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研究生：	方文翰 Fang, Wen-han
論文名稱：	以熱燈絲化學氣相沈積法成長超韌性奈米複合薄膜 Growth of Super-Tough Nanocomposite Films by Hot-Filament Chemical Vapor Deposition
指導教授：	洪昭南 Hong, Chau-Nan Franklin
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2008
畢業學年度：	96
語文別：	中文
論文頁數：	160
中文關鍵詞：	韌性、陶瓷、奈米複合、熱燈絲化學氣相沈積法
外文關鍵詞：	toughness, HFCVD, nanocomposite, ceramic
相關次數：	點閱：68 下載：5
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由於鑽石薄膜具有超高硬度、低磨擦係數、耐磨耗和抗腐蝕等特點，使其在切削工具、磨耗、散熱上皆廣泛的被應用。但由於鑽石本身的脆性本質使其破裂韌性相當低，而低韌性的缺點造成鑽石材料無法在高應力或高動力衝擊的環境下被使用。因此我們藉由熱燈絲化學氣相沈積系統去製備奈米鑽石/碳化矽或奈米鑽石/碳化鈦複合薄膜，期望能藉由微結構設計之概念，滿足特定的強化及韌化機制，進而達到提升單相奈米鑽石薄膜的硬度及韌性。
我們在最適化條件下製備出的奈米鑽石/碳化矽複合薄膜，相較於奈米鑽石薄膜，硬度從63.8GPa提升至78.5GPa，提升幅度為23%。至於韌性部份，我們以Vickers進行破裂韌性量測，藉由改變不同的施加荷重(500~10000mN)，來去觀察薄膜的破裂行為。相較於奈米鑽石薄膜在施加荷重1000 mN時即產生崩裂，奈米鑽石/碳化矽複合薄膜則可有效的承受荷重超過10000 mN卻還不會崩裂。推測複合薄膜韌性得以大幅提升的原因，主要是第二相的加入將能有效的抑制裂痕快速擴張，避免材料因裂痕快速擴張而產生崩裂，進一步的反轉脆性破壞的本質行為。

Diamond films are of significant interest for tribological applications because of their high hardness, chemical inertness, low friction coefficient and high wear resistance. But diamonds are brittle with low fracture toughness. This flaw limits the use of diamonds for applications in harsh environments of dynamic impacts and high stress concentrations. We can fabricate nanodiamond-SiC or nanodiamond-TiC composite films by hot-filament chemical vapor deposition. We expect that the ideas are designed by microstructure to satisfy the mechanisms of strength and toughness. And it can raise the hardness and toughness of nanodiamond films.

We fabricate nanodiamond-SiC composite films in the most optimized conditions. Compare with nanodiamond films, the hardness enhances from 63.8GPa to 78.5GPa. The enhancement scope achieves 23%. We measure the toughness by Vickers. We change the applied loading (500~10000mN) to observe the behavior about the fracture of the films. The nanodiamond films fracture when the applied loading is 1000mN. But the nanodiamond-SiC composite films don’t fracture when the applied loading is over 10000mN. The toughness of composite films can raise substantially because add the solute atoms to nanodiamond. It can inhibit the cracks expand rapidly and avoid fracture. And it also changes the nature of brittle fracture.

中文摘要.................................................Ⅰ
英文摘要.................................................Ⅱ誌謝.....................................................Ⅲ
目錄.....................................................Ⅳ
表目錄...................................................Ⅸ
圖目錄...................................................Ⅹ
第一章 緒論 ..............................................1
1 前言..................................................1
2 研究動機與目的……………………………………………………5
2.1 高韌性奈米鑽石之製備…………………………………………7
2.2 高韌性碳化矽/奈米鑽石複合薄膜之製備 ……………………7
2.3 高韌性碳化鈦/奈米鑽石複合薄膜之製備 ……………………8
2.4 奈米氮化鈦薄膜之製備…………………………………………8
第二章 理論基礎與文獻回顧 ...............................14
1 材料簡介............................................14 
1.1 鑽石（Diamond）....................................14
1.2 碳化矽 (Silicon Carbide) ..........................14
1.3 碳化鈦 (Titanium Carbide) . .......................15
1.4 氮化鈦 (Titanium Nitride) .........................15
2 化學氣相沈積法(Chemical Vapor Deposition) ...........16
2.1化學氣相沈積法之動力學分析..........................16
2.2 CVD法成長鑽石薄膜..................................19
2.3 CVD法成長奈米鑽石薄膜..............................19
3 薄膜成長機制.........................................20
3.1 單一相薄膜沈積機制................................ 20
3.2 複合薄膜沈積機構...................................22
4 奈米複合陶瓷（Ceramic Nanocomposites）...............23
4.1 複合材料...........................................23
4.2 奈米材料...........................................24
4.3 奈米複合材料.......................................25
5 奈米複合薄膜強化理論................................ 26
5.1 細晶強化...........................................27
5.2 奈米結晶/非晶複合結構強化..........................28
5.3 多層薄膜強化.......................................30
6 奈米複合薄膜韌化理論.................................31
6.1 裂縫牽制機構.......................................32
6.2 裂縫轉折機構...................................... 32
6.3 微裂縫韌化機構.................................... 34
6.4 晶粒大小之影響.................................... 34
7 破壞韌性理論.........................................35

第三章 實驗參數與研究方法................................49
1 實驗流程.............................................49
2 系統設備.............................................50
2.1 熱燈絲系統.........................................50
2.2 電源供應系統.......................................50
2.3 溫度量測系統.......................................50
2.4 真空系統配備.......................................51
2.4.1 抽氣系統.........................................51
2.4.2 壓力檢測系統.....................................51
2.4.3 反應氣體輸入系統.................................51
3 實驗材料.............................................52
3.1 實驗基板...........................................52
3.2 實驗氣體...........................................52
3.3 實驗藥品...........................................52
4 實驗步驟.............................................53
5 分析與鑑定...........................................54
5.1 表面型態觀察.......................................54
5.2薄膜相分析..........................................54
5.3 薄膜化學鍵結及元素組成分析.........................56
5.4 薄膜微結構分析.....................................57
5.6 薄膜機械性質測定...................................57
第四章 高韌性奈米鑽石薄膜之製備
1 前言.................................................61
2 甲烷濃度對奈米鑽石薄膜之影響.........................61
2.1 薄膜表面型態及表面粗糙度之分析.....................61
2.2 薄膜成長速率分析...................................63
2.3 薄膜結構分析.......................................64
2.4 薄膜機械性質分析...................................65
25 薄膜韌性分析........................................66
3 反應壓力對奈米鑽石薄膜之影響.........................75
3.1 薄膜表面型態及表面粗糙度之分析.....................75
3.2 薄膜成長速率分析...................................76
3.3 薄膜結構分析.......................................77
3.4 薄膜機械性質分析...................................78
4 基板溫度對奈米鑽石薄膜之影響.........................85
4.1 薄膜表面型態及表面粗糙度之分析.....................85
4.2 薄膜成長速率分析...................................86
4.3 薄膜結構分析.......................................86
4.4 薄膜機械性質分析...................................87
4.5 薄膜微結構之分析...................................87
第五章 高韌性奈米鑽石/碳化矽複合薄膜之製備...............95
1 前言.................................................95
2 矽源濃度對奈米鑽石/碳化矽複合薄膜之影響..............95
2.1 薄膜表面型態及表面粗糙度之分析.....................96
2.2 薄膜成長速率分析...................................97
2.3 薄膜結構分析.......................................98
2.4 化學鍵結及元素組成百分比之分析.....................99
2.5 薄膜微結構分析....................................100
2.6 薄膜機械性質分析..................................103
2.7 薄膜韌性分析......................................104
3 小結................................................106
第六章 高韌性奈米鑽石/碳化鈦複合薄膜之製備..............126
6-1 前言................................................126
2 鈦源濃度對奈米鑽石/碳化鈦複合薄膜之影響.............126
2.1 薄膜表面型態及表面粗糙度之分析....................126
2.2 薄膜成長速率分析..................................127
2.3 薄膜結構分析......................................128
2.4 化學鍵結及元素組成百分比之分析....................129
2.5 薄膜微結構分析....................................129
2.6 薄膜機械性質分析..................................130
2.7 薄膜韌性分析......................................131
第七章 奈米氮化鈦之製備.................................143
1 前言................................................143
2 鈦源濃度與基板溫度對奈米氮化鈦薄膜之影響............143
2.1 薄膜表面型態及成長速率之分析......................143
2.2 薄膜結構分析......................................144
2.3 薄膜化學鍵結及元素組成百分比之分析................145
第八章 結論.............................................151
第九章 參考文獻.........................................154
                                    

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