臺灣博碩士論文加值系統

由於鑽石具有許多無與倫比的物理及化學特性，因此有極高的應用潛力。但是傳統人工鑽石膜粗糙的刻面(facet)表面是應用上最大的問題之一。為了克服表面粗糙度的問題，近幾年來合成奈米晶鑽石(nano-diamond)成為相當熱門的研究主題，這是因為奈米晶鑽石不但可以大輻降低表面粗糙度，而且在許多方面具備了比微米晶鑽石更卓越的特性，因此在各種領域的應用上具有很大的潛力。元件用自然平坦的奈米晶鑽石膜，除了必須在孕核(nucleation)及成長(growth)階段分別具備高的孕核密度及高的二次再孕核(second order nucleation)密度外，為了達到商業應用的價值，也必須開發大面積、均勻高的奈米鑽石薄膜。
　　本論文研究的第一章為序論及技術背景，將針對研究動機及目前的技術發展做一完整的描述；第二章為實驗方法及分析方法的介紹；第三章將探討如何製備不同晶粒大小的人工鑽石膜，以及它們在表面形貌(SEM, AFM)、結晶結構(Raman, NEXAFS)及場發射(electron field emission)特性上的差異；第四章將探討不同前處理(pre-nucleation)步驟對於成長奈米晶鑽石膜孕核密度(SEM)、表面型態(AFM)以及附著力(nano-indentor)的影響；第五章為大面積、高均勻度奈米晶鑽石薄膜製備的研究，以光譜儀(optical emission spectroscopy, OES)分析不同成長條件對於成長速率(SEM)、薄膜應力、均勻度、結晶結構(Raman)等特性的影響，並以電磁場模擬來解釋腔體設計對電漿均勻度的重要性；第六章為奈米鑽石層狀結構高頻表面聲波(surface acoustic wave, SAW)元件研究；第七章為奈米鑽石膜的場發射特性研究；第八章為總結及未來展望；第九章為參考文獻。

Diamond and related materials grown have enormous potential applications due to their marvelous combination of physical and chemical properties. However, large roughness of microcrystalline diamond films makes them inapplicable in some specific applications. Recently, nanocrystalline diamond films with naturally smooth surface have been synthesized, which make low prime cost diamond wafer is possible for commercial applications.
The mortification of this research is looking for a possible method to fabricate low cost and applicable diamond wafer for commercial applications. In order to achieve this goal, a suitable nucleation and growth method is necessary. In this study, a very high nucleation density (>1011 sites/cm2) and good adhesion (~ 67 mN) are achieved successfully by modified ultrasonication method and BEN method. By controlling deposition parameters, reasonable deposition rate ~ 1.3 �慆/hr, and less than 50% thickness variation could be achieved for 4” wafer without substrate temperature control. With good microwave plasma reactor design and suitable substrate temperature controlling system, naturally smooth diamond film with large area (4”) uniformity is possible.
Diamond layered SAW resonator and electron field emission measurements are performed successfully by using nanocrysatlline diamond films without any post-processing for demonstrating the practicability of these naturally smooth artificial diamond films.
In brief, we develop a reliable and low cost processing procedure for depositing large area, uniform nanocrystalline diamond wafer with naturally smooth surface for commercial applications without expensive and time consuming post-processing.

摘要 I
致謝 III
目錄 IV
表目錄 X
圖目錄 XI
第一章 序論及技術背景 1
I-1 研究動機 1
I-2 鑽石的基本特性 1
I-2-1 鑽石的特性及相關應用 1
I-2-2 人工鑽石歷史 4
I-2-3 奈米晶鑽石膜 5
I-3 鑽石的孕核理論及方法 10
I-3-1 孕核理論 10
I-3-2 促進鑽石孕核的方法 12
I-3-2-1製造殘留高表面能或應力的缺陷 12
I-3-2-2 殘留鑽石晶種 13
I-3-2-3 表面被覆 13
I-3-2-4 偏壓輔助孕核 15
I-4 鑽石的成長理論及方法 18
I-4-1 傳統的微米晶鑽石 18
I-4-2 奈米晶鑽石 20
I-4-2-1 缺氫氣環境 20
I-4-2-2 高濃度含碳氣體 22
I-4-2-3 偏壓輔助成長 22
I-4-2-4 其它 23
I-5 表面聲波元件 25
I-5-1 何謂表面聲波元件 25
I-5-2 表面聲波元件用壓電材料 26
I-5-3 壓電－鑽石層式表面聲波元件 28
I-5-4 理論計算及範例 31
I-5-5 專利地圖 35
I-6 電子場發射特性 38
I-6-1 金屬的電子場發射理論 39
I-6-2 半導體的場發射理論 40
I-6-3 場發射材料的發展 42
I-7 其它應用 45
I-7-1 微機電系統(MEMS) 45
I-7-2 電化學電極 46
I-7-3 生化應用 47
第二章 實驗方法及分析 49
II-1孕核階段 49
II-1-1 超音波震盪法(U) 49
II-1-2超音波震盪法－鑽石/鈦懸浮液(U-m) 49
II-1-3 預積碳－超音波震盪法(PC-U) 50
II-1-4 偏壓輔助孕核法(BEN) 50
II-1-4-1 ASTeX 5400 MPECVD系統 50
II-1-4-2 偏壓輔助孕核實驗條件 51
II-2成長階段 52
II-2-1 微米晶、次微米晶及奈米晶鑽石膜 52
II-2-2 超奈米微晶鑽石膜 53
II-2-2-1 IPLAS CRYNNUS I MPECVD系統 53
II-2-2-2 鍍膜條件 55
II-2-2-3 超奈米微晶鑽石薄膜 56
II-3材料特性分析工具 56
II-3-1 二次電子顯微鏡(SEM) 57
II-3-2原子力顯微鏡(AFM) 57
II-3-3拉曼光譜儀(Raman spectrocope) 58
II-3-4近邊緣X射線吸收精細結構(NEXAFS) 58
II-3-5 X-ray繞射晶體結構分析(XRD) 59
II-3-6奈米壓痕儀(nanoindenter) 59
II-3-7雷射光槓桿儀 60
II-4表面聲波元件模擬、製程、量測 61
II-4-1 高指向性氮化鋁薄膜 61
II-4-2 IDT－氮化鋁－奈米晶鑽石層式表面聲波特性模擬 62
II-4-3 奈米晶鑽石層式表面聲波元件製程 63
II-4-4 奈米晶鑽石層式表面聲波元件特性量測 64
II-5電子場發射特性量測 64
II-5-1量測設備及方法 64
II-5-2 F-N圖及分析 65
II-5-3表面處理 66
第三章 從微米晶鑽石到奈米晶鑽石 68
III-1表面形貎 68
III-2結晶結構 73
III-2-1拉曼光譜 73
III-2-2NEXAFS 75
IV-3場發射特性 78
IV-4結論 82
第四章 鑽石的孕核研究 83
IV-1偏壓輔助孕核(BEN) 84
IV-1-1孕核行為 84
IV-1-1-1施加偏壓下電漿及基板行為 84
IV-1-1-2以偏壓電流曲線監測孕核行為 86
IV-1-1-3孕核行為 88
IV-1-2不同孕核條件的影響 93
IV-1-2-1偏壓電流行為 93
IV-1-2-2表面形貌及晶粒大小 95
IV-1-2-3結晶結構 97
IV-1-3結論 99
IV-2不同孕核方式 100
IV-2-1孕核密度及表面形貎 100
IV-2-2結晶結構 106
IV-2-3附著特性 107
IV-2-4結論 110
第五章 奈米晶鑽石薄膜 111
V-1奈米晶鑽石薄膜 112
V-1-1表面形貎及結晶結構 112
V-1-2鍍膜速率 116
V-1-3碳黑被覆問題 119
V-2鍍膜均勻度 121
V-2-1孕核均勻度 121
V-2-2鍍膜均勻度 126
V-2-2-1膜厚均勻度 127
V-2-2-2結晶結構均勻度 129
V-3微波腔體設計 131
V-3-1 TM102模態 131
V-3-2腔體尺寸參數 133
V-3-3基板載具參數 136
V-4結論 139
第六章 氮化鋁－奈米晶鑽石表面聲波元件 141
VI-1高指向性氮化鋁薄膜 142
VI-1-1氮化鋁/矽基板 142
VI-1-1-1 XRD結晶結構分析 142
VI-1-1-2 拉曼分析 143
VI-1-1-3 膜厚均勻度 145
VI-1-2氮化鋁/奈米晶鑽石/矽基板 148
VI-2氮化鋁－奈米晶鑽石表面聲波元件 151
VI-2-1氮化鋁－奈米晶鑽石表面聲波特性模擬 152
VI-2-2氮化鋁－奈米晶鑽石表面聲波元件製作 153
VI-2-3氮化鋁－奈米晶鑽石表面聲波特性量測 156
VI-2-3-1雷射脈衝激發表面聲波技術 156
VI-2-3-2層式表面聲波元件量測 159
VI-3結論 162
第七章 奈米晶鑽石場發射特性研究 163
VII-1偏壓大小影響 164
VII-1-1場發射特性 164
VII-2硼摻雜 166
VII-2-1場發射特性 167
VII-2-2結晶結構、導電度及表面型貎 169
VII-2-3改變偏壓大小對硼摻雜的影響 172
VII-3氮摻雜 175
VII-3-1場發射特性 175
VII-3-2導電度、結晶結構、鍍膜速率及晶粒大小 177
VII-4表面處理 182
VII-4-1場發射特性 182
VII-4-2親水性測試、結晶結構及表面型貎 183
VII-5結論 189
第八章 總結及未來展望 190
第九章 參考文獻 194
個人著作 208
個人簡歷 210

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