本論文研究以微波電漿輔助化學氣相沈積法（MPECVD），在甲烷/氬氣電漿中加入氫氣(甲烷/氬/氫=1/99-X/X)成長鑽石薄膜，結合穿透式電子顯微鏡(TEM)、掃瞄式電子顯微鏡(SEM)及即時電漿放射光譜(OES)，對鑽石薄膜特性及成長機制深入研究。第二部分，我們採取一種修改的成長薄膜方式，在矽(Si)基板成長UNCD作為核層來代替偏壓輔助成核過程，再以甲烷/氫氣電漿於UNCD核層上成長微米鑽石薄膜(MCD/UNCD/Si)，由於其異於一般的電子場發射特性，因此我們設計了一個實驗以試圖找出其原因。
研究中發現，我們對於在甲烷/氬氣電漿中加入氫氣，即使氫氣含量為0.1%也會使薄膜樣品上鑽石晶粒由圓形改變為片狀結構，並由OES顯示，微結構的形成，是經由鑽石表面碳氫化合物的黏附與侵蝕之間的競爭所造成的結果，而造成此差異的原因則是視腔體中氫氣電漿的活性決定，而氫氣電漿侵蝕鑽石表面碳氫化合物的想法，在第二部分以甲烷/氫氣電漿於UNCD核層上成長微米鑽石薄膜的方式中，此機制也扮演主要的角色，以致能造成如此特殊的成長方式及異於一般的場發射特性，相信由於這個機制的瞭解，將可以引導出更多的變化及鑽石薄膜特性的進步。

The modification on microstructure of diamond films due to the incorporation of H2 species into the Ar/CH4 ((CH4/Ar/ H2=1/99-X/X)) plasma was systematically investigated. How the characteristics of plasma modified the microstructure and the electron field emission properties of the diamond films were investigated using transmission electron microscopy. The possible mechanism for the modification of microstructure was discussed.
Micron-crystalline diamond (MCD) films with a unique microstructure were synthesized using a modified nucleation & growth process, in which a thin layer of ultrananocrystalline diamond (UNCD) was used as nucleation layer for growing diamond films in H2-plasma. This modified nucleation and growth process was adopted so as to improve the electron field emission (EFE) properties of diamonds films.
From study imply clearly that the transition in microstructure has already been initiated when only 0.1% H2 was incorporated into Ar-plasma. Large spherical clusters (plate grains), around 30 nm in size, were observed for UNCD01 films different from equi-axed geometry for D0 samples (UNCD). Optical emission spectroscopies indicated that addition of H2-species in the Ar/CH4 plasma lead to the decrease in CH-species and increase in atomic hydrogen species. The H2 containing plasma can partially etch away the hydrocarbons (trans-polyacetylene) adhered onto the diamond clusters such that the active-carbon-species in the plasma can attach to diamond surface anisotropically, forming plate diamond grains. The amount of plate-like grains increased with the H2-content in the plasma and evolved into dendrite geometry. In contrast, when H2 is increased, the proportion of atomic hydrogen is abundant and the plasma temperature of hydrogen species is high, so that the atomic hydrogen is very active and can efficiently etch the hydrocarbons adhered on the surfaces of diamonds. The C2-species can thus attach to the surface of diamonds, forming sp3-bonds, and enlarge the diamond grains isotropically. In the second part, by the same mechanism, thus obtained (MCD)UNCD diamond films consist of nano-sized diamond clusters surrounding the large diamond grains and exhibiting better electron field emission (EFE) properties than the conventional diamond materials with faceted grains.

目 錄

摘要 I
致謝 IV
目錄 V
圖目錄 VII
表目錄 X
第一章 序論 1
I.1 研究動機 1
I.2 鑽石薄膜的特性與應用 2
I.2-1 鑽石及鑽石薄膜的特性 2
I.2-2 鑽石薄膜之應用 4
I.2-3 微米及超奈米晶鑽石薄膜 6
I.3 微米及超奈米晶鑽石薄膜之合成方法與理論 8
I.3-1 鑽石薄膜相關合成方法 8
I.3-2 鑽石膜成核相關理論 13
I.4 電子場發射理論 20
I.4-1 金屬的場發射理論 20
I.4-2 半導體場發射的基本理論 22
I.5 鑽石薄膜在電子場發射特性上之應用 24
I.6 鑽石的負電子親和力特性 26
第二章 研究方法及實驗步驟 54
II.1 微波電漿CVD鍍鑽石薄膜結構及原理 54
II.1-1 IPLAS CRYNNUS I MPECVD 系統 54
II.1-2 ASTeX 5400 (5 kW) MPECVD 鍍膜系統 55
II.2 鑽石薄膜實驗方法 55
II.2-1 不同氫含量鑽石薄膜實驗方法 55
II.2-2 UNCD核層上成長MCD薄膜實驗方法 57
II.3 薄膜之特性分析 61
II.3-1 掃描式電子微顯微鏡(SEM) 62
II.3-2 拉曼光譜分析 63
II.3-3 穿透式電子顯微鏡 64
II.3-4 電子場發射特性之量測 66
II.3-5 電漿光發射光譜儀(OES) 67
第三章甲烷/氬氣電漿中成長不同氫含量鑽石薄膜 85
III.1 表面形貌分析 86
III.1-1 SEM 觀測結果 86
III.1-2 TEM 觀測結果 87
III.1-3 拉曼光譜 89
III.2 電子場發射特性量測(EFE) 90
III.3 電漿光發射光譜分析(OES) 91
III.4 極少氫含量的探討 92
III.5 成長機制的研究 94
III.6 結論 95
第四章 UNCD 核層上成長MCD 鑽石薄膜 114
IV.1 表面形貌及場發射特性 114
IV.1-1 動機 114
IV.1-2 結果與討論 116
IV.1-3 小結 118
IV.2 成長機制及結構分析(I) 118
IV.2-1 動機 118
IV.2-2 結果 119
IV.2-3 討論 122
IV.3 成長機制及結構分析(II) 123
IV.3-1 動機 123
IV.3-2 實驗方法 123
IV-3-3 結果及討論 124
IV.4 結論 125
第五章 總結 154
參考文獻 156

圖目錄
圖I-1 鑽石與石墨的結晶構造............................. 30
圖I-2 鑽石的相圖....................................... 31
圖I-3 鑽石的熱傳導係數................................. 32
圖I-4 微米至超奈米晶表面形態........................... 34
圖I-5 HRTEM 分析超奈米晶................................ 36
圖I-6 超奈米鑽石晶粒間距及及繞射圖 ..................... 36
圖I-7 不同波長超奈米晶Raman 光譜....................... 37
圖I-8 微米及超奈米晶鑽石NEXAFS 光譜.................... 37
圖I-9 C-H-O 圖.......................................... 38
圖I-10 微波電漿CVD 設備圖............................... 39
圖I-11 熱燈絲法設備圖................................... 39
圖I-12 微波電漿放電系統設備圖........................... 40
圖I-13 高週波電漿放電系統設備圖......................... 40
圖I-14 電子迴旋共振(ECR)設備圖.......................... 41
圖I-15 鑽石之椅狀堆積構造............................... 41
圖I-16 石墨及鑽石的活化能相對圖......................... 42
圖I-17 薄膜與基材之早期成核方式......................... 42
圖I-18 與基材不反應者之孕核、成長機制.................... 43
圖I-19 與基材形成碳化物之孕核、成長機制.................. 43
圖I-20 偏壓輔助孕核反應機制............................. 44
圖I-21 偏壓輔助孕核示意圖............................... 45
圖I-22 超音波震盪法..................................... 46
圖I-23 偏壓輔助孕核超音波震盪法......................... 47
圖I-24 金屬-真空能帶示意圖(a)未加電場(b)外加高電場....... 48
圖I-25 v(y),t2(y)和y 的關係圖............................ 50
圖I-26 半導體能帶圖..................................... 51
圖I-27 不考慮電場穿透的半導體場發射示意圖................ 51
圖I-28 考慮電場穿透下n 型半導體的場發射示意圖............ 52
圖I-29 有表面態的n 型半導體............................. 52
圖I-30 鉬尖端的薄膜場發射陰極........................... 53
圖I-31 典型的半導體能帶圖............................... 53
圖II-1 IPLAS CRYNNUS I MPECVD 系統...................... 70
圖II-2 IPLAS 鍍膜系統示意圖.............................. 71
圖II-3 ASTeX 5400 微波電漿鍍膜系統...................... 72
圖II-4 不同氫含量薄膜成長流程........................... 73
圖II-5 MCD 薄膜製備流程.................................. 75
圖II-6 實驗1 成長MCD 薄膜(ASTeX) ........................ 77
圖II-7 掃描式電子微顯微鏡(SEM) .......................... 78
圖II-8 拉曼光譜量測系統................................. 80
圖II-9 拉曼光譜量測系統示意圖........................... 80
圖II-10 穿透式電子顯微鏡量測系統......................... 81
圖II-11 穿透式電子顯微鏡的基本構造....................... 82
圖II-12 電子場發射特性量測示意圖......................... 83
圖II-13 Fowler-Nordheim plot ............................. 84
圖III-1 不同氫含量薄膜SEM ................................ 96
圖III-2 不同氫含量薄膜TEM ................................ 97
圖III-3 不同氫含量薄膜小倍率SAED ......................... 98
圖III-4 薄膜高解析TEM ................................... 99
圖III-5 薄膜暗場像...................................... 100
圖III-6 可見及紫外光拉曼光譜............................ 101
圖III-7 sp3/sp2 對H2含量................................. 102
圖III-8 場發射特性圖.................................... 103
圖III-9 ID/IG ,sp3/sp2 對H2含量........................... 104
圖III-10 不同H2含量的Ar/CH4 電漿光譜.................... 105
圖III-11 不含H2含量的Ar/CH4 電漿光譜.................... 106
圖III-12 不同氫含量OES 及CH/C2 ........................ .107
圖III-13 Ha/C2 & Te ...................................... 108
圖III-14 D0.1 穿透式電子顯微鏡............................ 109
圖III-15 極少氫含量 Raman spectra & EFE ................. 110
圖III-16 D0.1 微結構 ..................................... 111
圖III-17 D1 微結構 ...................................... 112
圖III-18 成長機制示意圖................................. 113
圖IV-1 MCD,UNCD, MCD/UNCD/Si 的掃描式電子微顯微鏡圖 ..... 127
圖IV-2 MCD,UNCD, MCD/UNCD/Si 的Raman spectra,EFE ........ 128
圖IV-3 MCD-p/UNCD/Si 的掃描式電子微顯微鏡圖 ............. 129
圖IV-4 MCD-p/UNCD/Si Raman spectra, EFE................. 130
圖IV-5 MCD-c/UNCD/Si 的掃描式電子微顯微鏡圖 ............. 131
圖IV-6 MCD-c/UNCD/Si Raman spectra, EFE ................. 132
圖IV-7 MCD-t/UNCD/Si 的掃描式電子微顯微鏡圖............. 133
圖IV-8 MCD-t/UNCD/Si Raman spectra, EFE ................ .134
圖IV-9 MCD-t/UNCD/Si 數據............................... 135
圖IV-10 MCD/UNCD/Si 截面圖.............................. 136
圖IV-11 A,B 區結構像.................................... 137
圖IV-12 結構分析(截面圖) ............................... 138
圖IV-13 不同厚度上視圖.................................. 139
圖IV-14 界面區域........................................ 140
圖IV-15 界面區域 (I) ................................... 141
圖IV-16 界面區域 (II) .................................. 142
圖IV-17 界面區域微結構 (II) ............................ 143
圖IV-18 穿透式電子顯微鏡試片製作示意圖................... 144
圖IV-19 2 μm 掃描式電子微顯微鏡圖....................... 145
圖IV-20 2 μm 側面圖..................................... 146
圖IV-21 2 μm 穿透式電子顯微鏡截面........................ 147
圖IV-22 2 μm 氫氣電漿侵蝕截面圖.......................... 148
圖IV-23 2 μm 掃描式電子微顯微鏡上視圖.................... 149
圖IV-24 2 μm MCD/UNCD/Si,UNCD Raman spectra 比較........ 150
圖IV-25 2 μm MCD/UNCD/Si,UNCD EFE 比較................... 151
圖IV-26 CH4/H2 電漿作用簡圖............................... 152
圖IV-27 MCD 成長及其表面的奈米團簇成因及過程簡圖......... 153
表目錄
表I-1 鑽石的各種性質..................................... 28
表I-2 鑽石的各種應用..................................... 29
表I-3 鑽石之耐熱衝擊指數比較............................. 32
表I-4 天然鑽石、鑽石膜及類鑽石膜之性質比較................ 33
表I-5 微米晶鑽石與超奈米晶鑽石的特性比較 ................. 35
表I-6 v(y),t(y)和t2(y)數值對照表......................... 47
表II-1 不同氫含量鍍膜參數................................ 74
表II-2 MCD/UNCD/Si、MCD 及 UNCD 孕核方式參數.............. 74
表II-3 鍍膜腔內升高微波功率程序.......................... 76
表II-4 MCD/UNCD/Si、UNCD 及MCD 成長參數.................. 79
表II-5 碳結構拉曼特性峰.................................. 79
表II-6 計算電子溫度相關資料.............................. 84

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