本研究主要是利用微波電漿化學汽相沉積系統中用純氫氣、氬氣與氮氣的三種氣氛下沉積鑽石薄膜並在製成過程中，用光發射光譜(opical emission spectropy) 觀察電漿成分及變化，藉此討論電漿與成長鑽石薄膜的關聯性。(i)在甲烷/氫氣電漿中主要是成長出0.5-1um柱狀的鑽石結構也發現隨著壓力變化，大晶粒比例開始變多,而且非鑽石之碳物種以外其他物種比例也開始變多。(ii)在甲烷/氬氣電漿中可成長出2-10 nm的超奈米球鑽石結構。壓力變化下雖然表面形貌與內部結構都相似，但是以150 torr的表面形貌看起來較密集。(iii)在甲烷/氮氣電漿中成功的長出鑽石薄膜，其結構為50-100 nm針狀鑽石結構。另外，也發現2-10 nm的超奈米球結構，在80 torr以後有發現參雜效果增加，在氮氣電漿會產生參雜的效果，導致在氮氣電漿成長之鑽石薄膜有較好的場發射特性。

This research discussed to growth behaviar of diamond films in methane /argon, methane/hydrogen or methane/nitrogen plasma by MPCVD (microwave plasma chemical vapor depositon)。We examined the optical emission spectrum as to investigate the correlation between plasma and characteristics of diamond films。(i)With methane/hydrogen plasma, we obtianed columnar like diamond films which grain size about 0.5~1 um, besides We found that the relative proportion of larger grains and non-diamond carbonspecies is increasing with pressure。(ii)With methane/argon plasma, we obtained ultrananocrystalline diamond film count grain size about 2~10 nm. With methane/nitrogen plasma, we obrained acicular diamond films crystalline grain size about 50-100 nm, coexisting with the ultrananocrystalline diamond grains with size about 2~10 nm。In addition, we found acicular diamond grains in 80 torr, where the doping effect operating。The diamond films have better field emission value due to doping effect in the methane and nitrogen plasma。

誌謝.......................................................I
中文摘要..................................................II
英文摘要.................................................III
目錄......................................................IV
表目錄...................................................VII
圖目錄................................................. VIII
第一章 緒論................................................1
1.1 前言...................................................1
1.2 鑽石的特性.............................................1
1.2.1 鑽石晶體結構.........................................2
1.2.2 石墨晶體結構.........................................2
1.2.3 鑽石的特性與應用.....................................3
1.2.4 鑽石薄膜在場發射特性上之應用.........................7
1.2.5 鑽石的負電子親和力特性...............................9
1.3 論文概要..............................................11
第二章 文獻回顧...........................................21
2.1 化學汽相沉積法的鑽石合成理論..........................21
2.1.1 化學汽相沉積法(CVD method)..........................21
2.1.2 電漿輔助化學汽相沉積法..............................22
2.1.3 微波電漿輔助化學汽相沈積技術........................23
2.1.4 電漿基本原理........................................24
2.2 鑽石薄膜的分類........................................27
2.2.1 微米晶鑽石膜與超奈米晶鑽石膜的比較..................27
2.2.2 鑽石薄膜的孕核的方法................................30
2.2.3 超音波振盪法-鑽石/鈦懸浮液(UM)......................32
第三章 研究方法與實驗步驟.................................35
3.1 實驗設備與方法........................................36
3.1.1 實驗流程 ...........................................36
3.1.2 實驗方法............................................36
3.2 實驗設備..............................................39
3.2.1 製程設備............................................39
3.3 分析設備..............................................40
3.3.1 掃描式電子顯微鏡(Scanning Electron Microscope,SEM)..40
3.3.2 穿透式電子顯微鏡( Transmission Electron Microscope,TEM)...........................................42
3.3.3 拉曼光譜分析(Raman Spectrum)........................43
3.3.4 電子場發射特性之量測(Field Emission,F-E)........... 45
3.3.5 光放射光譜之量測(Optical Emission Spectrum,OES).....46
第四章 光發射光譜觀察氫氣/氬氣/氮氣電漿不同壓力成長鑽石薄膜之研究
4.1 甲烷/氫氣電漿中用不同壓力成長鑽石薄膜.................57
4.1.1 光放射光譜 (Optical Emission Spectrum) 電漿成份分析........................................................58
4.1.2 掃描式電子顯微鏡(Scanning Electron Microscopy)表面形態探........................................................59
4.1.3 可見光拉曼光譜分析(Visible Raman spectrum)..........59
4.1.4 場發射特性量測 (Field  Emission)....................59
4.1.5 結果與討論..........................................60
4.2 甲烷/氬氣電漿中用不同壓力成長鑽石薄膜.................60
4.2.1 光放射光譜 (Optical Emission Spectrum) 電漿成份分析........................................................61
4.2.2 掃描式電子顯微鏡(Scanning Electron Microscopy)表面形態探........................................................62
4.2.3 可見光拉曼光譜分析(Visible Raman spectrum)..........62
4.2.4 場發射特性量測 (Field  Emission)....................63
4.2.5 結果與討論..........................................63
4.3 甲烷/氬氣電漿中用不同壓力成長鑽石薄膜.................64
4.3.1 光放射光譜 (Optical Emission Spectrum) 電漿成份分析........................................................64
4.3.2 掃描式電子顯微鏡(Scanning Electron Microscopy)表面形態探........................................................65
4.3.3 穿透式電子顯微鏡(Transmission ElectronMicroscopy)結構探討......................................................66
4.3.4 可見光拉曼光譜分析(Visible Raman spectrum)..........67
4.3.5 場發射特性量測 (Field  Emission)....................68
4.3.6 成長機制的研究......................................68
4.3.7結果與討論...........................................69
4.4 加總流量後甲烷/氬氣電漿中用不同壓力成長鑽石薄膜.......70
4.4.1 光放射光譜 (Optical Emission Spectrum) 電漿成份分析........................................................70
4.4.2 掃描式電子顯微鏡(Scanning Electron Microscopy)表面形態探........................................................71
4.4.3可見光拉曼光譜分析(Visible Raman spectrum)...........71
4.4.4 場發射特性量測 (Field  Emission)....................71
4.4.5結果與討論...........................................72
第五章 總結..............................................105
附錄一 ..................................................121
附錄二 ..................................................129



表目錄
表1-1 鑽石基本特性.........................................................................................14
表1-2 鑽石跟其他材料硬度質比較.................................................................16
表1-3 鑽石跟其他材料摩擦係數.....................................................................17
表1-4 鑽石跟其他材料的熱傳導係數的比較.................................................18表 2-1微米晶鑽石與超奈米微晶鑽石的特性比較………………………….34
表4-1 甲烷/氫氣 的實驗參數……………………………………………….73
表4-2 甲烷/氬氣 的實驗參數……………………………………………….78
表4-3 甲烷/氮氣 總流量100 sccm 實驗參數……………………………83
表4-4 60 toor到90 torr 內部結構與晶粒大小的比較圖………………96
表4-5 甲烷/氮氣 總流量141.4 sccm 實驗參數…………………………97
表4-6 氮氣電漿 總流量100 sccm 與 141.4 sccm 之比較……………104
表5-1 氫氣、氬氣與氮氣 電漿之比較……………………………………106



圖目錄
圖1-1面心立方晶體鑽石結構。………………………………………………12
圖1-2 (a) 立方晶鑽石原子結構。(b) 六方晶鑽石的原子結構。…………13
圖1-3石墨的原子結構。…………………………………………………….....13
圖1-4 金屬-真空能帶示意圖:(a).未加電場 (b)外加高電場………………..19
圖1-5 鉬尖端的薄膜場發射陰極…………………………………………….32
圖1-6 典型的半導體能帶圖:(a).正電子親合力……………………………...20
圖2-1低壓化學汽相沉積系統反應示意圖。………………………………….33
圖2-2 壓力與電子(Te)、離子(Ti)及中性粒子(Tn)溫度關係………………...33
圖2-3 超音波振盪法………………………………………………………….35
圖3-1 合成鑽石薄膜實驗流程圖…………………………………………….48
圖3-2 IPLAS 微波電漿化學汽相沉積系統示意圖………………………….49
圖3-3 本論文所採用IPLAS 微波電漿化學汽相沉積系統…………………50
圖3-4 掃描式電子顯微鏡(SEM)……………………………………………..51
圖3-5 穿透是電子顯微鏡(TEM)……………………………………………..52
圖3-6 穿透式電子顯微鏡的基本構造……………………………………….53
圖3-7 圖 3-7 拉曼(Raman)系統……………………………………………..54
圖3-8 拉曼系統示意圖……………………………………………………….54
圖3-9 電子場發射特性量測示意圖………………………………………….55
圖3-10 光放射光譜量測原理示意圖………………………………………...56
圖3-11 光放射光譜量測與腔體相對位置示意圖…………………………...56
圖4-1 甲烷/氫氣電漿的OES光譜 ………………………………………….73
圖4-2 物種變化與壓力關係圖……………………………………………….74
IX
圖4-3 為甲烷/氫氣CH光強度隨著壓力變化與氣體反應室的剖面相對位置圖……………………………………………………………………………….74
圖4-4 45 torr時CH光強度與氣體反應室的俯視相對位置圖………………75
圖4-5 55 torr時CH光強度與氣體反應室的俯視相對位置圖………………75
圖4-6 65 torr時CH光強度與氣體反應室的俯視相對位置圖………………75
圖4-7 75 torr時CH光強度與氣體反應室的俯視相對位置圖………………75
圖4-8 85 torr時CH光強度與氣體反應室的俯視相對位置圖………………75
圖4-9 95 torr時CH光強度與氣體反應室的俯視相對位置圖………………75
圖4-10 甲烷/氫氣 電漿45 torr到95 torr 的SEM圖……………………..…76
圖4-11 甲烷/氫氣 電漿可見光拉曼…………………………………………77
圖4-12 甲烷/氫氣 場發射特性圖……………………………………………77
圖4-13 甲烷/氫氣電漿的OES光譜…………………………………………78
圖4-14 物種變化與壓力關係圖……………………………………………...79
圖4-15 甲烷/氬氣CH光強度隨著壓力變化與氣體反應室的剖面相對位置圖…………………………………………………………………………….....79
圖4-16 120 torr時CH光強度與氣體反應室的俯視相對位置圖……………80
圖4-17 130 torr時CH光強度與氣體反應室的俯視相對位置圖……………80
圖4-18 140 torr時CH光強度與氣體反應室的俯視相對位置圖……………80
圖4-19 150 torr時CH光強度與氣體反應室的俯視相對位置圖……………80
圖4-20 160 torr時CH光強度與氣體反應室的俯視相對位置圖……………80
圖4-21 170 torr時CH光強度與氣體反應室的俯視相對位置圖……………80
圖4-22 甲烷/氫氣 電漿120 torr到170 torr 的SEM圖……………………81
圖4-23 甲烷/氬氣 電漿可見光拉曼…………………………………………81
X
圖4-24 甲烷/氫氣 場發射特性圖……………………………………………82
圖4-25 甲烷/氮氣電漿的OES光譜 …………………………………………83
圖4-26 物種變化與壓力關係圖……………………………………………...84
圖4-27 CN光強度隨著壓力變化與氣體反應室的剖面相對位置圖………..84
圖4-28 30 torr時CN光強度與氣體反應室的俯視相對位置圖……………..85
圖4-29 40 torr時CN光強度與氣體反應室的俯視相對位置圖…………….85
圖4-30 50 torr時CN光強度與氣體反應室的俯視相對位置圖……………..85
圖4-31 60 torr時CN光強度與氣體反應室的俯視相對位置圖……………..85
圖4-32 70 torr時CN光強度與氣體反應室的俯視相對位置圖……………..85
圖4-33 80 torr時CN光強度與氣體反應室的俯視相對位置圖……………..85
圖4-34 90 torr時CN光強度與氣體反應室的俯視相對位置圖…………….86
圖4-35 100 torr時CN光強度與氣體反應室的俯視相對位置圖……………86
圖4-36 110 torr時CN光強度與氣體反應室的俯視相對位置圖…………….86
圖4-37 甲烷/氮氣 總流量100 sccm電漿50 torr到100 torr 的SEM圖……87
圖4-38 甲烷/氮氣 總流量100 sccm電漿50 torr到100 torr 的SEM圖與TEM 明場相比較圖…………………………………………………………...88
圖4-39 60 torr時選區繞射圖的線性分析…………………………………....89
圖4-40 70 torr時選區繞射圖的線性分析…………………………………....89
圖4-41 80 torr時選區繞射圖的線性分析………………………………….....89
圖4-42 90-1 torr時選區繞射圖的線性分析……………………………….....89
圖4-43 90-2 torr時選區繞射圖的線性分析………………………………….89
圖4-44 甲烷氮氣電漿100 sccm 60 torr針狀鑽石的HRTEM的影像………90
圖4-45 甲烷氮氣電漿100 sccm 60 torr針狀鑽石邊緣HRTEM影像….......90
XI
圖4-46 甲烷氮氣電漿100 sccm 70 torr針狀鑽石的HRTEM的影像………91
圖4-47 甲烷氮氣電漿100 sccm 70 torr針狀鑽石邊緣HRTEM影像………91
圖4-48 甲烷氮氣電漿100 sccm 80 torr針狀鑽石的HRTEM的影像………92
圖4-49 甲烷氮氣電漿100 sccm 80 torr針狀鑽石邊緣HRTEM影像….......92
圖4-50 甲烷氮氣電漿100 sccm 90-1 torr針狀鑽石的HRTEM的影像…….93
圖4-51 甲烷氮氣電漿100 sccm 90-2 torr針狀鑽石邊緣HRTEM影像……93
圖4-52 甲烷/氮氣電漿60 torr到90 torr對針狀鑽石邊緣作整張FFT圖….94
圖4-53 甲烷/氮氣 總流量100 sccm的紫外光拉曼光譜……………………95
圖4-54 甲烷/氮氣 總流量100 sccm的場發射特性圖………………………95
圖4-55 甲烷/氮氣 100 sccm 電漿中CN自由基的光強度與場發射的起始電場作比對圖………………………………………………………………….....96
圖4-56 甲烷/氮氣總流量141.4 sccm電漿OES光譜 ………………………97
圖4-57 物種變化與壓力關係圖……………………………………………...98
圖4-58 為甲烷/氮氣總流量141.4 sccm CN光強度隨著壓力變化與氣體反應室的剖面相對位置圖……………………………………………………….....98
圖4-59 30 torr時CN光強度與氣體反應室的俯視相對位置圖…………….99
圖4-60 40 torr時CN光強度與氣體反應室的俯視相對位置圖…………….99
圖4-61 50 torr時CN光強度與氣體反應室的俯視相對位置圖…………….99
圖4-62 60 torr時CN光強度與氣體反應室的俯視相對位置圖…………….99
圖4-63 70 torr時CN光強度與氣體反應室的俯視相對位置圖…………….99
圖4-64 80 torr時CN光強度與氣體反應室的俯視相對位置圖…………….99
圖4-65 90 torr時CN光強度與氣體反應室的俯視相對位置圖……………100
圖4-66 100 torr時CN光強度與氣體反應室的俯視相對位置圖…………100
XII
圖4-67 110 torr時CN光強度與氣體反應室的俯視相對位置圖…………100
圖4-68 甲烷/氮氣總流量141.4 sccm電漿50 torr到100 torr的SEM圖…..101
圖4-69 甲烷/氮氣 總流量141.4 sccm的紫外光拉曼光譜………………...102
圖4-70 甲烷/氮氣 總流量141.4 sccm的場發射特性圖…………………...102
圖4-71 甲烷/氮氣 總流量100與141.4 sccm的場發射特性圖……………103
圖4-72 甲烷/氮氣 141.4 sccm 電漿中CN自由基的光強度與場發射的起始電場作比對圖………………………………………………………………...103
圖5-1 氫氣、氬氣與氮氣電漿之光發射光譜比較………………………….105
圖5-2 氫氣、氬氣與氮氣電漿之拉曼光譜比較…………………………….107
圖5-3 氫氣、氬氣與氮氣電漿之場發射特性比較………………………….107

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