以物理氣相沉積鍍製之薄膜往往會產生殘留應力。降低殘留應力的方式包含在基板與硬膜之間加入金屬介層，或者製造梯度性漸層與建構性介層。然而，利用建構性介層的殘留應力釋放機制仍未知。本研究之目的為提出一個物理模式以解釋導致上層硬膜應力釋放之能量釋放機制。鍍覆於矽基板之氮化鈦鋯/氮化鈦/鈦為本研究的模式材料。雷射曲率法與平均X光應變法(AXS)分別為量測薄膜整體應力與各層薄膜應力之方法。實驗結果顯示使用鈦/氮化鈦時，上層氮化鈦鋯之應力比使用單層鈦介層時還低。最低的氮化鈦鋯之應力為氮化鈦300奈米厚之三層試片T3，其值為-2.18 GPa。三層系列試片中，氮化鈦的應力隨著其厚度呈現線性上升。在我們提出的物理模式中，我們假設上層硬膜減少的彈性能與基板減少的彈性能皆轉換為鈦介層的塑性功。模式中也提出一個計算氮化鈦鋯/氮化鈦複合薄膜彈性能之方法。本研究發現氮化鈦的角色為能量通道，能夠將氮化鈦鋯的能量有效的傳遞至鈦介層。因此，氮化鈦鋯/氮化鈦/鈦三層試片中的能量釋放效率遠高於氮化鈦鋯/鈦雙層式片。另外，氮化鈦過渡層的加入使得主要能量釋放比例反轉。三層試片中的主要能量釋放比例在上層硬膜中，而雙層試片中的主要能量釋放比例則在基板中。

Residual stress is usually generated in hard coatings deposited by physical vapor deposition. Residual stress can be alleviated by introducing a metal interlayer between coating and substrate or by creating functionally graded coating and coating architecture. However, the underlying stress relief mechanism of architected coatings has not been fully explored. This study aims to establish an energy-based physical model to explain the energy relief mechanism in architected coatings that results in stress relief of the hard coating. TiZrN/TiN/Ti tri-layer coating on Si substrate was chosen as the model system. Laser curvature method and the average X-ray strain method combined with nanoindentation were used to measure the residual stress of the entire coating and individual layers, respectively. Experimental results showed that the stress in TiZrN coating was further reduced by introducing a Ti/TiN architected interlayer as compared with adding a Ti interlayer. The tri-layer specimen with TiN thickness of 300 nm showed the largest stress relief among all specimens, where the TiZrN coating had the lowest stress, -2.18 GPa. The stress of TiN transitional layer in the tri-layer specimens linearly increased with TiN thickness. Our physical model postulated that the relief of stored elastic energy in the top coating and in the Si substrate were both converted into the plastic work of Ti interlayer. A methodology for calculating stored energy in TiZrN/TiN composite coating was proposed. The TiN transitional layer served as an energy channel that effectively transferred the stored energy in TiZrN to the Ti interlayer. Therefore, the efficiency of energy relief in TiZrN/TiN/Ti tri-layer coating was significantly higher than that of TiZrN/Ti bilayer coating. Furthermore, the addition of TiN transitional layer reversed the major fraction of energy relief from the substrate to the top coating.

致謝 i
摘要 ii
Abstract iii
Contents iv
List of Figures vi
List of Tables vii
Chapter 1 Introduction 1
Chapter 2 Literature Review 3
2.1 Characteristics of Transition Metal Nitrides 3
2.2 Characteristics of TiZrN Coatings 6
2.2.1 Structure 6
2.2.2 Properties 8
2.3 Residual Stress in Thin Films 8
2.4 Measurement of Residual Stress in Thin Films 9
2.4.1 Laser Curvature Method (LCM) 9
2.4.2 Grazing Incidence X-ray cos2αsin2ψ Method 10
2.4.3 Average X-ray Strain (AXS) Method 13
2.5 Stress Relief in Hard Coatings by Metal Interlayer 15
2.6 Functionally Graded and Architected Coatings 16
Chapter 3 Theoretical Basis 19
3.1 Stored Elastic Energy of Hard Coatings 19
3.2 Plastic Work of Ti 20
3.3 Energy Conservation 20
3.4 Stored Elastic Energy in a Composite Coating 21
Chapter 4 Experimental Procedures 24
4.1 Sample Preparation and Film Deposition 24
4.2 Characterization of Compositions and Structure 28
4.2.1 Electron Probe Microanalysis (EPMA) 28
4.2.2 X-Ray Diffraction (XRD) and Grazing Incidence X-Ray Diffraction (GIXRD) 28
4.2.3 Field Emission Gun Scanning Electron Microscope (FEG-SEM) 29
4.2.4 Atomic Force Microscope (AFM) 29
4.3 Characterization of Mechanical Properties 30
4.3.1 Hardness and Young’s Modulus: Nanoindentation 30
4.3.2 Residual Stress: Laser Curvature and Average X-Ray Strain Methods 30
4.3.2.1 Laser Curvature Method (LCM) 30
4.3.2.2 Average X-Ray Strain (AXS) 33
Chapter 5 Results 34
5.1 Chemical Compositions and Structure 37
5.1.1 Chemical Compositions 37
5.1.2 Crystal Structure 37
5.1.3 Microstructure 40
5.1.4 Surface Roughness 42
5.2 Mechanical Properties 44
5.2.1 Hardness and Young’s Modulus 44
5.2.2 Residual Stress 44
Chapter 6 Discussion 48
6.1 The Difference of Measured Residual Stress: LCM vs XRD 48
6.2 Effect of TiN Sublayer on Residual Stress of TiZrN/TiN Bilayer Specimen 49
6.3 The Efficiency of Energy Relief by Ti Interlayer 51
6.3.1 Stored Elastic Energy and Energy Relief in the Bilayer TiZrN/Ti Coating 51
6.3.2 Stored Elastic Energy and Energy Relief in the Tri-layer TiZrN/TiN/Ti Coatings 51
6.3.3 The Maximum Plastic Work of Ti and Efficiency of Energy Relief 52
6.4 The Extent of Stress and Energy Relief by Ti/TiN Architected Interlayer 55
Chapter 7 Conclusions 58
References 59
Appendix A 2D AFM Images 67
Appendix B High-γ GIXRD Plots 68
Appendix C AXS Linear Regression Fitting 71

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