本論文的研究目的是使用高功率脈衝磁控濺鍍系統(HPPMS)製備不含有釩金屬相之氮化釩鍍層，並且藉由調控佔空比改善鍍層結構與性質。此外，為了防止氮化釩鍍層之氧化，本研究引入氮化鈦覆蓋層，並且探討覆蓋層對氮化釩鍍層機械與磨潤性質之影響。試片製備於矽與AISI D2鋼基材上並鍍製300奈米氮化鈦覆蓋氮化釩鍍層。結果顯示降低佔空比至3%，能夠製備具有光滑表面之緻密鍍層，表示電漿能量的增加比伴隨而來的離子撞擊效應對成膜有更顯著的影響。D2鋼的試片上的氮化釩具有(200)織構，而矽基板試片則呈現較弱之(200)與隨機織構，這可能是因為D2鋼試片之離子穿隧效應比矽基板試片更顯著。磨耗試驗的結果顯示所有鍍層的磨耗率都極低僅有0.1×10-6 mm3N-1m-1，其原因可能是磨耗試驗過程中氮化釩會產生自潤滑之氧化相，而氧化相主導並顯著提高鍍層之耐磨性。留在磨道上的氮化鈦碎屑可能會增加氮化釩鍍層之摩擦係數，但添加氮化鈦覆蓋層對氮化釩鍍層之耐磨性沒有影響，因此氮化鈦覆蓋層可以作為裝飾性之保護鍍層。另外，利用光學曲率法與平均應變法測量之氮化釩鍍層殘餘應力顯示出很大的差距，我們提出了循環功率誘發疲勞(PCIF)之機制來解釋此差距。由於HPPMS製程中的循環功率可能會引起作用於矽基材之交替彎曲負載，導致矽基板試片上產生高週疲勞裂縫成長，因而緩解矽基材彎曲，並降低整體殘餘應力。

The purposes of this study were to produce VN coatings without retained vanadium (V) metal phase using high power pulsed magnetron sputtering (HPPMS), by which structure and properties of the coatings could be improved by controlling duty cycle. Moreover, to prevent the VN coatings from oxidation in the ambient air, a TiN capping layer was introduced on the VN coating and the effect of capping layer on mechanical and tribological properties of the bilayer VN coatings was investigated as well. The specimens were deposited on Si and D2 steel substrates with or without TiN capping layer. Denser VN coatings with smoother surface could be produced with decreasing duty cycle from 9 to 3%, indicating that the increase in energy of the plasma species by the HPPMS process played a more significant effect than the accompanying ion-peening. The VN coatings on D2 steel showed (200) texture and the coatings on Si presented less (200) or nearly random texture, which could be attributed to the more significant ion channeling effect on the specimens on D2 steel than that on Si substrate. All VN coatings prepared by HPPMS with or without TiN capping layer showed extremely low wear rate of 0.1×10-6 mm3N-1m-1. The self-lubricating vanadium oxides formed by tribochemical reaction or exposing to the ambient air could dominate and significantly enhance the wear resistance of VN coatings. Adding a TiN capping layer did not significant affect the wear rate of VN coatings, although the friction coefficient of VN may be increased by the TiN debris left on the wear track. Therefore, the TiN capping layer can serve as a decorative and protective coating. The results showed a large deviation between the residual stresses measured by LCM and AXS methods for the specimens on Si substrate. A power-cycle induced fatigue (PCIF) mechanism was proposed to explain the deviation, where alternating bending load caused by the power cycle of HPPMS process may induce high-cycle fatigue crack growth on the Si substrate, thereby relaxing the curvature of the substrate and decreasing the overall residual stress.

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 VN.....................................3
2.2 Fracture Toughness of VN..................................5
2.3 Self-lubricating Property of VN...........................6
2.4 Tribological Behavior.....................................8
2.4.1 Adhesion Strength.......................................8
2.4.2 Wear Resistance.........................................9
2.5 High Power Pulsed Magnetron Sputtering (HPPMS)...........11
2.6 Effects of Process Parameters............................12
2.6.1 Nitrogen Flow Rate.....................................12
2.6.2 Duty Cycle and Average Power of HPPMS..................13
Chapter 3 Experimental details...............................15
3.1 Substrate Preparation....................................15
3.2 Deposition Procedures....................................15
3.2.1 High Power Pulsed Magnetron Sputtering (HPPMS).........20
3.2.2 Monitoring of HPPMS....................................20
3.3 Characterization Methods for Structure and Compositions..20
3.3.1 Compositions...........................................20
3.3.2 Compositional Depth Profiles...........................22
3.3.3 Compositions within wear tracks........................22
3.3.4 Crystal Structure......................................22
3.3.5 Cross-sectional Microstructure and Surface Morphology..24
3.3.6 Surface Roughness......................................24
3.4 Characterization Methods for Properties..................25
3.4.1 Hardness and Young’s modulus...........................25
3.4.2 Residual Stress........................................25
3.4.3 Electrical Resistivity.................................27
3.4.4 Adhesion Strength......................................28
3.4.5 Wear Resistance........................................30
Chapter 4 Results............................................32
Part I: Peak Power Density and Plasma Compositions..............32
4.1 Peak Power Density.......................................32
4.2 Plasma Compositions......................................34
Part II: Specimens deposited on Si substrates...................36
4.3 Chemical compositions and Structure......................36
4.3.1 Chemical Compositions..................................36
4.3.2 Crystal Structure......................................36
4.3.3 Microstructure.........................................42
4.3.4 Surface Roughness......................................42
4.4 Properties...............................................45
4.4.1 Hardness, Young’s modulus and Electrical Resistivity...45
4.4.2 Residual Stress........................................45
Part III: Specimens deposited on D2 steel substrates............48
4.5 Chemical Compositions and Structure......................48
4.5.1 Chemical Compositions..................................48
4.5.2 Crystal Structure......................................51
4.5.3 Microstructure.........................................54
4.5.4 Surface Roughness......................................55
4.6 Properties...............................................57
4.6.1 Hardness and Young’s modulus...........................57
4.6.2 Residual Stress........................................59
4.6.3 Adhesion Strength......................................61
4.6.4 Wear Resistance........................................63
Chapter 5 Discussion.........................................72
5.1 Effect of Duty Cycle.....................................72
5.1.1 Deposition and Texture Evolution on Si and D2 Steel....72
5.1.2 Properties of VN Coatings..............................75
5.2 Tribological Behavior....................................75
5.2.1 Wear Resistance........................................75
5.2.2 Role of TiN Capping Layer..............................77
5.3 Residual Stress..........................................78
5.3.1 Power-Cycle Induced Fatigue (PCIF).....................78
5.3.2 Effect of TiN Capping Layer on Residual Stress.........82
Chapter 6 Conclusions........................................85
Reference.......................................................86
Appendix A Optical Emission Spectra..........................93
Appendix B XPS Spectra.......................................95
Appendix C 2D AFM Images.....................................98
Appendix D 2D profiles of wear tracks.......................100

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