MSC) model results in the length of phonon confinement, which is consistent with the disk like crystal observed in the SEM micrograph. We also observe the A1g line broadening with the decreasing crystal size, and the red shift in A1g line position due to residual stresses and phonon confinement.
Analysis of PL spectra of TiO2 nanorods indicates a weak contribution in UV emission due to the lattices of rutile, anatase, and the mixed phase. They exhibit strong green emissions at wavelength 503, 515, 511 nm because of the surface oxygen vacancies.
中文摘要……………………………………………….............……...Ⅰ
英文摘要……………………………………………………................Ⅲ
目錄…………………………………………………………................ Ⅳ
圖目錄………………………………………………………................Ⅶ
表目錄……………………………………………………....….... .…ⅩⅡ

第一章 緒論…...…………………………………………............…....1
1.1二氧化鈦晶體結構………………………………………………..….1
1.2二氧化銥晶體特性及應用………………………………………..….4
1.3一維奈米材料…………………………………………………….…..7
1.4一維奈米材料的成長機制…………………………………...….….10
第二章 實驗原理與文獻回顧……………………………..................16
2.1化學氣相沉積法………………………………………………….....16
2.2TTIP反應機制………………….…………………………………..18
2.3文獻回顧……………………………………………………….........19
2.4研究動機………………………………………………….…………21
第三章 實驗步驟和分析方法……………………………........….22
3.1實驗材料與樣品…………………………………………….………22
3.2實驗設備………………………………………………………….…24
3.3實驗流程…………………………….………………………….…...26
3.4實驗步驟…………………………………………………………….27
3.4.1晶片潔淨處理……………………………………………………27
3.4.2FTO導電玻璃退火處理…………………………………….…...27
3.4.3二氧化鈦奈米桿之沉積步驟……………………………........…28
3.5分析儀器…………………………………………………………….30
第四章 結果與討論…………………………………………...........35
4.1二氧化鈦一維奈米桿成長與分析……….…………………………35
4.1.1二氧化鈦奈米桿成長形貌FE-SEM電鏡圖………...………….36
4.1.2二氧化鈦奈米桿XRD分析……………………………………..45
4.1.3二氧化鈦奈米桿Raman分析……………………………….…..49
4.2二氧化鈦奈米桿成長於不同退火溫度的FTO之影響…....….......54
4.2.1 FTO退火處理…………………………………………………...54
4.2.2二氧化鈦奈米桿成長於不同退火溫度的FTO…………………56
4.3利用SC model分析拉曼散射特性……...............…………………60
4.3.1分析樣品的成長條件………………………..…………………..60
4.3.2 SC model分析方程式………………...…………………………62
4.3.3 SC model分析結果探討……………...…………………………64
4.4二氧化鈦奈米桿PL激發光譜分析………...........................……...70
4.4.1金紅石結構二氧化鈦奈米桿PL激發光譜分析………….……70
4.4.2銳鈦礦結構二氧化鈦奈米桿PL激發光譜分析…….…………74
4.4.3金紅石結構與銳鈦礦結構共存的PL激發光譜分析……….…77
第五章 結論…...…………………......................................................79
參考文獻………..........................................…………………………..81
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