本研究目的在於不使用金屬鈦介層，並藉由調整製程參數，在非平衡磁控濺鍍系統中沉積氮化鈦厚膜。主要控制參數之一是調整渦輪分子幫浦與鍍膜腔體間閘閥開口大小，其二是直接降低渦輪分子幫浦轉速；氮氣與氩氣則以固定比例隨之調整流量，以維持鍍膜製程中固定之工作壓力。本研究成功沉積出膜厚7微米且殘餘壓應力低於2 GPa的厚膜。大部分的試片都呈現隨機織構。氮鈦比例介於1.0-1.1之間。且硬度均介於23-27 GPa之間，不隨著厚度有著明顯改變。所有試片都有著相當低的電阻介於14~25 µΩ-cm。各系列試片之殘餘壓應力大致隨著厚度上升而下降。進一步分析膜厚7微米試片的應力梯度，發現殘餘壓應力會沿著厚度上下波動，此現象可能致使膜厚高達7微米而不會剝落，其原因可能是鍍膜過程中發生了應力釋放的機制。透過選擇適當的參數，在鍍膜過程中渦輪分子幫浦的消耗功率可以有效降低，並且可以延長其所需保養之時限。本研究中的製程參數範圍相當寬廣，對於工業應用相當有益。

The objective of this study was to deposit thick TiN film without using Ti interlayer by adjusting process parameters of unbalanced magnetron sputtering (UBMS) system. The controlling deposition parameter was either the opening of gate valve between turbomolecular pump (TP) and deposition chamber or the pumping speed of TP. The flux of argon and nitrogen was adjusted at a fixed ratio to maintain the same working pressure in the chamber. The results showed that TiN film with a thickness of 7 μm could be successfully deposited and the residual stress was less than -2 GPa.. From XRD pattern, most of samples were with random texture. The N/Ti ratios of all samples were ranged from 1.0 to 1.1. Nanoindentation data ranging from 23~27 GPa indicated that hardness of the films was not related to the film thickness. All samples exhibited low electrical resistivity ranging from 14 to 25 µΩ-cm. The compressive residual stress of the TiN coatings mostly decreased with thickness for all three series of specimens. The stress gradient of the sample with a thickness of 7 m showed that the residual stress was fluctuated along the thickness. This stress fluctuating behavior may enable the growth of TiN coating up to 7 μm without spallation. By selecting proper operational parameters, the energy consumption of TP during deposition could be reduced and the maintenance duration of TP could be prolonged as well. The processing window for depositing thick TiN coatings in this research was quite wide, which is beneficial to the industrial applications.

摘要 i
Abstract ii
致謝 iii
Content v
List of Figures vii
List of Tables ix
Chapter 1 Introduction 1
Chapter 2 Literature Review 3
2.1 Characteristics of TiN…………………………………………………………… 3
2.2 Deposition of Thick TiN Coatings with and without Ti interlayer…………… 6
2.3 Effect of Deposition Parameters………………………………………………... 7
2.4 Change of Texture with Thickness……………………………………………… 10
Chapter 3 Experimental Details 15
3.1 Substrate Preparation…………………………………………………………… 15
3.2 Coating Process………………………………………………………………….. 15
3.3 Characterization methods for structure and composition……………………. 18
3.3.1 Field-Emission Gun Scanning Electron Microscopy (FEG-SEM)…….. 18
3.3.2 X-Ray Photoelectron Spectroscopy (XPS)……………………………… 18
3.3.3 X-Ray Diffraction (XRD) and Glancing Incidence XRD (GIXRD)…... 18
3.3.4 Atomic Force Microscopy………………………………………………... 19
3.4 Characterization Methods for Properties……………………………………… 19
3.4.1 Hardness………………………………………………………………….. 19
3.4.2 Residual Stress: Laser curvature method………………………………. 20
3.4.3 Residual Stress: XRD cos2αsin2y method………………………………. 22
3.4.4 Layer-by-Layer Method………………………………. ………………... 23
3.4.5 Electrical resistivity………………………………………………………. 24
3.4.6 Coloration………………………………. ……………………………….. 26
Chapter 4 Results 27
4.1 Structure and Chemical Compositions………………………………………… 27
4.2 Properties………………………………. ……………………………………….. 40
4.3 Energy Consumption of Turbomolecular Pump………………………………. 44
Chapter 5 Discussion 46
5.1 Stress Gradient in TiN Coating…………………………………………………. 46
5.2 Processing Parameters for Depositing Thick TiN Films……………………… 47
5.3 Energy Saving During Deposition……………………………………………… 51
Chapter 6 Conclusions 52
References 53
Appendix A The GIXRD patterns 61
Appendix B The Fitting Curves of Lattice Constant 63
Appendix C Surface Morphology 66
Appendix D Calculations about Gas Flow data 69
Appendix E Fracture Toughness 70

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