超硬刀、模具材料大多是瓷金(cermet)或陶瓷(ceramic)所構成，兩者硬度約在1300~1500HV，各刀、模具上經過表面改質(surface modification)即成了進一步提升刀、模具材效率的重要技術，其中類鑽碳膜、氮化鈦膜及氮化鋁鈦薄膜有著非常優異的機械性質，所以為了因應耐磨、耐熱等各種加工環境，本實驗將在可導電氧化鋯基材上鍍覆更硬的單層膜、抗沾黏的單層膜或設計多元膜、多層膜以觀察其微結構、機械性質及高溫性質。
本研究藉由直流(DC)磁控濺鍍法於可導電氧化鋯上濺鍍氮化鈦薄膜、氮化鋁鈦薄膜及類鑽碳薄膜，在控制濺鍍參數，如工作壓力、氣體流量、輸出功率、基板溫度及濺鍍時間，以得到1~2μm厚氮化物膜及含鈦類鑽碳薄膜，隨後再對薄膜做持溫(600oC)處理以觀察其受熱後之性質及結構的變化。除了做硬度量測外，另外以拉曼光譜儀(Raman)、X-光繞射儀(X-ray Diffraction, XRD)、熱重分析(Thermogravity Analysis, TGA)、掃描式電子顯微鏡(Scanning Electron Microscope, SEM)觀察硬膜之相結構(phases)及薄膜生長型態(film morphology)以及薄膜受熱性質。
實驗結果顯示，可導電氧化鋯基材的硬度值約在1300~1500HV，經反應性磁控濺鍍氮化鈦薄膜後提升至2000~2100HV，增加率達60%，氮化鋁鈦鍍覆於可導電氧化鋯基材強度也提升至2000HV左右◦而濺鍍含鈦類鑽碳薄膜後硬度提升(2100~ 2300HV)的同時其摩擦係數的降低也將助於工(模)具元件耐摩性之增加 ◦X-光繞射分析指出當Al元素加入TiN薄膜後，其結晶格子參數將減低，掃描電鏡也清楚顯示氮化物膜的柱狀組織。而於600oC耐熱試驗後之微組織觀察發現氮化鈦薄膜與可導電氧化鋯基材界面間會有剝離的現象以及硬度降低發生，而氮化鋁鈦及含碳類鑽碳薄膜則較沒有這種現象的發生，於TGA試驗也顯示三者在氮氣及氧氣環境中，呈現增加之趨勢，且以TiN增加量最多。

Cermets and ceramics have been widely applied in tool and may have higher performance through the surface modification such as depositing nitrides, carbides and diamond materials. The zirconia with electric conductivity may be used for the tool materials and can obtain higher hardness, more abrasive resistance, higher anti-sticking properties and better high temperature properties after surface modification in addition to electric-discharge machining properties.
This study is to deposite the nitride(TiN, TiAlN) and diamond-like carbon films on the electrically conductive zirconia by DC magnetron reactive sputtering. The 1-2μm thickness of hard films may be obtained by controlling the process variables such as working pressure, inlet gas ratio, input energy and deposition time. The micro-hardnesses may be measured by Vickers hardness tester. X-ray diffraction (XRD) and scanning electron microscope(SEM) are used to evaluate the phases and morphologies of hard films. The post thermal treatments and Thermogravity Analysis(TGA) are also performed for hard films to examine the high temperature properties.
The results indicate the TiN and TiAlN hard films have hardnesses of 2000-2100HV with 60% higher than electrically conductive zirconia and DLC has hardness of 2100-2300HV and lower friction coefficient. The XRD analyzes the decreasing lattice constant of TiN with aluminum elements and the SEM observes sound boundary between films and substrates and columnar structures of the nitride films. The TiN films after thermal treatment at 600oC are found to have small decohesion or micro- cracks between films and substrate and the decreasing hardness, theses results don’t exist for TiAlN and DLC films. The TGA curves reveal the increasing weights of TiN, TiAlN and DLC and TiN has the largest increment.

目錄
摘要....................................................I
ABSTRACT................................................II
誌謝 ................................................III
目錄 ................................................IV
表目錄 ................................................V
圖目錄 ................................................VI
第1章 緒論 ........................................1
1.1 前言 ........................................1
第2章 薄膜生成及濺鍍之基礎理論及文獻回顧 ................4
2.1 電漿生成理論 .................................4
2.2 電漿濺鍍法(Sputtering Deposition) .................4
2.3 薄膜沉積原理 .................................6
2.4 鍍層微結構之模型 .................................8
2.5 氧化鋯基本結構及性能 .........................9
2.6 氮化鈦鍍膜性質 .................................10
2.7 氮化鋁鈦鍍膜性質 .................................11
2.8 碳的結構及型態 .................................11
第3章 實驗方法及設備 .................................28
3.1 實驗流程 .........................................28
3.2 鍍膜 .........................................28
3.3 性能測試 .........................................31
第4章 結果與討論 .................................41
4.1 可導電氧化鋯硬膜濺鍍之設計 .........................41
4.2 維氏硬度量測分析 .................................42
4.3 X光繞射分析 .................................42
4.4 拉曼光譜分析 .................................43
4.5 鍍層掃描電鏡(SEM)分析 .........................44
4.6 耐熱性能分析 .................................45
第5章 結論 .........................................63
參考文獻 .................................................64

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