研究目的為探討基板偏壓對於氮化鈦鋯薄膜結構與性質之影響，本實驗是利用非平衡磁控濺鍍法將奈米晶氮化鈦鋯 (TiZrN) 薄膜鍍著於(100)矽晶片上，並且應用不同的基板偏壓，範圍由－35V至－150V，實驗結果指出，所有的試片都存在高強度的(111)織構。在本研究中，我們發現當基板偏壓超過－35V以上，氮化鈦鋯薄膜的性質會顯著的改善，在－40V至－120V之間，氮化鈦鋯薄膜保持著優良的性質，包含：高硬度、高輝度、低電組及平坦的表面。在此區間，氮化鈦鋯薄膜的平均硬度為35.5 GPa，平均電阻為33.5μΩ-cm、輝度達到80以上而且薄膜粗糙度介於0.5nm至0.6nm之間。在大範圍的應用偏壓中，氮化鈦鋯薄膜保持優良的性質，這指出製程參數範圍非常廣。然而當基板偏壓達到－150V，有結構損傷以及薄膜剝落的現象發生，透過拉塞福背向散射分析儀(RBS)的結果與掃描式電子顯微鏡(SEM)也可以驗證此結構損傷現象。對於保護鍍附層，必須要有低的殘餘應力來防止薄膜剝落，藉由控制基板偏壓可以將殘餘應力控制在較低的值。在此研究中隨著基板偏壓由－65V下降至－35V，殘餘應力逐漸下降，在低偏壓－40V和－45V時，氮化鈦鋯薄膜可以同時獲得高硬度以及較低的殘餘應力，硬度與殘餘應力分別為33.4～34.5GPa和－2.7～－3.7GPa。

The objective is to investigate the substrate bias effect on the structure and properties of the TiZrN thin films. The TiZrN thin films were deposited by DC unbalanced magnetron sputtering system (UBMS) with dual guns (Ti,Zr) targets onto Si (100) substrates at different substrate bias ranging from －35V to －150V. Experimental results indicated that all the specimens have strong (111) texture in XRD patterns. In this study, we discovered a transition bias of －35 V, above which a significant improvement of properties was found, including high hardness, excellent brilliance, low resistivity and fine surface morphology. Within the bias range of －40 to －120 V, the hardness of TiZrN films is around 35.5 GPa, the resistivity is about 33.5μΩ-cm, and the brilliance is larger than 80. The roughness is between 0.5 nm and 0.6 nm. The TiZrN films maintain excellent properties through a large range of applying bias, indicating that the process window is considerable wide. However, structure damage and thin film delamination were found when substrate bias reached －150V. The RBS result and SEM image further support the structure damage at －150 V. For protective coatings, low residual stress is required to avoid delamination. By adjusting substrate bias, residual stress can be controlled to lower value. In this study, the residual stress of TiZrN films gradually decreases with decreasing the substrate bias ranging from －65V to －35V. The TiZrN thin films with high hardness, lower residual stress could be obtained simultaneously at low substrate bias of －40V and －45V, the hardness and residual stress are 33.4～34.5GPa and －2.7 ～－3.7GPa, respectively.

Contents
摘要 i
Abstract ii
致謝 iii
Contents v
List of Figures viii
List of Tables……………………………………………………………............................................. v
Chapter 1 Introduction 1
Chapter 2 Literature Review 2
2.1 Unbalance magnetron sputtering system (UBMS) 2
2.2 Characteristics of transition metal nitride (TiN and ZrN) 3
2.3 Characteristics of TiZrN 6
2.4 Effect of substrate bias on thin films 9
2.5 Low substrate bias voltage applied in hard coating 12
Chapter 3 Experimental Details 13
3.1 Experimental Apparatus and Specimen Preparation 13
3.2 Characterization Methods 17
3.2.1X-ray photoelectron spectroscopy (XPS) 17
3.2.2 X-ray diffraction (XRD) 17
3.2.3 Glancing Incidence X-ray diffraction (GIXRD) 18
3.2.4 Field emission gun scanning electron microscopy (FEG-SEM) 19
3.2.5 Atomic Force Microscopy (AFM) 19
3.2.6 Rutherford backscattering spectroscopy (RBS) 19
3.3 Characterization Methods for Properties of TiZrN films 20
3.3.1Resistivity (Four-point probe) 20
3.3.2Hardness (Nanoidentation) 22
3.3.3 Laser Curvature Method (Residual Stress) 22
3.3.4 Coloration 24
Chapter 4 Results 25
4.1 Structure 25
4.1.1 Chemical Compositions (XPS) 25
4.1.2 N/(Ti+Zr) ratio and Packing Factor (RBS) 25
4.1.3 XRD 30
4.1.4 GIXRD 35
4.1.5 SEM 38
4.1.6 AFM 43
4.2 Properties 44
4.2.1 Hardness 44
4.2.2 Residual stress 45
4.2.2 Resistivity 46
4.2.2 Coloration 47
Chapter 5 Discussion 49
5.1 Nanostructure of TiZrN 49
5.2 Properties of TiZrN 52
5.2.1 Residual stress 52
5.2.2 Hardness 53
5.2.4 Coloration 58
5.3 Summary of effect bias 60
Chapter 6 Conclusions 61
References 62
Appendix A The XPS deconvolution spectra 70
Appendix B The GIXRD patterns 79
Appendix C AFM-3D images 83
Appendix D RBS results 85

List of Figures
Fig. 2.1 The structure diagram of TiN and ZrN 4
Fig. 2.2 The binary phase diagram of Ti-N system 5
Fig. 2.3 The binary phase diagram of Zr-N system 5
Fig. 2.4 Result of the XRD pattern for the TiZrN(200), TiN(200) and ZrN(200). 7
Fig. 2.5 The XRD patterns of TiZrN films with different gun power of Zr target 8
Fig. 2.6 The XRD patterns for all samples with the nitrogen flow rate ranging from 0 to 2.5 sccm 8
Fig. 2.7 The surface structures of TiN films with different substrate bias. 10
Fig. 2.8 Schematic diagram of <220> channeling direction 11
Fig. 2.9 Potentiodynamic polarization curves of TiN coated and uncoated samples were carried out in 3.5% NaCl 11
Fig.2.10 The variation of residual stress and hardness of TiAlN films with different bias 12
Fig. 3.1 Schematic diagram of the UBMS system 14
Fig. 3.2 The experimental flow chart 16
Fig. 3.3 Schematic diagram of four-point probe. 21
Fig. 3.4 Schematic diagram of the laser curvature system. 23
Fig. 3.5 Schematic diagram of the L*a*b* color space 24
Fig. 4.1 The XPS deconvolution spectra of (a) Ti-2p peak (b) Zr-3d peak of B75 sample 26
Fig. 4.2The XPS deconvolution spectra of (c) N-1s peak (d) O-1s peak of B75 sample 27
Fig. 4.3 The RBS spectrums of TiZrN films (a) B35 (b) B75 28
Fig. 4.4 The packing factor of the TiZrN films with respect to substrate negative bias. 29
Fig. 4.5 The X-ray diffraction patterns of samples B35~B150 33
Fig. 4.6 The grain size of the TiZrN films with respect to substrate negative bias. 34
Fig. 4.7 The FWHM with respect to substrate negative bias. 34
Fig. 4.8 The GIXRD patterns of (a) B35 (b) B75 (c) B150 specimens 37
Fig. 4.9 The cross-sectional images of the TiZrN films for all samples 40
Fig. 4.10 The SEM surface image of TiZrN films deposition with different substrate bias：B35, B40, B85 and B150 41
Fig. 4.11 The SEM surface image of B150 specimen：partial region delamination 42
Fig. 4.12 The deposition rate of TiZrN films with respect to substrate negative bias. 42
Fig. 4.13 The 3D surface images of B35, B40, B85 and B150 by AFM 43
Fig. 4.14 Hardness of TiZrN films with respect to substrate negative bias. 44
Fig. 4.15 The residual stress of TiZrN films with respect to substrate negative bias. 45
Fig. 4.16 The electrical resistivity of TiZrN films with respect to substrate negative bias 46
Fig. 4.17 The variation of color with different substrate bias 48
Fig. 5.1 The residual stress and hardness with respect to substrate bias 53
Fig. 5.2 The variation surface area of contact with different grain size. 56
Fig. 5.3 The resistivity of the TiZrN films with respect to packing factor. 58
Fig. 5.4 The relationship between incident light and roughness of thin films 59
Fig. A.1 The XPS deconvolution spectra of B35 specimen 70
Fig. A.2 The XPS deconvolution spectra of B40 specimen 71
Fig. A.3 The XPS deconvolution spectra of B45 specimen 72
Fig. A.4 The XPS deconvolution spectra of B55 specimen 73
Fig. A.5 The XPS deconvolution spectra of B65 specimen 74
Fig. A.6 The XPS deconvolution spectra of B85 specimen 75
Fig. A.7 The XPS deconvolution spectra of B95 specimen 76
Fig. A.8 The XPS deconvolution spectra of B120 specimen 77
Fig. A.9 The XPS deconvolution spectra of B150 specimen 78
Fig. B.1 The GIXRD patterns of B35, B40 and B45 samples 79
Fig. B.2 The GIXRD patterns of B55-B75 samples 80
Fig. B.4 The GIXRD patterns of B85-B120 samples 81
Fig. B.5The GIXRD patterns of B150 sample 82
Fig. C.1 The AFM 3D images of sample B35-B65 83
Fig. C.2 The AFM 3D images of sample B75-B150 84
Fig. D.1 The RBS results of B35-B65 samples 85
Fig. D.2 The RBS results of B75-B150 samples 86

List of Tables
Table 2.1 Summary of characteristics of TiN and ZrN 3
Table 3.1 The deposition condition of TiZrN with various substrate bias 15
Table 3.2 The deposition condition of TiZrN thin films 15
Table 3.3 The correction factor at different ds 21
Table 4.1 Summary of the experimental results. 31
Table 5.1 The residual stress, grain size and hardness at different substrate bias. 56
Table 5.2 The roughness and brilliance at different substrate bias 59
Table 5.3 Effect of substrate bias for TiZrN thin films in different regions 60

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