本研究之目的為探討鋯介層對於上方氮化鋯薄膜殘留應力之影響。並判斷含鋯介層之氮化鋯薄膜之可用性，從過去研究發現鍍覆在矽基材或其他冶金基材之金屬介層可以大幅釋放上方薄膜之殘留應力並改善薄膜之附著性，並且在工業上介層厚度往往控制在50至300奈米之間，然而，很少文獻精確地分別計算上層薄膜與金屬介層之殘留應力。本研究中，利用兩種非破壞性方法分別量測雙層薄膜中各自地殘留應力以及整體殘留應力，光學曲率法量測整體薄膜之平均殘留應力；新開發之X光平均應變量測法結合奈米壓印法可準確地分別量測上層氮化鋯薄膜以及鋯介層之殘留應力，根據整體之平均應力以及上層氮化鋯薄膜與鋯介層各自地應力，並可以量化鋯介層對於上方氮化鋯薄膜應力釋放之程度，由結果可以得知，鋯介層可以大幅釋放上層氮化鋯薄膜之殘留應力，然而，卻發現在Z12, Z22, Z23以及Z33試片中超過一半之試片發生脫膜現象。因此，可以認定鋯介層無法改善上方氮化鋯薄膜之附著性，此脫膜現象是由其儲存能大於介面破裂韌性而導致，另外，觀察到氮化鋯薄膜與鋯介層間之介面破裂韌性遠遠小於單層氮化鋯薄膜破裂韌性，並且估計出其介面破裂韌性為約2.8J/m2，因此我們可以判定，薄膜內殘留應力大小對於含鋯介層之氮化鋯薄膜的附著性僅是間接因素，界面破裂韌性才是影響薄膜附著性的最主要原因。

The purpose of this study was to investigate the effect of Zr interlayer on the residual stress of the upper ZrN thin film and to evaluate the usability of ZrN/Zr bilayer coatings. It is commonly acknowledged that using a metal interlayer can relieve the residual stress and enhance the adhesion of transition metal-nitride hard coatings on metallic or Si substrates. The interlayer thickness usually ranges from 50 to 300 nm. However, there were few studies on the separate measurement of stresses in the top coating and interlayer. In this study, two nondestructive stress measurement techniques were applied to obtain the residual stress in the entire bilayer specimen and the individual layers. The wafer curvature method was used to measure the bulk average stress of the specimen and a newly developed average X-ray strain (AXS) technique combining with nanoindentation was adopted in accurately determining the stresses in ZrN thin film and Zr interlayer, respectively. From the bulk average stress of the entire specimen and the stresses in ZrN coating and Zr interlayer, the extent of stress relief by Zr interlayer could be quantitatively revealed. The results showed that the Zr interlayer could significantly relieve the residual stress of the upper ZrN thin film, whereas delamination was found to occur in more than 50% of samples Z12, Z22, Z23 and Z33. Therefore, adding a Zr interlayer could not improve the adhesion of the top ZrN film. The delamination was due to the stored energy exceeding the interfacial fracture toughness of the ZrN/Zr interface. The interfacial fracture toughness was much lower than the fracture toughness of the monolayer ZrN thin film, and estimated to be about 2.8 J/m2. The residual stress of the film was an indirect factor for the delamination of bilayer specimen. The major factor that determined the adhesion of the bilayer ZrN/Zr coating was the interfacial fracture toughness of the ZrN/Zr interface.

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 of ZrN and coatings ............... 3
2.2 Measurement of residual stress .................... 5
2.2.1 Wafer curvature method .......................... 5
2.2.2 Grazing Incidence XRD Method .................... 6
2.2.3 The Averaged X-ray Strain (AXS) ................. 8
2.3 Effect of the metal interlayer on upper film ..... 10
2.4 Theoretical basis of the interfacial fracture toughness ............................................ 11
Chapter 3 Experimental Procedures .................... 16
3.1 Specimen Preparation and Deposition Process ...... 16
3.2 Characterization for structure and composition ... 20
3.2.1 Auger Electron Spectroscopy (AES) .............. 20
3.2.2 X-ray Photoelectron Spectroscopy (XPS) ......... 20
3.2.3 X-ray Diffraction (XRD) ........................ 21
3.2.4 Grazing Incidence X-ray Diffraction (GIXRD) .... 22
3.2.5 Field-Emission Scanning Electron Microscopy (FEG-SEM) and Dual Beam (focused ion beam & electron beam) System (FIB/SEM) ..................................... 22
3.2.6 Atomic Force Microscopy (AFM) .................. 23
3.3 Characterization for Properties .................. 23
3.3.1 Nano-indentation (NIP) ......................... 23
3.3.2 Optical Laser Curvature Method ................. 24
3.3.3 XRD cos2αsin2ψ method .......................... 26
3.3.4 Electrical Resistivity ......................... 27
3.3.5 Contact angle test ............................. 29
3.3.6 Measurement of the interfacial fracture toughness . ...................................................... 30
Chapter 4 Results .................................... 31
4.1 Chemical compositions ............................ 34
4.2 Crystal structure ................................ 37
4.3 Roughness ........................................ 39
4.4 Microstructure ................................... 41
4.5 Surface and Fracture Morphology .................. 43
4.6 Mechanical Properties ............................ 46
4.6.1 Hardness and young’s modulus ................... 46
4.6.2 Residual stress by laser curvature method (ORS)
...................................................... 47
4.6.3 X-ray residual stress (XRS) .................... 50
4.6.4 Electrical Resistivity ......................... 55
4.6.5 Contact angle test ............................. 57
Chapter 5 Discussion ................................. 58
5.1 Stress relief of bilayer ZrN/Zr specimens ........ 58
5.2 The delamination of specimens and interfacial fracture toughness ................................... 61
Chapter 6 Conclusions ................................ 71
Chapter 7 References ................................. 72
Appendix ............................................. 77
Appendix A. Deconvolution XPS spectra of samples ..... 77
Appendix B. The SEM image of the samples ............. 98
Appendix C. AXS regression line ...................... 99

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