鑽石擁有高硬度、極佳耐磨耗、良好場發射性、高導熱等優點。應用在表面聲波元件、微機電元件、生醫材料、場發射元件等材料，薄膜是需要的良好場發射性、導電性鑽石。鑽石薄膜依據表面形貌可以分為微晶鑽石（MCD）、奈米晶鑽石（NCD）、超奈米晶鑽石（UNCD），其中超奈米晶鑽石具備更低的良好場發射性、表面粗糙度及較佳的導電性質。 
　　在我們成長鑽石薄膜所使用的系統(Innovative Plasma system,IPLAS)，是屬於微波電漿輔助化學汽相沉積法(Microwave Plasma enhanced Chemical Vapor Deposition,      MPECVD)。一般而言，我們用一定比例的氬氣及甲烷來成長UNCD，但後來發現，當我們將成長好的UNCD再進行不同氣氛的微波電漿處理，薄膜的場發射特性優於原本的UNCD薄膜。因此我們藉由拉曼光譜、電漿光發射光譜、掃描式電子顯微結構、穿透式電子顯微結構、電子能量損失譜等，來探討當我們對UNCD進行微波電漿處理後，對其微結構以及場發射特性有著什麼樣的變化。
　　本實驗針對不同的鑽石薄膜基板分別進行甲烷/氬氣/氫氣及甲烷/氮氣兩種混合氣體電漿並施加偏壓處理後，觀察發現場發射起始電場呈現相同趨勢的變化，利用穿透式電子顯微鏡觀測樣品，加上場發射起始電場與霍爾量測等結果，顯示出使用電漿處理對於不同薄膜基板造成改質或是成長之程度有所不同，發現以小顆粒鑽石晶粒為主且擁有充足晶界空間之鑽石薄膜對於其改質的效果越好，改善電子場發射特性的效果最佳。

Diamond films possess high hardness, god tribological properties, super electron field (EFE) properties and high thermal conductivity. They have great potential for applications such as electron field emitters, microelectromechanical devices, biomaterials, surface acoustic wave devices. Diamond films can be microcrystalline (MCD), nanocrystalline (NCD) an ultrananocrystalline (UNCD), among which the UNCD films exhibit the most smooth surface, the best conductivity and moreover, the best EFE properties.

目錄

第1章 研究動機.........................................1
第2章 序論.............................................2
   2.1 鑽石薄膜的特性與應用.............................2
      2.1.1 鑽石及鑽石薄膜的特性........................2
      2.1.2 鑽石薄膜之應用.............................5
      2.1.3 微米微晶及超奈米微晶鑽石薄膜................7
   2.2 微米微晶及超奈米微晶鑽石薄膜之合成方法與理論.......9
      2.2.1 鑽石薄膜相關合成方法........................9
      2.2.2 鑽石薄膜成核相關理論........................15
第3章 研究方法與實驗步驟................................39
   3.1 微波電漿輔助化學汽相沉積法鍍鑽石薄膜結構及原理.....40
   3.2 鑽石薄膜實驗方法................................41
   3.2.1 浮液之製備及孕核(超音波震盪法(UM)-鑽石/鈦懸浮液)..............................41
      3.2.2 鍍膜流程..................................42
   3.3 電漿光發射光譜量測..............................44
   3.4 薄膜特性之分析..................................45
      3.4.1 掃描式電子顯微鏡...........................45
      3.4.2 穿透式電子顯微鏡...........................46
         3.4.2.1 觀測試片製作..........................52
      3.4.3 拉曼光譜..................................53
      3.4.4 電子能量損失譜............................54
      3.4.5 電子場發射量測............................55
　　　3.4.6 霍爾量測..................................55
第4章 電漿處理對UNCD薄膜特性之研究.....................61
   4.1 實驗步驟與參數.................................61
   4.2 樣品分析.......................................62
      4.2.1 電漿光發射光譜分析.........................62
      4.2.2 偏壓電流分析...............................62
      4.2.3 拉曼光譜分析...............................63
      4.2.4 掃描式電子顯微結構分析......................63
      4.2.5 穿透式電子顯微結構分析......................63
      4.2.6 電子能量損失譜分析..........................64
      4.2.7 電子場發射分析..............................65
      4.2.8 霍爾量測分析...............................65
   4.3 結果...........................................65
第5章 電漿處理對NCD薄膜特性之研究........................79
   5.1 實驗步驟與參數...................................79
   5.2 樣品分析........................................79
      5.2.1 電漿光發射光譜分析..........................79
      5.2.2 偏壓電流分析...............................80
      5.2.3 拉曼光譜分析...............................80
      5.2.4 掃描式電子顯微結構分析......................80
      5.2.5 穿透式電子顯微結構分析......................81
      5.2.6 電子能量損失譜分析..........................82
      5.2.7 電子場發射分析.............................82
      5.2.8 霍爾量測分析...............................82
   5.3 結果...........................................83
第6章 電漿處理對熱燈絲系統製UNCD薄膜特性之研究...........96
   6.1 實驗步驟與參數..................................96
   6.2 樣品分析.......................................96
      6.2.1 電漿光發射光譜分析.........................96
      6.2.2 偏壓電流分析...............................97
      6.2.3 拉曼光譜分析...............................97
      6.2.4 掃描式電子顯微結構分析......................97
      6.2.5 穿透式電子顯微結構分析......................98
      6.2.6 電子能量損失譜分析..........................99
      6.2.7 電子場發射分析.............................99
      6.2.8 霍爾量測分析...............................99
   6.3 結果..........................................100
第7章 結論...........................................112
參考文獻.............................................113

圖目錄
圖 2-1 鑽石的結晶構造.................................25
圖 2-2 石墨的結晶構造.................................25
圖 2-3 鑽石的熱傳導係數................................26
圖 2-4 微米晶至超奈米晶鑽石表面型態.....................28
圖 2-5 以HRTEM分析超奈米晶鑽石晶粒及晶界[29]............29
圖 2-6 超奈米晶鑽石晶粒間距及繞射圖[29].................29
圖 2-7 不同波長之超奈米晶鑽石薄膜拉曼光譜[33]...........30
圖 2-8 C-H-O三相圖[36]...............................30
圖 2-9 微波電漿CVD設備[40]............................31
圖 2-10 熱燈絲法設備[41]..............................31
圖 2-11 微波電漿放電系統設備[42].......................32
圖 2-12 高週波電漿放電系統設備[43]......................32
圖 2-13 電子迴旋共振設備[44]...........................33
圖 2-14 鑽石之椅狀堆積構造.............................33
圖 2-15 石墨及鑽石的活化能相對圖........................34
圖 2-16 薄膜與基材之早期成核方式[55]....................34
圖 2-17 與基材不反應者之孕核及成長機制[2]................35
圖 2-18 與基材形成碳化物之孕核及成長機制[2]..............35
圖 2-19 偏壓輔助孕核法的反應機制[63]....................36
圖 2-20 偏壓輔助成核示意圖[66].........................36
圖 2-21 超音波震盪法[72]..............................37
圖 2-22 偏壓輔助孕核超音波震盪法[72]....................38
圖 3-1 IPLAS CRYMMUS I MPECVD系統....................57
圖 3-2 IPLAS系統示意圖................................57
圖 3-3 水冷分流閥.....................................58
圖 3-4 電源控制箱.....................................58
圖 3-5 氣體壓力控制器.................................58
圖 3-6 MFC氣體流量控制器..............................59
圖 3-7 掃描式電子顯微鏡...............................59
圖 3-8 穿透式電子顯微鏡...............................59
圖 3-9 拉曼系統及示意圖...............................60
圖 3-10 場發射量測系統................................60
圖 4-1 UNCDTKU系列薄膜流程............................67
圖 4-2 UNCDTKU系列薄膜參數............................67
圖 4-3成長UNCDTKU及兩種電漿處理之電漿發射光譜...........68
圖 4-4 UNCDTKU薄膜進行電漿處理之輔助偏壓電流............68
圖 4-5 UNCDTKU系列薄膜之拉曼光譜.......................69
圖 4-6 UNCDTKU薄膜之掃描式電子顯微結構..................69
圖 4-7 HiDTKU薄膜之掃描式電子顯微結構..................70
圖 4-8 N2-UNCDTKU薄膜之掃描式電子顯微結構...............70
圖 4-9 UNCDTKU薄膜之穿透式電子顯微結構明場像及暗場像.....71
圖 4-10 HiDTKU薄膜之穿透式電子顯微結構明場像及暗場像.....71
圖 4-11 N2-UNCDTKU薄膜之穿透式電子顯微結構明場像及暗場像.71
圖 4-12 UNCDTKU薄膜之高解析度影像......................72
圖 4-13 HiDTKU薄膜之高解析度影像.......................73
圖 4-14 N2-UNCDTKU薄膜之高解析度影像....................74
圖 4-15 UNCDTKU系列薄膜之Low Loss電子能量損失譜.........75
圖 4-16 UNCDTKU系列薄膜之Core Loss電子能量損失譜........75
圖 4-17 UNCDTKU系列薄膜之電子場發射圖...................76
圖 4-18 UNCDTKU系列薄膜之霍爾量測.......................77
圖 4-19 UNCDTKU薄膜示意圖..............................77
圖 4-20 HiDTKU薄膜示意圖...............................77
圖 4-21 N2-UNCDTKU薄膜示意圖...........................78
圖 5-1 NCDNTUT薄膜進行電漿處理流程......................84
圖 5-2 NCDNTUT薄膜進行電漿處理之參數....................84
圖 5-3 NCDNTUT薄膜進行電漿處理之電漿光譜................85
圖 5-4 NCDNTUT薄膜進行電漿處理之輔助偏壓電流.............85
圖 5-5 NCDNTUT系列薄膜之拉曼光譜........................86
圖 5-6 NCDNTUT薄膜之掃描式電子顯微結構..................86
圖 5-7 HiDNTUT薄膜之掃描式電子顯微結構..................87
圖 5-8 N2-NCDNTUT薄膜之掃描式電子顯微結構...............87
圖 5-9 NCDNTUT薄膜之穿透式電子顯微結構明場像及暗場像......88
圖 5-10 HiDNTUT薄膜之穿透式電子顯微結構明場像及暗場像.....88
圖 5-11 N2-NCDNTUT薄膜之穿透式電子顯微結構明場像及暗場像..88
圖 5-12 NCDNTUT薄膜之高解析度影像.......................89
圖 5-13 HiDNTUT薄膜之高解析度影像.......................90
圖 5-14 N2-NCDNTUT薄膜之高解析度影像....................91
圖 5-15 NCDNTUT系列薄膜之Low Loss電子能量損失譜.........92
圖 5-16 NCDNTUT系列薄膜之Core Loss電子能量損失譜........92
圖 5-17 NCDNTUT系列薄膜之電子場發射圖...................93
圖 5-18 NCDNTUT系列薄膜之霍爾量測.......................94
圖 5-19 NCDNTUT薄膜示意圖..............................94
圖 5-20 HiDNTUT薄膜示意圖..............................94
圖 5-21 N2-NCDNTUT薄膜示意圖...........................95
圖 6-1 UNCDZUT薄膜進行電漿處理流程.....................101
圖 6-2 UNCDZUT薄膜進行電漿處理之參數...................101
圖 6-3 UNCDZUT薄膜進行電漿處理之電漿光譜................102
圖 6-4 UNCDZUT薄膜進行電漿處理之輔助偏壓電流.............102
圖 6-5 UNCDZUT系列薄膜之拉曼光譜.......................103
圖 6-6 UNCDZUT薄膜之掃描式電子顯微結構.................103
圖 6-7 HiDZUT薄膜之掃描式電子顯微結構..................104
圖 6-8 N2-UNCDZUT薄膜之掃描式電子顯微結構..............104
圖 6-9 UNCDZUT薄膜之穿透式電子顯微結構明場像及暗場像.....105
圖 6-10 HiDZUT薄膜之穿透式電子顯微結構明場像及暗場像.....105
圖 6-11 N2-UNCDZUT薄膜之穿透式電子顯微結構明場像及暗場像.105
圖 6-12 UNCDZUT薄膜之高解析度影像......................106
圖 6-13 HiDZUT薄膜之高解析度影像.......................107
圖 6-14 N2-UNCDZUT薄膜之高解析度影像...................108
圖 6-15 UNCDZUT系列薄膜之Low Loss電子能量損失譜.........109
圖 6-16 UNCDZUT系列薄膜之Core Loss電子能量損失譜........109
圖 6-17 UNCDZUT系列薄膜之電子場發射圖...................110
圖 6-18 UNCDZUT系列薄膜之霍爾量測......................111

表目錄
表 2-1 鑽石的各種性質[1]...............................23
表 2-2 鑽石的各種應用[13]..............................24
表 2-3 鑽石之耐熱衝擊指數比較...........................26
表 2-4 天然鑽石、鑽石膜及類鑽石膜性質比較................27
表 2-5 微米晶鑽石與超奈米晶鑽石的特性比較[28]............28
表 3-1 結構對應拉曼峰值................................56

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