臺灣博碩士論文加值系統

本研究利用反應式磁控濺鍍系統及組合式方法成長一系列不同碳含量之二氧化鈦薄膜(TiO2-xCx:C)，碳的來源為使用石墨靶並和金屬鈦靶在氦與氧氣的電漿氣氛下進行共濺鍍。主要研究目標為藉由組合式濺鍍的方法，期望能夠摻雜更多的碳進入純銳鈦礦(anatase)的二氧化鈦薄膜裡，並研究不同碳含量的TiO2-xCx:C薄膜之成分、結構、光學性質以及光觸媒活性。
使用X光繞射分析(XRD)、Raman光譜儀、EDS與X光射線光電子能譜儀(XPS)分析薄膜的結構及表面組成，以場發射掃描式電子顯微鏡觀察薄膜的表面型態。用紫外光-可見光吸收光譜儀(UV-Visible spectrum)量測薄膜在不同光源下的吸收。光觸媒活性分析則分別在紫外光與可見光光源下進行亞甲基藍(methlene blue)溶液的分解反應及銀離子還原實驗。
TiO2-xCx:C薄膜中接近鈦靶的試片，由於受到電漿直接轟擊的影響，試片結構雖為純Anatase相但晶體結構中有著許多缺陷，致使其能隙從2.6 eV上升至3.2 eV。當試片的含碳量逐漸增加，其結晶性也漸漸變好，使其具有較佳可見光與紫外光的亞甲基藍降解效果。當試片碳含量快速大幅提升時，其結構也由純anatase相轉變成類非晶質相，能隙則從3.2 eV下降至2.6 eV；雖然在亞甲基藍的降解效果上沒有優於結晶性好的試片，但在光還原銀離子的實驗中，可發現大量的奈米銀線產生，其銀還原量也隨著碳含量的增加而上升。
TiO2-xCx:C薄膜在經500oC八小時的退火處理過後，結晶性良好的試片仍然為純anatase相；但在碳含量較高的試片，其結構由非晶質相轉變成anatase與rutile混相，碳原子百分比也由原本的40%降至5%，且在表面形貌上，由於表面碳與晶界碳氣化的因素，使得薄膜表面有規律性的裂縫產生，增加了薄膜整體的表面積，亦使可見光的亞甲基藍降解效率產生大幅的提升，活性最佳的試片甚至比紫外光下降解能力最好的試片擁有更好的分解效率。

A series of combinatorial carbon-incorporated titanium oxide (TiO2-xCx:C) thin-films were prepared on silicon and quartz substrates by sputtering a metallic titanium target and a graphite target simultaneously in a gas mixture of argon and oxygen. The aims of this study are to study the effect of carbon content in the TiO2-xCx:C films by dope more carbon in titanium and to understand the relationship between the film composition, structure and optical properties and the film photocatalytic performance.
XRD, Raman and TEM are used to characterize the structure of the TiO2-xCx:C films. The composition of the films are measured using EDS and XPS. SEM and FESEM are used to observe the surface morphology. UV-Visible spectroscopy is used to measure the absorption at different wavelengths. The photocatalytic properties are characterized by the degradation of methylene-blue (MB) solution and sliver ion reduction.
All the TiO2-xCx:C films possess anatase phase of varying crystallinity. The film close to the Ti target has oxygen deficient anatase phase and contain the least carbon content. The film close to graphite target has the highest carbon content up to 40 at% and exhibits amorphous-like phase. The microstructure of the films consists of columnar grains and the grain size decreases with carbon content. With increasing carbon content , the optical band-gap energy of TiO2-xCx:C films varies from 2.6 up to 3.2 eV , and then descends to 2.5 eV. The photocatalytic activity of TiO2-xCx:C films is related to the carbon content and film crystallinity. In the photoreduction of silver-ions, more Ag particles and nano-wires and formed on the films with higher carbon concentration under visible-light illumination. In degradation of methylene blue (MB), the best photocatalytic activity is obtained in the film of the best crystallinity with a low carbon content about 3%.
After annealing at 500oC for 8h, the carbon content of the TiO2-xCx:C film of the most carbon decreases from 40% to 5%, and the film structure transforms from amorphous-like phase into anatase and rutile mixed-phase, and its morphology transforms from flat and dense surface to porous columnar grains. Thus, its surface area increase largely and its photocatalytic activity in degradation of methylene-blue (MB) under visible-light illumination is greatly enhanced.

第一章 前言
1.1概述……………………………………………………………1
1.2研究動機………………………………………………………2
1.3研究規劃………………………………………………………3

第二章 基礎理論與文獻回顧
2.1二氧化鈦簡介…………………………………………………7
2.1.1二氧化鈦的物理性質………………………………………7
2.1.2二氧化鈦的光化學性質……………………………………11
2.2二氧化鈦光催化原理…………………………………………12
2.3影響二氧化鈦光催化活性的因素……………………………14
2.3.1 TiO2 的晶型結構…………………………………………14
2.3.2添加劑的影響………………………………………………15
2.4文獻回顧………………………………………………………15
2.4.1 碳摻雜產生TiC鍵…………………………………………16
2.4.2 碳摻雜產生CO32-鍵………………………………………17
2.4.3碳披覆於二氧化鈦表面……………………………………17
2.4.4 TiC鍵碳摻雜與碳披覆……………………………………18

第三章 實驗方法
3.1實驗設備………………………………………………………19
3.1.1反應式濺鍍…………………………………………………21
3.1.2磁控濺鍍……………………………………………………21
3.2材料選擇與準備………………………………………………22
3.3濺鍍製程………………………………………………………22
3.4分析方法………………………………………………………24
3.4.1 X光繞射分析儀……………………………………………24
3.4.2拉曼光譜儀…………………………………………………26
3.4.3 X射線光電子能譜儀………………………………………27
3.4.4 紫外光/可見光吸收光譜儀分析…………………………28
3.4.5場發射掃描式電子顯微鏡…………………………………29
3.4.6表面粗度儀…………………………………………………29
3.4.7光觸媒薄膜銀還原實驗……………………………………30
3.4.8光觸媒薄膜分解亞甲基藍實驗……………………………31
3.4.9光源…………………………………………………………33

第四章 結果與討論
4.1 組合式碳摻雜之二氧化鈦薄膜的製備…………………… 35
4.1.1結構與組成之分析…………………………………………35
4.1.2光學性質之分析……………………………………………52
4.1.3光觸媒活性之分析..………………………………………55
4.2組合式共濺鍍薄膜經退火處理後之影響……………………63
4.3綜合討論………………………………………………………75
4.3.1晶格缺陷對組合式共濺鍍薄膜結構與性質的影響………78
4.3.2不同碳含量組合式共濺鍍薄膜退火的比較………………82

第五章 結論與未來工作
5.1結論…………………………………………………………85
5.2未來工作……………………………………………………88
參考文獻 …………………………………………………………89

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