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。
因此本論文中利用IPLAS系統微波電漿輔助化學汽相沉積法沉積鑽石薄膜於不同前處理碳化鎢铣，以其能得到較佳前處理條件使鑽石薄膜鍍於碳化鎢铣刀有較佳之附著力讓碳化鎢铣刀的工作壽命延長。
實驗故分成三大部分，第一部分為碳化鎢铣刀利用不同前處理方式後沉積鑽石薄膜，再利用掃描式電子顯微鏡（SEM）、拉曼光譜（Raman），評估碳化鎢铣刀在不同的前處理下鑽石薄膜分別最佳沉積條件。考慮有無孕核以及孕核時間長短和前處理步驟的順序對於鑽石薄膜在碳化鎢铣刀上的影響，P45-EP20s為碳化鎢铣刀系列的最佳條件。
第二部分則是利用氮化物作為緩衝層，並為使鑽石薄膜沉積在緩衝層上其附著力和沉積速率等能更加提升，我們對緩衝層上進行不同前處理種類。而實驗中所使用的氮化物緩衝層為氮化鈦以及氮化鉻，考慮長時間酸洗會導致铣刀本身剛性降低以及緩衝層變薄使其抑制鈷擴散的能力降低，以及鑽石薄膜能均勻且完整連續的包覆铣刀，且無脫膜、分層等問題，P45-EP20s為氮化物緩衝層系列的最佳條件。
最後的部分為將各系列最佳前處理條件之铣刀鍍上一微米厚的鑽石薄膜進行切削測試，測試铣刀的工作壽命是否延長以及鑽石薄膜的附著力與耐磨耗度的優劣。碳化鎢铣刀C20-P45-EP20s以及氮化鉻緩衝層铣刀P45-EP20s在低走速高磨耗的測試下依然有不錯表現，僅刃部有輕微脫膜現象甚至只有鑽石薄膜隨刃角鈍化。另外由於氮化物緩衝層的品質不夠好導致鑽石薄膜在切削測試中比現不如預期，也因此可以顯出濺鍍氮化物於碳化铣刀的前處理其重要性。

Diamond and related materials grown have enormous potential application due to their marvelous combination of physical and chemical properties. However, large roughness of microcrystalline diamond films makes them inapplication in some specific applications.Recently, nanocrystalline diamond films with naturally smooth surface have been synthesized, which has more advantages and  potential applications than microcrystalline diamond films.
In brief, we develop a reliable pretreat processing procedure for depositing uniform, smooth surface and good adhesion nanocrystalline diamond films on tungsten carbide drills.

摘要	I
Abstract	II
致謝	III
目錄	IV
圖目錄	VII
表目錄	X
第一章 研究動機	1
第二章 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	8
2.2.1鑽石薄膜相關合成方法	8
2.2.2 鑽石薄膜成核相關理論	12
第三章 研究方法及實驗步驟	37
3.1 微波電漿CVD 鍍鑽石薄膜結構及原理	37
3.2 鑽石薄膜實驗方法	38
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)	38
3.2.2 鍍膜流程	38
3.3 薄膜之特性分析	40
3.3.1 掃描式電子顯微鏡	40
3.3.2 拉曼光譜分析（Raman Spectrum）	41
第四章 碳化鎢铣刀沉積鑽石薄膜研究	48
4.1 實驗步驟	49
4.1.1 前處理	49
4.1.2 MPECVD 鍍膜	50
4.2 碳化鎢铣刀樣品分析	52
4.2.1 掃描式電子顯微鏡結構分析	52
4.2.2 拉曼光譜分析	54
4.3 結果	55
第五章 氮化物緩衝層铣刀沉積鑽石薄膜研究	65
5.1 實驗步驟	66
5.1.1 前處理	66
5.1.2 MPECVD 鍍膜	67
5.2 鍍有氮化鈦緩衝層之碳化鎢铣刀樣品分析	68
5.2.1 掃描式電子顯微鏡結構分析	68
5.2.2 拉曼光譜分析	70
5.3 鍍有氮化鉻緩衝層之碳化鎢铣刀樣品分析	71
5.3.1 掃描式電子顯微鏡結構分析	71
5.3.2 拉曼光譜分析	72
5.4 結果	73
第六章 鑽石鍍膜铣刀切削測試	93
6.1 鑽石薄膜沉積速率測試	93
6.1.1 碳化鎢铣刀	93
6.1.2 氮化鈦緩衝層之碳化鎢铣刀	94
6.1.3 氮化鉻緩衝層之碳化鎢铣刀	95
6.2 鑽石鍍膜铣刀切削測試	95
6.2.1 掃描式電子顯微鏡結構分析	96
6.2.2 拉曼光譜分析	97
6.2.3 光放射光譜分析	98
6.2.4 光學顯微鏡結構分析	98
6.2.5 切削測試基板分析	99
6.2.6 掃描式電子顯微鏡結構分析	100
6.2.7 拉曼光譜分析	101
6.3 結果	102
第七章 結果討論與未來展望	114
參考文獻	116

圖目錄
圖1-1 不同氫氣含量對鑽石薄膜顆粒大小及表面形貌之影響	3
圖1-2 不同氫氣含量鑽石薄膜拉曼光譜	3
圖2-1 鑽石的結晶構造	20
圖2-2 石墨的結晶構造	20
圖2-3 鑽石的熱傳導係數	21
圖2-4 微米微晶至超奈米微晶鑽石薄膜表面型態	24
圖2-5 以HRTEM分析超奈米微晶鑽石晶粒及晶界	25
圖2-6 超奈米微晶鑽石晶粒間距及繞射圖	26
圖2-7 不同波長的超奈米微晶鑽石薄膜拉曼光譜	26
圖2-8 C-H-O三相圖	27
圖2-9 微波電漿CVD設備圖	27
圖2-10 熱燈絲法設備圖	28
圖2-11 微波電漿放電系統設備圖	28
圖2-12 高週波電漿放電系統設備圖	29
圖2-13 電子迴旋共振設備圖	29
圖2-14 鑽石之椅狀堆積構造	30
圖2-15 石墨及鑽石的活化能相對圖	30
圖2-16 薄膜與基材之早期成核方式	31
圖2-17 與基材不反應者之孕核、成長機制	31
圖2-18 與基材形成碳化物之孕核、成長機制	32
圖2-19 偏壓輔助孕核法的反應機制	33
圖2-20 偏壓輔助成核示意圖	34
圖2-21 超音波振盪法	35
圖2-22 偏壓輔助孕核法超音波振盪法	36
圖3-1 IPLAS CRYNNUS I MPECVD系統	43
圖3-2 IPLAS系統示意圖	44
圖3-3 碳化鎢铣刀鍍鑽石薄膜特殊長條型溝槽基板載台	45
圖3-4 掃描式電子微顯微鏡（SEM）	46
圖3-5 拉曼系統	47
圖3-6 拉曼系統示意圖	47
圖4-1 碳化鎢铣刀實驗流程圖	56
圖4-2 已前處理未鍍膜之碳化鎢铣刀	58
圖4-3 鑽石鍍膜於已酸洗之碳化鎢铣刀之頂部	59
圖4-4 鑽石鍍膜於已酸洗之碳化鎢铣刀之頂部	60
圖4-5 鑽石鍍膜於已酸洗之碳化鎢铣刀之頂部	61
圖4-6 鑽石鍍膜於已前處理之碳化鎢铣刀-铣刀外觀	63
圖4-7 已鍍鑽石薄膜之碳化鎢铣刀不同前處理之拉曼光譜	64
圖5-1 氮化物緩衝層铣刀實驗流程圖	74
圖5-2 已前處理未鍍膜之氮化鈦緩衝層碳化鎢铣刀	76
圖5-3 鑽石鍍膜於已前處理之氮化鈦緩衝層碳化鎢铣刀	78
圖5-4 鑽石鍍膜於已前處理之氮化鈦緩衝層碳化鎢铣刀	80
圖5-5 鑽石鍍膜於已前處理之氮化鈦緩衝層碳化鎢铣刀-铣刀外觀	82
圖5-6 已鍍鑽石薄膜之氮化鈦緩衝層碳化鎢铣刀不同前處理之拉曼光譜	83
圖5-7 已前處理未鍍膜之氮化鉻緩衝層碳化鎢铣刀	85
圖5-8 鑽石鍍膜於已前處理之氮化鉻緩衝層碳化鎢铣刀	87
圖5-9 鑽石鍍膜於已前處理之氮化鉻緩衝層碳化鎢铣刀	89
圖5-10 鑽石鍍膜於已前處理之氮化鉻緩衝層碳化鎢铣刀-铣刀外觀	91
圖5-11 已鍍鑽石薄膜之氮化鉻緩衝層碳化鎢铣刀不同前處理之拉曼光譜	92
圖6-1 不同沉積時間P45-EP20s碳化鎢铣刀截面	103
圖6-2 不同沉積時間C20-P45-EP20s碳化鎢铣刀截面	104
圖6-3 不同沉積時間P45-EP20s之氮化鈦緩衝層碳化鎢铣刀截面	105
圖6-4 不同沉積時間P45-EP20s之氮化鉻緩衝層碳化鎢铣刀截面	106
圖6-5 不同前處理條件碳化鎢铣刀-切削測試前	108
圖6-6 不同前處理條件碳化鎢铣刀之拉曼光譜-切削測試前	109
圖6-7 不同前處理條件碳化鎢铣刀之光放射光譜	109
圖6-8 光學顯微鏡觀察碳化鎢铣刀外觀	110
圖6-9切削測試後之無銅基板	111
圖6-10 不同前處理條件碳化鎢铣刀-切削測試後	112
圖6-11不同前處理條件碳化鎢铣刀之拉曼光譜-切削測試後	113

表目錄
表2-1 鑽石的各種性質	18
表2-2 鑽石的各種應用	19
表2-3 鑽石之耐熱衝擊指數比較	21
表2-4 天然鑽石、鑽石膜及類鑽石膜之性質比較	23
表2-5 微米微晶鑽石與超奈米微晶鑽石的特性比較	25
表3-1 結構的各種拉曼峰值	46
表4-1 代號示意表	56
表5-1 代號示意表	74
表6-1碳化鎢铣刀平均膜厚及沉積速率表	104
表6-2氮化物緩衝層之碳化鎢铣刀平均膜厚及沉積速率表	106
表6-3 铣刀切削參數表	110

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