臺灣博碩士論文加值系統

鑽石薄膜具有優異之物理、化學、機械性質，因而擁有甚高應用潛力，所以鑽石薄膜之合成為目前熱門之研究課題；尤其是鑽石薄膜具有好的電子場發射特性，適於製作場發射元件，更是重要的研究方向。而化學汽相沉積法(Chemical Vapor Deposition, CVD)是成長鑽石薄膜諸多方法中最廣為使用之合成技術。
本論文研究中，我們使用微波電漿輔助化學汽相沉積法(Microwave Plasma Enhanced Chemical Vapor Deposition, MPECVD)成長鑽石薄膜，探討在不同超奈米晶鑽石(UNCD)薄膜上成長微米晶鑽石(MCD)薄膜的生長機制、微結構特性及其對MCD/UNCD複合鑽石薄膜場發特性的影響。我們並使用拉曼光譜，場發射掃描電子顯微術(FESEM)，可見光發射光譜(OES)與穿透式電子顯微術(TEM)分析鑽石薄膜結構特性，以探討其成長機制。
本研究是首先在矽基板上成長一層超奈米晶鑽石(UNCD)薄膜作為晶核，再沉積一層微米晶鑽石(MCD)薄膜以合成MCD/UNCD複合鑽石，並探討第二階段沉積微米晶鑽石製程對MCD/UNCD複合鑽石場發特性的影響。第一部分的研究探討在氫氣/甲烷電漿中添加不同比例氬氣之效應；可以發現在添加50 %氬氣時，MCD/UNCD複合式鑽石有最佳之電子場發射特性：(MCD50)1h/UNCD1h薄膜之起始電場為6.50 V/μm；(MCD50)1h/UNCD3h薄膜之起始電場為5.0 V/μm。從TEM分析知是由於其含有較其他添加比例來得多的MCD/UNCD雙相晶，使得晶界形成奈米石墨相所致。第二部分的研究探討當選定50 %的氬氣添加為最佳化的鍍膜參數後，改變沉積MCD時間的效應，發現沉積一小時的MCD/UNCD複合鑽石薄膜，仍舊擁有最佳之場發射特性。
本研究所開發之MCD/UNCD複合鑽石薄膜最佳場發射性可以達到：起始電場為5.0 V/μm；在27.5 V/μm外加電場，場發射電流密度可達0.70 mA/cm2。

Diamond films possess excellent physical, chemical, and mechanical properties, such that the syntheses of diamond films have been the focus of research. Moreover, the diamond films own marvelous field emission properties and have great patential for the application on the electron field emission devices. The chemical vapor deposition (CVD) has been the most widely utilized process for growing the diamond films.
In this study, we used microwave plasma enhanced chemical vapor deposition (MPECVD) technique to synthesize microcrystalline diamond/ultrananocrystalline diamond (MCD/UNCD) composite films, for the purpose of investigating the growth mechanism and the related microstructural characteristics of the MCD/UNCD composite films. We first grow ultrananocrystalline diamond (UNCD) thin films as nucleation layers, followed by a secondary MPECVD process for growing microcrystalline diamond (MCD) thin films. We used Raman spectroscopy, field emission scanning electron microscopy (FESEM), optical emission spectroscopy (OES), and transmission electron microscopy (TEM) to characterize the MCD/UNCD thin films. The growth mechanism was discussed based on these investigations.
In the first part of research, different proportion of argon (0-90 %) was added into CH4/H2 plasma for the deposition of the secondary MCD layer. Among them, the 50% Ar plasma results in the best electron field emission properties, that is, the turn-on field of 6.50 V/μm for (MCD50)1h/UNCD1h and of 5.0 V/μm for (MCD50)1h/UNCD3h films. TEM examinations indicated that the two step MPECVD process markedly modified the gannular structure of UNCD films, resulting in large-grain/small-grain duplex microstructure. In the second part of research, we changed the deposition time for growing the MCD layer (with 50% Ar plasma). We observe that 1 h deposition of MCD layer leads to the best electron field emission properties. The best electron field emission properties obtainable are：turn-on field of 5.0 V/μm with EFE current density of 0.70 mA/cm2 at an applied field of 27.5 V/μm.

中文摘要………………………………………………………I
英文摘要………………………………………………………II
誌謝……………………………………………………………III
目錄……………………………………………………………IV
圖目錄…………………………………………………………VII
表目錄…………………………………………………………XI

第一章 緒論…………………………………………………………………………1
1.1鑽石薄膜的特性與應用…………………………………………………………1
1.1.1 鑽石及鑽石薄膜的特性……………………………………………………1
1.1.2 鑽石薄膜之應用……………………………………………………………3
1.1.3 微米及超奈米晶鑽石薄膜…………………………………………………5
1.2 微米及超奈米晶鑽石薄膜之合成方法與理論………………………………8
1.2.1 合成鑽石薄膜之方法………………………………………………………8
1.2.2 鑽石膜成核相關理論……………………………………………………10

第二章 實驗方法…………………………………………………………………33
2.1薄膜製備…….………………………………………………………………33
2.1.1 實驗設備與方法…………………………………………………………33
2.1.1.1 實驗設備………………………………………………………33
2.1.1.2 實驗方法………………………………………………………35
2.2 薄膜物性量測…………………………………………………………39
2.2.1光學發射光譜(Optical Emission Spectra, OES)………………40
2.2.2拉曼光譜(Raman spectra)..…………………………………………43
2.2.3掃描式電子顯微結構(Scanning Electron Microstructure, SEM)…45
2.2.4電子場發射(Electron Field Emission, EFE)……………………46
2.2.5穿透式電子顯微結構( Transmission Electron Microstructure, TEM)…51

第三章 實驗結果與討論…………………………………………………………67
3.1成長微米晶鑽石薄膜以及成長超奈米晶鑽石薄膜…………………………67
3.1.1成長微米晶鑽石以及超奈米晶鑽石薄膜與其特性研究……………67
3.1.1.1光學發射光譜分析………………………………………………………67
3.1.1.2拉曼光譜分析……………………………………………………………69
3.1.1.3掃描式電子顯微結構分析………………………………………………70
3.1.1.4電子場發射分析…………………………………………………………70
3.2在成長微米晶鑽石薄膜中添加不同比例之氬氣……………………………71
3.2.1沉積1小時超奈米晶鑽石上成長1小時微米晶鑽石薄膜與其特性研究…71
3.2.1.1光學發射光譜分析………………………………………………………71
3.2.1.2拉曼光譜分析……………………………………………………………73
3.2.1.3掃描式電子顯微結構分析………………………………………………74
3.2.1.4電子場發射分析…………………………………………………………75
3.2.1.5穿透式電子顯微結構分析………………………………………………77
3.2.2 沉積3小時超奈米晶鑽石上成長1小時微米晶鑽石薄膜與其特性研究…85
3.2.2.1拉曼光譜分析……………………………………………………………85
3.2.2.2掃描式電子顯微結構分析………………………………………………86
3.2.2.3電子場發射分析…………………………………………………………87
3.3改變沉積微米晶鑽石薄膜之時間……………………………………………88
3.3.1沉積1小時超奈米晶鑽石上成長1小時微米晶鑽石薄膜與其特性研究…89
3.3.1.1拉曼光譜分析……………………………………………………………89
3.3.1.2掃描式電子顯微結構分析………………………………………………89
3.3.1.3電子場發射分析…………………………………………………………90
3.3.2沉積3小時超奈米晶鑽石上成長1小時微米晶鑽石薄膜與其特性研究…90
3.3.2.1拉曼光譜分析……………………………………………………………90
3.3.2.2掃描式電子顯微結構分析………………………………………………91
3.3.2.3電子場發射分析…………………………………………………………91

第四章 總結與展望………………………………………………………………143
4.1 結論…………………………………………………………………………143
4.1.1在成長微米晶鑽石薄膜中添加不同比例之氬氣…………………143
4.1.2改變沉積微米晶鑽石薄膜之時間…………………………………144

4.2 未來展望……………………………………………………………………144

第五章 參考文獻…………………………………………………………………146


次研究
S1臨場監控脈衝雷射鍍膜法合成光電用氧化鋅薄膜的電漿發射光譜………157
S2脈衝雷射鍍膜法合成氧化鋅薄膜的晶相與電性研究………………………161
S3 CVD鑽石薄膜隨甲烷流量變化之物性研究…………………………………165
S4 Flow rate dependant growth and structural properties of CVD diamond films, NDNC 2008…169
本研究發表於美國國際期刊之重要研究成果
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