本論文研究鈦鋁碳氮化合物奈米結構鍍層。首先利用電漿化學氣相沉積法製備TiN、TiC與TiCxN1-x薄膜，探討梯度中介層與咖啡豆表面型態對Ti-C-N鍍層優選方向的影響。結果顯示咖啡豆表面型態乃成分變化造成的微雙晶所致，此微結構並強化了TiC0.62N0.38與TiC0.75N0.25鍍層的(422)優選取向。當引入梯度中介層之後，由於底層與梯度層作用力的影響，TiC鍍層的優選取向由(220)轉為(200)，TiN鍍層的優選取向則由(200)轉為(220)。殘留應力對此結果有其影響。
接著探討Ti-Al-N鍍層之奈米結構與機械性質。以X光繞射、掃瞄式電子顯微鏡與穿透式電子顯微鏡分析相與顯微結構，另以奈米壓痕搭配原子力顯微鏡分析鍍層硬度與簡約彈性模數。高解析電子顯微鏡影像顯示當鋁含量達Al/(Al+Ti)=0.63時，晶粒尺寸可小於10 nm。以奈米壓痕量測硬度則顯示顯微結構是影響鍍層硬度的主要因素。
最後，鑑定一新的介穩相TiAlCN；利用四氯化鈦、三氯化鋁、甲烷與氮氣為反應源開發一新奈米複合材料TiAlCN/a-C。在此部分中以氫氣為載流氣體，基板溫度為500 ℃，電漿功率為100 W。鍍層以X射線繞射、拉曼光譜、X光電子能譜、穿透式電子顯微鏡及掃瞄式電子顯微鏡分析結構。顯示具B1-NaCl結構的TiAlCN奈米晶粒間含有非晶質碳相，且鍍層為(200)優選方向的柱狀晶型態。以奈米壓痕測試硬度顯示鍍層硬度較TiN高。顯微結構對機械性質影響，特別是陶瓷鍍層室溫下的塑性行為，也於文中討論。

Titanium-aluminum-carbonitride system nanostructured coatings are investigated in this study. Firstly the effects of graded interlayer and coffee-bean-like morphology on the preferred orientation of Ti-C-N coatings are discussed. TiN, TiC, and TiCxN1-x were prepared by plasma-enhanced chemical vapor deposition. The results showed that the topography of the TiCxN1-x, which resembled coffee beans, resulted from a twinning core structure that caused the dendritic grain shape and enhanced the (422) texture of TiC0.62N0.38 and TiC0.75N0.25. As graded coating was used as a transition layer, the texture of TiC was changed from (111) to (200), and TiN was changed from (200) to (111) due to the pseudomorphic forces provided by the first layer plus graded layer. The residual stress contributions to this phenomenon are also discussed.
Then the nanostructured and the corresponding mechanical behavior of Ti-Al-N coatings are investigated. The phase and microstructure of Ti1-xAlxN deposited were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Film hardness and reduced elastic modulus were measured by nanoindentation interfaced with an atomic force microscopy. High-resolution transmission electron micrograph shows that the grain size of Ti1-xAlxN decreased to less than 10 nm as aluminum contents in the film increased up to the ratio of Al/(Al+Ti)=0.63. The hardness measurement shows that the microstructure feature is the major factor to determine the film hardness.
Finally, a new metastable phase of TiAlCN is identified and a new nanocomposite, titanium aluminum carbonitride/amorphous-carbon, is invented using titanium tetrachloride, aluminum trichloride, methane and nitrogen as reactants. In this study hydrogen was used as carrier gases. A substrate temperature of 500 ℃ and an RF power of 100 W were used in all depositions. The films were characterized by X-ray powder diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. The results show that nanograins of titanium aluminum carbonitride with B1-NaCl structure are embedded in an amorphous carbon matrix. The coatings have a (200) preferred orientation with columnar cross-section morphology. Mechanical properties were analyzed by nanoindentation and hardness was demonstrated to increase via this microstructure design approach. The effects of microstructure on mechanical properties, especially the high plasticity property at room temperature, are also determined.

中文摘要 I
英文摘要 II
總目錄 IV
表目錄 VII
圖目錄 VIII
符號與中英名詞對照表 XI
第一章 序論 1
第二章 理論基礎 5
2-1 電漿原理 5
2-1-1 電漿的產生與電漿化學 5
2-1-2 電漿的描述 7
2-2 薄膜的形成機制 10
2-2-1 薄膜成長的優選方向與型態 10
2-2-2 溫度的影響 13
2-3 奈米材料 13
2-4 B1-NaCl結構 17
2-5 價電子濃度 17
2-6 梯度功能材料 18
第三章 實驗方法與步驟 19
3-1 實驗流程 19
3-2 系統設計 20
3-3 材料的選擇 22
3-4 實驗參數與步驟 24
3-5 薄膜性質分析 26
3-5-1 X射線繞射分析 26
3-5-2 掃瞄式電子顯微鏡分析 27
3-5-3 穿透式電子顯微鏡分析 27
3-5-4 二次離子質譜分析 27
3-5-5 化學分析用電子能譜分析 27
3-5-6 拉曼光譜分析 28
3-5-7 輝光放電分光分析 29
3-5-8 奈米壓痕 29
3-5-9 厚度與刮痕剖面量測 30
3-5-10 殘留應力分析 30
3-5-11 薄膜優選方向 31
3-5-12 鍍層附著性測試 31
第四章 Ti-C-N鍍層梯度中介層與表面型態對優選方向的影響 32
4-1 Ti-C-N系統單層鍍層結構與優選方向 33
4-2 梯度中介層對鍍層優選方向的影響 34
4-3 Ti-C-N咖啡豆狀表面型態 38
第五章 Ti-Al-N 鍍層奈米微結構與硬度關係之探討 44
5-1 文獻回顧 44
5-2 TiAlN奈米結構薄膜 45
5-3 鍍層微結構與機械性質的關係 55
第六章 Ti-Al-C-N鍍層TiAlCN介穩相結構鑑定與TiAlCN/a-C奈米複合鍍層結構及其性質之探討 60
6-1 TiAlCN介穩相結構之鑑定 62
6-2 TiAlCN/a-C奈米複合薄膜顯微結構之分析 68
6-3 奈米複合鍍層奈米壓痕分析 72
6-4 奈米複合鍍層之室溫塑性變形 75
第七章 結論 88
參考文獻 90
自述 99
著作 99
誌謝 101
授權書 102

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