氮化鈦鋯(Titanium Zirconium Nitride, TiZrN) 是由氮化鈦(Titanium Nitride, TiN)與氮 化鋯(Zirconium Nitride, ZrN)組合而成的復合材料，兩者都同屬於元素週期表中第IV族的過渡金屬氮化物，他們具有非常類似的特性，擁有高硬度、高耐磨性、低摩擦係數、低電阻率、金黃色外觀以及優異的耐腐蝕特性。由於Zr原子比Ti原子大約7%，且結構都同屬於面心立方結構中的八面體格隙，在結合過程中會產生固溶強化機制，因此TiZrN三元薄膜復合材料能夠擁有更高的硬度以及更耐磨等特性，能夠在更嚴苛更惡劣 的環境中發揮其性能。高功率脈衝磁控濺鍍(High-Power Impulse Magnetron Sputtering, HiPIMS)為一種新型的薄膜濺鍍技術，HiPIMS使用脈衝的模式，在極小的佔空比中產生 極高的電流與功率，可以大幅的降低靶面過熱的問題，且相較於傳統濺鍍擁有更高的離化率與電漿密度等優勢，能夠在較低溫的製程環境下製備出高致密度、高硬度且高品質的薄膜。本研究使用 HiPIMS 系統進行雙靶材反應性濺鍍沉積TiZrN薄膜;調整靶材的電源功率來改變薄膜的成份與結構。利用X射線繞射儀(X-ray diffraction)、拉曼光譜儀(Raman Spectrometer)以及掃描式電子顯微鏡(Scanning Electron Microscope, SEM)分析薄膜的結構、鍵結以及橫截面形貌。透過奈米壓痕機(Nanoindentation)分析薄膜的硬度以及彈性模數，並根據不同鈦鋯的成份進行磨耗試驗，分析薄膜在常溫下耐磨性以及高溫對薄膜的影響。
研究結果顯示在不同鈦鋯電源功率沉積TiZrN薄膜，隨著調整Zr靶的電源功率從1kW到2kW，可以從成份上觀察到Zr的含量有逐步的提升，Zr成功以不同比例參雜進入TiN當中。在X光繞射圖譜中，薄膜由TiZrN(111)為優選方位主導薄膜吸附與生長，且當Zr功率增加時，TiZrN(111)面有向ZrN(111)面偏移的趨勢，而在拉曼光譜儀中的一階聲學與光學訊號帶也呈現相同趨勢。透過掃描式電子顯微鏡觀察薄膜的橫截面，薄膜的結構呈現在Zone T與Zone 2之間，主要歸因於HiPIMS工藝的高離化率以及高離子動能。使用奈米壓痕機進行硬度與彈性模數分析，觀察到TiZrN薄膜硬度均有32 GPa以上，最高硬度達到36.8 GPa。在磨耗試驗中，Ti0.7Zr0.3N 顯示了較低的摩擦係數，但Ti0.5Zr0.5N薄膜的磨損量相較於Ti0.7Zr0.3N薄膜小了約10 %，H/E比值可以有效的用於預測其摩擦學性能。TiZrN薄膜經過500 oC 熱處理過後，薄膜會生成氧化物造成體積膨脹，相較於在室溫下的環境，高溫熱處理後的Ti0.5Zr0.5N薄膜成長幅度高於Ti0.7Zr0.3N薄膜，主要原因為薄膜內部擁有較多的Zr，容易生成更多的ZrO2相使薄膜增厚。

Titanium Zirconium Nitride (TiZrN) is a composite material composed of Titanium Nitride (TiN) and Zirconium Nitride (ZrN). Both of these compounds belong to the transition metal nitrides in the IVth group of the periodic table and share similar characteristics. They are known for their high hardness, excellent wear resistance, low friction coefficient, low electrical resistivity, a golden appearance, and outstanding corrosion resistance.Due to the larger size of Zr atoms compared to Ti atoms (about 7% larger), and their common face-centered cubic structure with octahedral interstitial sites, the combination of these elements results in a solid solution strengthening mechanism. As a result, TiZrN ternary thin film composites exhibit higher hardness and improved wear resistance, making them suitable for more demanding and harsh environments.High-Power Impulse Magnetron Sputtering (HiPIMS) is a novel thin film deposition technique that utilizes a pulsed mode, generating high current and power at extremely low duty cycles. This technology significantly reduces issues related to target overheating and offers advantages such as higher ionization rates and plasma density compared to traditional sputtering methods. This enables the production of high-density, high-hardness, and high-quality thin films in lower temperature processing environments.In this research, a HiPIMS system was used to deposit TiZrN thin films with dual-target reactive sputtering. The power supply to the dual targets was adjusted to vary the film's composition and structure. The structure, bonding, and cross-sectional morphology of the films were analyzed using X-ray diffraction, Raman spectroscopy, and Scanning Electron Microscopy (SEM). Nanoindentation was used to determine the film's hardness and elastic modulus, and wear tests were conducted for different TiZr compositions to assess the film's wear resistance at room temperature and elevated temperatures.
The results of the study show that by adjusting the Zr target's power from 1 kW to 2 kW, a gradual increase in Zr content in the TiZrN films can be observed. TiZrN (111) orientation dominates the film's adsorption and growth, and as Zr power increases, there is a trend towards deviation from TiZrN (111) orientation toward ZrN (111) orientation. This trend is also reflected in the Raman spectra. Cross-sectional observations of the films show a structure that lies between Zone T and Zone 2, primarily due to the high ionization rates and ion kinetic energies in the HiPIMS process.The hardness of the TiZrN films is consistently above 32 GPa, with the highest hardness reaching 36.8 GPa. In wear tests, Ti0.5Zr0.5N exhibits lower friction coefficients, with about 10% less wear compared to Ti0.7Zr0.3N, indicating the effectiveness of the H/E ratio in predicting their tribological performance. After heat treatment at 500°C, the films experience oxidation and volume expansion. Ti0.5Zr0.5N film growth is more pronounced than Ti0.7Zr0.3N film, mainly due to the higher Zr content, which leads to the formation of more ZrO2 phases and thicker films at elevated temperatures.

摘要...i
Abstract...iii
誌謝...v
目錄...vi
表目錄...viii
圖目錄...ix
第一章 緒論...1
1.1前言...1
1.2 研究動機與目的...3
第二章 基礎原理與文獻回顧...4
2.1金屬氮化物...4
2.1.1氮化鈦(TiN)...5
2.1.2氮化鋯(ZrN)...7
2.1.3氮化鈦鋯(TiZrN)...8
2.2薄膜技術與理論...12
2.2.1薄膜成長機制...12
2.2.2薄膜成長結構...13
2.3薄膜沉積技術...15
2.3.1化學氣相沉積...15
2.3.2物理氣相沉積...16
2.4磁控濺鍍...18
2.4.1濺鍍電源...19
2.4.2高功率脈衝磁控技術...21
第三章 實驗方法與步驟...25
3.1試片準備與前處理...25
3.2實驗細節與流程...25
3.3薄膜結構分析...27
3.3.1 X-射線繞射...27
3.3.2掃描式電子顯微鏡...28
3.3.3拉曼光譜...29
3.4薄膜機械性質分析...30
3.4.1薄膜厚度量測...30
3.4.2奈米壓痕...31
3.4.3磨耗試驗...32
第四章 結果與討論...34
4.1不同電源功率下沉積TiZrN薄膜的成份與結構分析...34
4.2不同電源功率下沉積TiZrN薄膜機械性質分析...41
4.3不同鋯含量TiZrN薄膜的高溫以及磨耗試驗...43
4.3.1不同鋯含量TiZrN薄膜的的成份鑑定...43
4.3.2不同鋯含量TiZrN薄膜的磨耗分析...45
4.3.3不同鋯含量TiZrN薄膜對於高溫的影響...48
第五章 結論...49
參考文獻...50
Extended Abstract...55

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