鑽石是一種擁有高導熱以及高耐磨性的材料，在工業領域應用上極為廣泛。也因此，能夠大面積生長鑽石薄膜是一個很重要的研究領域。鑽石薄膜依據表面形貌可以分為微晶鑽石（MCD）、奈米晶鑽石（MCD）、超奈米晶鑽石（UNCD），而其中超奈米晶鑽石具備更低的表面粗糙度以及優秀的導電性質，在微機電、聲波元件等領域更具有應用的潛力。

　　熱燈絲化學氣相沈積系統是以化學氣相沈積方法成長鑽石中較早發展的系統，他具備有設備架構簡單、便宜，容易製成大面積等優點，然而在成長超奈米晶鑽石方面，由於熱燈絲系統相較於微波電漿系統而言，在高含量之氬氣環境下產生C2物種的比率並不高，造成超奈米晶鑽石並不容易成長。本論文將利用自行組建之熱燈絲系統，透過一系列的氣體變化來尋找可能的奈米晶成長條件，並透過微波電漿系統輔助氣體分子解離，來達成以熱燈絲成長超奈米晶鑽石之目的。 

　　實驗將分成三部分，第一部份利用最容易成長鑽石的氫氣－甲烷環境，改變不同基板溫度與燈絲溫度，來尋找在這一套熱燈絲系統上的成長條件。第二部份為在不變動基板溫度、氣體流量氣壓等條件下逐步增加氬氣含量，成長鑽石薄膜並檢測其拉曼峰值與表面形貌。第三部份為先利用微波電漿源輔助解離氣體分子，在透過熱燈絲系統進行再次活化，在高氬氣環境下成長薄膜並與第二部份的結果進行比較。

Diamond films are high thermal conductivity and high tribological characteristics. They have great potential for industrial applications. The capability for growing diamond d films in large area is an important research issue. The granular structure of diamond films varied with the growth parameters. Among the microcrystalline diamond (MCD), nanocrystalline diamond (NCD) and ultrananocrystalline diamond (UNCD), the UNCD films possess characteristics of extreme smooth surface and superb electrical conductivity, which is very useful for device application.

    Hot filament chemical vapor deposition HFCVD process is simple, low cast and has large area capability. However, this process cannot produce C2 species and therefore is difficult in growing diamond with nano-sized grains. 

    In this research, we re-design an HF-CVD system, explored the effect of growing parameters in microstructure development of diamond films. Moreover, we introduce C2 species, which were produced by MWCVD process into the HFCVD system so as to reduce the grain size of the diamond films. This research included 3 points: (I) We grow diamond films using CH4/H2 gas and optimize the growth parameter by systematic varying the substrate temperature and filament temperature. (II) With fixed substrate temperature, we add Ar gas into CH4/H2 Gas to systematically control the morphology of diamond films. (III) We introduce C2 species into HF-CVD system by exciting the CH4/Ar/H2 gas into plasma using microwave CVD process, so that granular structure of diamond films can be modified.
 

目錄
摘要	I
Abstract:	II
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	4
2.1 鑽石薄膜的特性與應用	4
2.1.1 鑽石及鑽石薄膜的特性	4
2.1.2 鑽石薄膜之應用	6
2.1.3 微米晶及超奈米晶鑽石薄膜	7
2.2 微米晶及超奈米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	13
第 3 章 研究方法與實驗步驟	37
3.1 熱燈絲化學氣相沉積系統結構與原理	37
3.1.1 燈絲前處理	38
3.2 熱燈絲化學氣相沉積系統實驗流程	39
3.2.1 孕核懸浮液製備與基板孕核前處理	39
3.2.2 鍍膜流程	39
3.3 薄膜特性分析	40
3.3.1 掃描式電子顯微鏡表面分析	40
3.3.2 拉曼光譜分析	41
3.4 電漿光激發光譜量測	42
第 4 章 氫氣－甲烷環境下，溫度與燈絲溫度對成膜影響之研究	49
4.1 實驗參數與步驟	49
4.2 樣品分析	51
4.2.1 掃描式電子顯微鏡表面分析	51
4.2.2 拉曼光譜分析	51
4.3 結果	52
第 5 章 氬氣－氫氣－甲烷環境下，氣體比例對成膜影響之研究	59
5.1 實驗參數與步驟	59
5.2 樣品分析	60
5.2.1 掃描式電子顯微鏡表面分析	60
5.2.2 拉曼光譜分析	61
5.2.3 穿透式顯微鏡分析	61
5.3 結果	62
第 6 章 微波電漿源輔助解離氣體再以熱燈絲系統成模之研究	73
6.1 實驗參數與步驟	73
6.2 光激發光譜分析	75
6.3 樣品分析	75
6.2.1 掃描式電子顯微鏡分析	75
6.2.2 拉曼光譜分析	75
6.2.3 穿透式電子顯微鏡分析	76
6.4 結果	76
第 7 章 結論與未來展望	88
7.1 結論	88
7.2 未來展望	88
參考文獻	90


圖目錄
圖 1-1 線性微波源電漿示意圖[87]	3
圖 2-1 鑽石的結晶構造[89]	21
圖 2-2 石墨的結晶構造[89]	21
圖 2-3 鑽石的熱傳導係數[89]	22
圖 2-4 微米微晶至超奈米微晶鑽石薄膜表面型態[89]	24
圖 2-5 以HRTEM分析超奈米微晶鑽石晶粒及晶界[29]	25
圖 2-6 超奈米微晶鑽石晶粒間距及繞射圖[29]	26
圖 2-7 不同波長的超奈米微晶鑽石薄膜拉曼光譜[33]	26
圖 2-8 C-H-O三相圖[36]	27
圖 2-9 微波電漿CVD設備圖[40]	27
圖 2-10 熱燈絲法設備圖[41]	28
圖 2-11 微波電漿放電系統設備圖[42]	28
圖 2-12 高週波電漿放電系統設備圖[43]	29
圖 2-13 電子迴旋共振設備圖[44]	29
圖 2-14 鑽石之椅狀堆積構造[89]	30
圖 2-15 石墨及鑽石的活化能相對圖[89]	30
圖 2-16 薄膜與基材之早期成核方式[55]	31
圖 2-17 與基材不反應者之孕核、成長機制[2]	31
圖 2-18 與基材形成碳化物之孕核、成長機制[2]	32
圖 2-19 偏壓輔助孕核法的反應機制[63]	33
圖 2-20 偏壓輔助成核示意圖[66]	34
圖 2-21 超音波振盪法[72]	35
圖 2-22 偏壓輔助孕核法超音波振盪法[72]	36
圖 3-1 熱燈絲系統示意圖	43
圖 3-2 載台與電極實照	43
圖 3-3 質量流量控制器－控制面板	44
圖 3-4 MKS 600 Series pressure controller	44
圖 3-5 測溫裝置示意圖	44
圖 3-6 測溫裝置實照	45
圖 3-7 燈絲碳化時之電流操作與溫度反應關係圖	46
圖 3-8 ZEISS SIGMA Series 掃描式電子顯微鏡系統	46
圖 3-9 EnSpectr R532 拉曼測量系統	47
圖 4-1 第一組 – 燈絲-基板距離變化結果之SEM影像圖	55
圖 4-2 第一組 - 基板溫度變化結果之拉曼光譜圖	56
圖 4-3 第二組 - 基板溫度變化結果之SEM影像圖	57
圖 4-4 第二組 - 基板溫度變化結果之拉曼光譜圖	58
圖 5-1 氬氣對基板升溫影響比較圖	64
圖 5-2 氬氣－氫氣比例變化結果之拉曼光譜圖	65
圖 5-3 氬氣－氫氣比例變化結果之SEM影像圖	66
圖 5-4 Ar80% - 明場與暗場相	67
圖 5-5 Ar80% - HRTEM	69
圖 5-6 Ar90% - 明場與暗場相	70
圖 5-7 Ar90% - HRTEM	71
圖 5-8 Ar80% 與Ar90% - Core-energy electron loss spectra	72
圖 5-9 Ar80% 與Ar90% - low-energy electron loss spectra	72
圖 6-1 微波電漿之光激發光譜	78
圖 6-2 微波電漿成長鑽石薄膜之拉曼光譜 (325 nm)	79
圖 6-3 微波電漿成長鑽石薄膜之SEM影像	79
圖 6-4 微波電漿源熱燈絲系統示意圖與工程模擬圖	80
圖 6-5 共振腔與金屬網	80
圖 6-6 紅外線測溫儀與觀測窗	80
圖 6-7 觀測窗觀察燈絲情況	81
圖 6-8 微波電漿在不同壓力下之光激發光譜變化	81
圖 6-9 以微波電漿源輔助解離之光激發光譜	82
圖 6-10 複合氣相沉積系統成長鑽石薄膜之SEM影像	83
圖 6-11 複合氣相沉積系統成長鑽石薄膜之拉曼光譜	83
圖 6-12 HBAr90-370-D45 - 明場與暗場相	84
圖 6-13 HBAr90-370-D45 - HRTEM	86
圖 6-14 HBAr90-370-D45 - Core-energy electron loss spectra	87
圖 6-15 HBAr90-370-D45 - low-energy electron loss spectra	87

表目錄
表 1-1 不同條件下在表面附近的各種物種濃度[86]	3
表 2-1 鑽石的各種性質[1]	19
表 2-2 鑽石的各種應用[13]	20
表 2-3 鑽石之耐熱衝擊指數比較[89]	22
表 2-4 天然鑽石、鑽石膜及類鑽石膜之性質比較[89]	23
表 2-5 微米微晶鑽石與超奈米微晶鑽石的特性比較[28]	25
表 3-1 鎢與碳化鎢材料特性	45
表 3-2 結構的各種拉曼峰值	47
表 3-3 微波電漿成長鑽石常見的光激發光譜峰值表[88]	48
表 4-1 第一組 – 燈絲-基板距離變化參數	54
表 4-2 第二組 - 基板溫度變化參數	54
表 5-1 不同氣體之導熱係數	64
表 5-2 氬氣－氫氣比例變化參數	64
表 6-1 微波電漿系統成長參數	78
表 6-2 以微波電漿源輔助解離之實驗參數	82

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