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。
第一部份，我們首先探討不同基板對場發射性的影響包括矽基板、不施加偏壓成核UNCD的矽基板以及施加偏壓成核(Bias Enhanced Nucleation, BEN)UNCD的矽基板，接者在這三種基板上利用(i)甲烷(CH4)與氮氣(N2)以及(ii)滲入少量氫氣以施加固定負偏壓成長(BEG)成長的鑽石薄膜進行比較。
第二部份，我們找出最佳條件基板，繼續利用(i)甲烷(CH4)與氮氣(N2)以及滲入(ii)少量氫氣以負偏壓成長(BEG)製程，不同時間成長鑽石薄膜。去探討不同時間對微結構、場發射性以及導電性的的影響。
研究發現不同的基板對於鑽石薄膜的表面形貌、電子場發射特性有很大的影響。而以不施加偏壓成核UNCD基板利用甲烷(CH4)與氬氣(N2)電漿BEG成長出來的鑽石薄膜場發射特性優於一般UNCD，場發射特性最佳(σ=1099(1/Ωcm),E_0=2.48(V/μm))。利用穿透式電子顯微鏡(TEM)分析UNCD基板上利用甲烷(CH4)與氮氣(N2)固定施加負偏壓(BEG)30min成核成長出來的薄膜，鑽石結晶粒為針狀結構且其外面包一層石墨。晶粒尺寸約150nm，比一般甲烷(CH4)與氬氣(Ar)電漿成長出來的UNCD 晶粒尺寸約100nm很明顯較細長，滲入少量氫氣(0.1%H_2)，則可針狀鑽石晶粒之尺寸度幅減少至50nm，因此場發射特性大幅減少(σ=384/Ωcm),E_0=7.54μm))。

Diamond films possess high hardness, god tribological properties, superb 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.
In first part of research, we investigated the effect of different substrate materials on the growth behavior of UNCD films. We grew diamond films on (i) bare-Si, (ii) UNCD coated Si (non-biased) and (iii) UNCD/SI (bias grown) using CH4(6%)/N2 plasma, without bias or under bias. In the second part of research, based on the optimum parameters developed in the first part of research, we bias-enhanced grew diamond films on UNCD/Si (without bias) for 10-60 min, examine the development of microstructure of the UNCD films and the related EFE properties. We observed that the CH4/N2 beg-grown diamond films on UNCD (no bias)?Si substrates exhibit superior conductivity/EFE properties to other kind of diamond films.
We examined the granular structure of thus obtained UNCD films using TEM and observed that these films contain needle-like diamond grains encased with nano-graphitic layers. The size of needle-like diamond grains is 5 nm in diameters and ~150 nm in length, which has better aspect ratio than conventional diamond films with wire-like granules structure. The incorporation of 0.1%H2 resulted in needle-like diamond grains of smaller aspect ratio, which degraded the conductivity/EFE properties of the UNCD films.

目錄
摘要	II
Abstract:	III
致謝	IV
目錄	V
圖目錄	VII
表目錄	IX
第 1 章 研究動機	1
第 2 章 序論	5
2.1 鑽石薄膜的特性與應用	5
2.1.1 鑽石及鑽石薄膜的特性	5
2.1.2 鑽石薄膜之應用	8
2.1.3 微米微晶及超奈米微晶鑽石薄膜	10
2.2 微米微晶及超奈米微晶鑽石薄膜之合成方法與理論	12
2.2.1 鑽石薄膜相關合成方法	12
2.2.2 鑽石薄膜成核相關理論	19
第 3 章 研究方法及實驗步驟	44
3.1 微波電漿CVD 鍍鑽石薄膜結構及原理	45
3.2 鑽石薄膜實驗方法	46
3.2.1 懸浮液之製備及孕核：(超音波震盪法(UM)-鑽石/鈦懸浮液)	46
3.2.2 鍍膜流程	47
3.3 薄膜之特性分析	51
3.3.1 掃描式電子顯微鏡（圖3-5）	51
3.3.2 拉曼光譜分析（Raman Spectrum）	52
第 4 章 不同基板偏壓成長滲入少量氫氣(H2)N-UNCD對場發射性之研究	60
4.1 實驗步驟	60
4.2 樣品分析	63
4.2.1 OES光放射光譜分析	63
4.2.2 偏壓電流分析	63
4.2.3 掃描式電子顯微結構分析	63
4.2.4 拉曼光譜分析	64
4.2.5 電子場發射分析	64
4.3 結果	64
第 5 章 不同時間偏壓成長滲入少量氫氣(H2)的N-UNCD對場發射性、導電性之研究	75
5.1 實驗步驟	75
5.2 樣品分析	76
5.2.1 OES光放射光譜分析	76
5.2.2 偏壓電流分析	76
5.2.3 掃描式電子顯微結構分析	76
5.2.4 拉曼光譜分析	77
5.2.5 電子場發射分析	77
5.2.6 Hall measure分析	77
5.3 結果	78
第 6 章 結果討論與未來展望	97
第 7 章 參考文獻	98

 
圖目錄
圖 1-1偏壓成長薄膜 偏壓成長薄膜 偏壓成長薄膜 偏壓成長薄膜 偏壓成長薄膜 偏壓成長薄膜 對鑽石薄膜顆粒大小及表面形貌之影響 對鑽石薄膜顆粒大小及表面形貌之影響 對鑽石薄膜顆粒大小及表面形貌之影響 ................................ ..... 3
圖 1-2 鑽石薄膜拉曼光譜 ................................ ................................ ................................ .... 3
圖 1-3場發射圖 ................................ ................................ ................................ ..................... 4
圖 1-4 F4 F -N圖 ................................ ................................ ................................ ......................... 4

圖 2-1鑽石的結晶構造 [85] ................................ ................................ ................................ ... 29
圖 2-2石墨的結晶構造 [85] ................................ ................................ ................................ ... 29圖 2-3鑽石的熱傳導係 數[85] ................................ ................................ ............................... 30
圖 2-4 微米晶至超奈鑽石薄膜表面型態 微米晶至超奈鑽石薄膜表面型態 ................................ .......................... 32
圖 2-5以 HRTEM 分析超奈米微晶鑽石粒及界 分析超奈米微晶鑽石粒及界 [29] ................................ ....................... 33
圖 2-6超奈米微晶鑽石粒間距及繞射圖 超奈米微晶鑽石粒間距及繞射圖 [29] ................................ ................................ ... 34
圖 2-7不同波長的超奈米微晶鑽石薄膜拉曼光譜 不同波長的超奈米微晶鑽石薄膜拉曼光譜 [33] ................................ ....................... 34
圖 2-8C -H-O三相圖 [36] [36] ................................ ................................ ................................ ......... 34
圖 2-9微波電漿 CVD 設備圖 [40] [40] ................................ ................................ ........................... 35
圖 2-10 10 熱燈絲法設備圖 [41] ................................ ................................ ................................ 35
圖 2-11 11 微波電漿放系統設備圖 微波電漿放系統設備圖 [42] ................................ ................................ ................ 36
圖 2-12 12 高週波電漿放系統設備圖 高週波電漿放系統設備圖 [43] ................................ ................................ ............ 36
圖 2-13 電子迴旋共振設備圖 [44] [44] ................................ ................................ ......................... 37
圖 2-14 鑽石之椅狀堆積構造 [85] [85] ................................ ................................ ......................... 37
圖 2-15 石墨及鑽的活化能相對圖 石墨及鑽的活化能相對圖 [85] ................................ ................................ ............. 38
圖 2-16 薄膜與基材之早期成核方式 薄膜與基材之早期成核方式 [55] ................................ ................................ ............. 38
圖 2-17 與基材不反應者之孕核、成長機制 與基材不反應者之孕核、成長機制 [2] ................................ ................................ .. 39
圖 2-18 與基材形成碳化物之孕核、長機制 與基材形成碳化物之孕核、長機制 [2] ................................ .............................. 39
圖 2-19 偏壓輔助孕核法的反應機制 偏壓輔助孕核法的反應機制 [63] ................................ ................................ ............. 40
圖 2-20 偏壓輔助成核示意圖 [66] [66] ................................ ................................ ......................... 41
圖 2-21 超音波振盪法 [72] ................................ ................................ ................................ ..... 42
圖 2-22 偏壓輔助孕核 法 超音波振盪法 超音波振盪[72] ................................ ................................ ......... 43
圖 3-1 IPLAS CRYNNUS I MPECVD1 IPLAS CRYNNUS I MPECVD 1 IPLAS CRYNNUS I MPECVD 1 IPLAS CRYNNUS I MPECVD 系統 ................................ ................................ ............. 54
圖 3-2 IPLAS2 IPLAS 系統示意圖 ................................ ................................ ................................ ... 55
圖 3-3 IPLAS3 IPLAS 實驗前部分 儀器示意圖 儀器示意圖 ................................ ................................ ............... 56
圖 3-4 IPLAS4 IPLAS 電源控制、 Vacuum controller Vacuum controller Vacuum controller 示意圖 ................................ .................... 56
圖 3-5掃描式電子微顯鏡（ SEM ） ................................ ................................ ................. 57
圖 3-6拉曼系統 ................................ ................................ ................................ ................... 58
圖 3-7拉曼系統示意圖 ................................ ................................ ................................ ....... 58
圖 3-8電子場發射(EFE)特性量測系統 ................................ ................................ ............. 59
圖 4-1偏壓系統示意圖 ................................ ................................ ................................ ....... 65
圖 4-2 不同基板成長 N-UNCD UNCD 光放射譜 ................................ ................................ ........ 65
VI
圖 4-3 不同基板成長 N-UNCD UNCD ퟎ.ퟏ%푯ퟐ光放射譜 ................................ ......................... 66
圖 4-4 不同基板成長 N-UNCD UNCD ퟏ%푯ퟐ光放射譜 ................................ ............................. 66
圖 4-5不同基板偏壓成長 N-UNCD 之電流趨勢 ................................ ................................ . 67
圖 4-6不同基板偏壓成長 N-UNCD ퟎ.ퟏ%푯ퟐ之電流趨勢 ................................ .................. 67
圖 4-7不同基板偏壓成長 N-UNCD ퟏ%푯ퟐ之電流趨勢................................ ...................... 68
圖 4-8不同基板氮氣電漿成長 與偏壓成長的 掃描式電子顯結構 ................................ ... 68
圖 4-9不同基板摻入ퟎ.ퟏ%푯ퟐ電漿成長 與偏壓成長的 掃描式電子顯結構 ................... 69
圖 4-10 不同基板摻入ퟏ%푯ퟐ電漿成長 與偏壓成長的 掃描式電子顯結構 ..................... 69
圖 4-11 不同基板氮氣電漿成長 與偏壓成長拉曼光譜 ................................ ..................... 70
圖 4-12 不同基板摻入ퟎ.ퟏ%푯ퟐ氮氣電漿成長 與偏壓成長拉曼光譜 ............................. 70
圖 4-13 13 不同基板摻入ퟏ%푯ퟐ氮氣電漿成長 與偏壓成長拉曼光譜 ................................ 71
圖 4-14 14 不同基板氮氣電漿偏壓成長場發射圖 氮氣電漿偏壓成長場發射圖 ................................ ................................ 72
圖 4-15 15 不同基板氮氣電漿成長場發射圖 氮氣電漿成長場發射圖 ................................ ................................ ........ 72
圖 4-16 16 不同基板摻入ퟎ.ퟏ%푯ퟐ氮氣電漿偏壓成長場發射圖 氮氣電漿偏壓成長場發射圖 ................................ ........ 73
圖 4-17 17 不同基板摻入ퟎ.ퟏ%푯ퟐ氮氣電漿成長場發射圖 氮氣電漿成長場發射圖 ................................ ................ 73
圖 4-18 18 不同基板摻入ퟏ%푯ퟐ氮氣電漿偏壓成長場發射圖 氮氣電漿偏壓成長場發射圖 ................................ ............ 74
圖 4-19 不同基板摻入ퟏ%푯ퟐ氮氣電漿成長場發射圖 氮氣電漿成長場發射圖 ................................ ..................... 74
圖 5-1不同時間成長 N-UNCD UNCD光放射譜 ................................ ................................ ......... 80
圖 5-2 不同時間成長 N-UNCD UNCD ퟎ.ퟏ%푯ퟐ光放射譜 ................................ ......................... 80
圖 5-3 不同時間成長 N-UNCD UNCD ퟏ%푯ퟐ光放射譜 ................................ ............................. 81
圖 5-4不同時間偏壓成長 N-UNCD 之電流趨勢 ................................ ................................ . 81
圖 5-5不同時間偏壓成長 N-UNCD ퟎ.ퟏ%푯ퟐ之電流趨勢 ................................ .................. 82
圖 5-6不同時間偏壓成長 N-UNCD ퟏ%푯ퟐ之電流趨勢................................ ...................... 82
圖 5-7不同時間氮氣電漿成長 與偏壓成長的 掃描式電子顯結構 ................................ ... 83
圖 5-8不同時間摻入ퟎ.ퟏ%푯ퟐ電漿成長 與偏壓成長的 掃描式電子顯結構 ................... 83
圖 5-9不同時間摻入ퟏ%푯ퟐ電漿成長 與偏壓成長的 掃描式電子顯結構 ....................... 84
圖 5-10 10 不同時間氮氣電漿成長拉曼光譜 氮氣電漿成長拉曼光譜 ................................ ................................ ........ 84
圖 5-11 11 不同時間氮氣電漿偏 壓成長拉曼光譜 ................................ ................................ 85
圖 5-12 不同時間摻入ퟎ.ퟏ%푯ퟐ氮氣電漿成長拉曼光譜 氮氣電漿成長拉曼光譜 ................................ ................. 85
圖 5-13 13 不同時間摻入ퟎ.ퟏ%푯ퟐ氮氣電漿偏 壓成長拉曼光譜 ................................ ........ 86
圖 5-14 不同時間摻入ퟏ%푯ퟐ氮氣電漿成長拉曼光譜 氮氣電漿成長拉曼光譜 ................................ ..................... 86
圖 5-15 不同時間摻入ퟏ%푯ퟐ氮氣電漿偏 壓成長拉曼光譜 ................................ ............. 87
圖 5-16 不同時間氮氣電漿偏壓成長場發射圖 氮氣電漿偏壓成長場發射圖 ................................ ................................ . 87
圖 5-17 不同時間氮氣電漿成長場發射圖 氮氣電漿成長場發射圖 ................................ ................................ ......... 88
圖 5-18 不同時間摻入ퟎ.ퟏ%푯ퟐ氮氣電漿偏壓成長場發射圖 氮氣電漿偏壓成長場發射圖 ................................ ......... 88
圖 5-19 不同時間摻入ퟎ.ퟏ%푯ퟐ氮氣電漿成長場發射圖 氮氣電漿成長場發射圖 ................................ ................. 89
圖 5-20 不同時間摻入ퟏ%푯ퟐ氮氣電漿偏壓成長場發射圖 氮氣電漿偏壓成長場發射圖 ................................ ............. 89
圖 5-21 不同時間摻入ퟏ%푯ퟐ氮氣電漿成長場發射圖 氮氣電漿成長場發射圖 ................................ ..................... 90
圖 5-22 22 U基板氮氣電漿偏壓成 氮氣電漿偏壓成 10 min -明暗場圖(surface) ................................ .... 91
圖 5-23 23 U基板氮氣電漿偏壓成 氮氣電漿偏壓成 10 min -HR圖(surface) ................................ ........... 92
VII
圖 5-24 24 U基板氮氣電漿偏壓成 10 min -明暗場圖(interface) ................................ .. 92
圖 5-25 25 U基板氮氣電漿偏壓成 10 min - HR圖(interface) ................................ ....... 93
圖 5-26 26 U基板氮氣電漿偏壓成 30 min -明暗場圖(surface) ................................ ...... 93
圖 5-27 27 U基板氮氣電漿偏壓成 30 min -HR圖(surface) ................................ ............. 94
圖 5-28 28 U基板氮氣電漿偏壓成 60 min -明暗場圖(surface) ................................ ...... 94
圖 5-29 29 U基板氮氣電漿偏壓成 60 min -HR圖(surface) ................................ ............. 95
圖 5-30 30 U基板氮氣電漿偏壓成 60 min -明暗場圖(interface) ................................ .. 95
圖 5-31 31 U基板氮氣電漿偏壓成 60 min -HR圖(interface) ................................ ......... 96
表目錄
表 2-1鑽石的各種性質 [1] ................................ ................. 27
表 2-2鑽石的各種應用 13] ................................ ................. 28
表 2-3鑽石之耐熱衝擊指數比較 鑽石之耐熱衝擊指數比較 [85] ................................ ......... 30
表 2-4 天然鑽石、膜及類之性質比較 天然鑽石、膜及類之性質比較 [85] .......................... 31
表 2-5微米晶鑽石與超奈的特性比較 微米晶鑽石與超奈的特性比較 [28] [28] ......................... 33
表 3-1結構的各種拉曼峰值 ................................ ............... 57
表 4-1實驗參數值 ................................ ....................... 62
表 5-1不同時間氮氣電漿成長 與偏壓氮氣電漿成長 與偏壓hall measure hall measure 實驗參數 實驗參數 .............. 90
表 5-2不同時間摻入ퟎ.ퟏ%푯ퟐ氮氣電漿成長 與偏壓氮氣電漿成長 與偏壓hall measure hall measure 實驗參數 實驗參數 .. 90
表 5-3不同時間摻入ퟏ%푯ퟐ氮氣電漿成長 與偏壓氮氣電漿成長 與偏壓hall measure hall measure 實驗參數 實驗參數 .... 91

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