本研究目的是利用內能致裂法量測氮氧化鋯硬膜的破裂韌性並探討氧對於破裂韌性的影響。氮氧化鋯薄膜利用非平衡磁控濺鍍系統在四種不同氧流量以及固定的氮氣、氬氣流量下進行沉積。結果發現破裂韌性與織構相關，具有(111)織構之氮化鋯薄膜的破裂韌性為26.7±2.1 J/m2, 而具有(200)織構之氮化鋯薄膜則為9.0±0.9 J/m2。含有少許氮氧化鋯相之氮氧化鋯薄膜的破裂韌性介於 8.7±0.9到8.9±0.6 J/m2之間，其氮氧化鋯相可以降低作為裂縫前進驅動力的殘餘應力，使得臨界厚度上升，因而維持與具有(200)織構之氮化鋯相近的破裂韌性值。氧氣流以及氧含量都會影響氮氧化鋯薄膜的結構和伴隨的性質。氧氣流主要會干擾鋯吸附原子的遷移進而影響後續薄膜沉積，因此，氮氧化鋯薄膜的織構由(111)轉換成(200)，其電阻因氧氣流干擾造成結晶度的下降而上升。在氮氧化鋯薄膜中的氧含量隨著氧流量的上升而增加，由於在本實驗使用較低能量的鍍膜參數，因此氧化相的形成並不如先前研究顯著。薄膜斷面顯示主裂縫是階梯式成長而非表面散裂，原因是因為試片的邊緣應力遠大於縱深應力梯度產生的剪應力所致。

The objectives of this research were to measure the fracture toughness (Gc) of Zr(N,O) hard coatings using internal energy induced cracking (IEIC) method, and investigate the effect of oxygen on the fracture toughness of the Zr(N,O) coatings. Zr(N,O) coatings were deposited by unbalanced magnetron sputtering with different oxygen flow rates while maintaining constant nitrogen and argon flow rates. The results showed that Gc was texture dependent; for ZrN coatings with (111) texture was 26.7±2.1 J/m2 while that for coatings with (200) texture was 9.0±0.9 J/m2. The fracture toughness of Zr(N,O) coatings with small amount of zirconium oxynitride was between 8.7±0.9 and 8.9±0.6 J/m2. The oxynitride could decrease the residual stress which was the driving force for crack propagation, and thereby allowing the critical thickness to increase. Therefore, the fracture toughness remained nearly the same as that of ZrN with (200) texture. Both oxygen flow and oxygen contents were found to affect the structure and the accompanying properties of the Zr(N,O) coatings. Oxygen flow mainly disturbed the migration of Zr adatoms and the subsequent film formation; consequently, the texture of Zr(N,O) films switched from (111) to (200), and the electrical resistivity increased because of the decrease of crystallinity due to the effect of oxygen flow. The oxygen contents of the Zr(N,O) films increased, but not substantially, with increasing oxygen flow rate. Since lower energy processing parameters were used in this study, the formation of oxide or oxynitride phases was not as distinct as that in our previous studies. The fractography showed that the main crack propagated stepwise instead of by surface spallation, which could be due to the stress distribution in the specimen where the edge stress was much larger than the shear stress induced by the in-depth stress gradient.

摘要 i
Abstract ii
Content iii
List of Figures vi
List of Tables x
Chapter 1 Introduction 1
Chapter 2 Literature Review 3
2.1 Characteristics ZrN and Zr(N,O) 4
2.2 Preferred Orientation of ZrN 9
2.3 Measurement of Fracture Toughness 10
2.3.1 Experimental Methods 10
2.3.2 Theoretical Calculation 19
Chapter 3 Theoretical Basis 21
3.1 Assumptions of the Fracture Model 21
3.2 Energy Release Rate Approach 22
3.3 Griffith’s Criterion Approach 25
Chapter 4 Experimental Details 29
4.1 Specimen Preparation and Deposition Process 29
4.2 Characterization for Composition and Structure 32
4.2.1 X-ray Photoelectron Spectroscopy (XPS) 32
4.2.2 Auger Electron Spectroscopy (AES) 34
4.2.3 X-ray Diffraction (XRD) and Grazing Incident X-ray Diffraction (GIXRD) 34
4.2.4 Field-Emission Gun Scanning Electron Microscopy (FEG-SEM) and Dual beam (Focused Ion Beam & Electron Beam) System (FIB/SEM) 35
4.2.5 Atomic Force Microscopy (AFM) 36
4.3 Characterization for Properties 36
4.3.1 Hardness and Young’s Modulus 36
4.3.2 Residual Stress 37
4.3.2.1 Laser Curvature Method 37
4.3.2.2 XRD cos2αsin2ψ Method and Layer-by-layer Method 38
4.3.3 Fracture Toughness Measurement 42
4.3.4 Electrical Resistivity 42
Chapter 5 Results 45
5.1 Chemical Compositions 49
5.2 Crystal Structure and Texture 52
5.3 Microstructure 55
5.4 Surface Roughness 60
5.5 Fracture Topography 63
5.6 Mechanical Properties 69
5.6.1 Residual Stress 70
5.6.2 Hardness and Young’s Modulus 75
5.6.3 Stored Energy and Fracture Toughness 75
5.7 Electrical Resistivity 78
Chapter 6 Discussion 80
6.1 Effect of Oxygen on Structure and Properties of Zr(N,O) Thin Films 80
6.1.1 Oxide Phase Formation 80
6.1.2 Switch of Preferred Orientation 81
6.1.3 Compositional Variation and Distribution with Different Oxygen Flow Rates 83
6.1.4 Effect of Oxygen on Electrical Resistivity 84
6.2 Fracture Toughness of ZrN and Zr(N,O) Thin Films 87
6.2.1 Effect of Preferred Orientation and Oxynitride on the Fracture Toughness of ZrN and Zr(N,O) Thin Films 87
6.2.2 Critical Stored Energy vs. Critical Stress Intensity Factor 89
6.2.3 Fracture Pattern and Uncertainty of Fracture Toughness 90
6.3 Hardness and Residual Stress 93
Chapter 7 Conclusions 97
References 98
Appendix A Deconvoluted Results of XPS Spectra 105
Appendix B The XRD & GIXRD Patterns 110
Appendix C SEM Images 114
Appendix D XRD cos2αsin2ψ 122

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