臺灣博碩士論文加值系統

類鑽碳（Diamond-like Carbon, DLC）膜有硬度高、絕緣、耐磨耗、熱導性佳、抗氧化、耐化學侵蝕等特性，因此已被廣泛應用在工業界上，然而對其同時有高硬度及導電性質的應用卻比較少見，因此本研究利用平板式RF電漿，以苯及乙炔為碳源，並添加氮氣，且於高溫下沈積類鑽碳膜，得到硬度高且導電良好的膜，其電阻率可達54 W-cm並有18.1 GPa的高硬度。
本文討論氮氣對類鑽碳膜導電性及硬度的影響，發現在添加的氮含量愈高時，其電阻率愈低，而其硬度也隨著氮的增加而下降。本研究由紅外線光譜儀解釋類鑽碳膜電阻率下降的趨勢先急後緩，N-H的出現說明其原因可能是由於氫終止未飽和鍵所致。由拉曼光譜分析的結果可知道sp2/sp3比例隨著氮含量增加而增加，因此導電度隨著氮含量的增加而提高，類鑽碳膜石墨化及CºN的生成使得類鑽碳膜交聯程度下降，而硬度下降。
以苯為碳源所沈積之類鑽碳膜內有類似碳洋蔥狀的石墨結構，TEM分析的結果發現，即使在低溫的成長環境下，也有發現此結構，本研究認為苯本身的六圓環結構提供了容易形成石墨結構的機制，而以乙炔為碳源卻不易形成；螢光效應對拉曼光譜的影響說明了自我偏壓對氫含量的影響，低自我偏壓下所沈積之類鑽碳膜內也沒有發現石墨結構，因此本研究提出以苯為碳源及高自我偏壓是此石墨結構生成的關鍵。

Diamond-like carbon (DLC) films are commonly used in industry because its high hardness, resistivity, and heat conductivity, good for wear, abrasion, chemical oxidation, and erosion. However, its application for both high hardness and electrical conductivity is few. In this study, we use capacitive RF plasma to deposit DLC films by benzene and acetylene, and add nitrogen gas at high temperature. The prepared DLC film shows high hardness and good conductivity. It could reach resistivity of 54 W-cm and hardness of 18.1 GPa in the case.
We discussed the effects of nitrogen on conductivity and hardness of DLC. Increasing nitrogen concentration decreases its resistivity and hardness. It’s resistivity decreases fast initially, and than slowing down. We expressed the reason by IR analysis. The appearance of N-H bond shows the reason is caused by the termination of dangling bonds by hydrogen. Raman analysis showed the ratio of sp2/sp3 is increasing by nitrogen concentration, and its conductivity increased. Graphitization and formation of CºN bonds decrease the cross-linking of DLC, and hardness decreases.
We found graphitic structure as carbon onion-like in DLC films using benzene as carbon sources. We found graphitic structure at low depositing temperature using TEM analysis. We thought that the ring structure of benzene supplied the mechanism of forming graphitic structure. It’s not easy to become such structure using acetylene as carbon source. Hydrogen concentration is influenced by high self-bias. The intensity of photoluminescence is caused by hydrogen, and we measured the slope of Raman spectrum to discuss the effect of self-bias to hydrogen content. TEM analysis found no graphitic structure in DLC films at low depositing self-bias. And we proposed the key factors of forming graphitic structure were benzene its self and high self-bias.

目 錄

中文摘要 I
英文摘要 II
誌謝 IV
總目錄 V
表目錄 VIII
圖目錄 IX

第一章 緒論 1
1-1 前言 1

第二章 理論基礎 3
2-1 類鑽碳膜 3
2-2 類鑽碳膜的導電機制 8
2-2-1 VA族元素的摻雜 8
2-3 電漿化學 10
2-4 平板式RF電漿 17

第三章 實驗參數與研究方法 19
3-1 實驗流程 19
3-2 實驗設計 20
3-2-1 加入氮的構想 20
3-2-2 碳源的選擇 20
3-2-3 高溫鍍膜的想法 21
3-2-4 高自我偏壓（self-bias）的實驗 21
3-2-5 實驗參數 22
3-3 系統設備 23
3-4 實驗材料 24
3-4-1 實驗氣體 24
3-4-2 基板材料 24
3-5 實驗操作 26
3-5-1 基板前處理 26
3-5-2 實驗操作步驟 26
3-5-3 TEM試片的準備與分析 27
3-6 分析與鑑定 28
3-6-1 表面型態觀察 28
3-6-2 成長速率測定 28
3-6-3 薄膜結構分析 28
3-6-4 薄膜組成及鍵結型態分析 30
3-6-5 殘留應力測試 31
3-6-6 硬度值測定 31
3-6-7 微結構分析 32
3-6-8 電性量測 32
第四章 結果與討論 35
4-1 前言 35
4-2 添加氮對苯所沈積之類鑽碳膜的影響 36
4-2-1 鍍膜速率及氮含量的討論 36
4-2-2 氮含量對類鑽碳膜導電性的討論 37
4-2-3 紅外線光譜（IR）分析 38
4-2-4 拉曼光譜（Raman）分析 39
4-2-5 氮含量對類鑽碳膜硬度的討論 40
4-3 添加氮對乙炔所沈積之類鑽碳膜的影響 48
4-3-1導電度 48
4-3-2 硬度 48
4-3-3 紅外線光譜分析 49
4-3-4 拉曼光譜分析 49
4-3-5 類鑽碳膜光學能隙的討論 50
4-4 石墨結構的分析 56
4-4-1 TEM影像圖 56
4-4-2 EELS（Electron energy loss spectroscopy）分析 57
4-4-3石墨結構生成的關鍵 58
4-4-3~1 苯環本身的結構 58
4-4-3~2 自我偏壓的效應 59
第五章 結論 70
第六章 參考文獻 72
自述 77

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