本研究目的在於探討競爭成長理論於氮化釩薄膜織構演變之適用性以及織構對於薄膜機械性質之影響。考量到相似的原子排列，岩鹽結構的氮化釩(200)面可能會隨著BCC結構的釩金屬(110)模板成長，除了競爭成長機制之外，底材金屬的模板效應也可能是一個影響其氮化物織構的重要因子。對於有著(200)到隨機織構的氮化釩薄膜(區域I)，隨著氮氣流量的提升，氮化釩薄膜逐漸由(200)轉變為隨機織構。具有強烈(111)織構的氮化釩薄膜(區域II)則可透過提升氮氣流量和降低鍍膜溫度以及基板偏壓等低能量參數下製備。
區域I的薄膜微結構為具有緻密柱狀晶以及平滑表面的zone T結構，而區域II的薄膜微結構屬於具有鬆散的柱狀晶以及粗糙表面的zone I結構。在區域I的薄膜硬度均超過30 GPa且和織構關係不大，而區域II的硬度相當低且與織構相關，僅有5.7到11.4 GPa。區域I的殘留應力隨著(111)織構係數增加由-5.66 GPa降至-2.66 GPa，而區域II的殘留應力則因為鬆散的結構而大部分被釋放，其值落在-0.44 GPa到0.45 GPa。排除純(111)織構的試片，不足計量比的試片其電阻率均比計量比的試片高，此外鬆散的微結構也會造成電阻率提升。

The purposes of this study were to investigate the applicability of competitive growth theory on the texture evolution of VN thin films and the effect of texture on the mechanical properties of VN thin films. Considering the similarity of atomic configuration, the formation of (200) plane of VN (NaCl structure) may follow the (110) template in vanadium metal (BCC structure). In addition to the competitive growth theory, the template effect due to base metal may be an important factor for the texture evolution of the corresponding transition-metal nitrides. For the VN thin films with texture ranging from (200) to random (region I), the preferred orientation gradually changes from (200) to random texture with increasing nitrogen flow rate. VN thin films with (111)-dominant texture can be deposited with increasing nitrogen flow rate and under low energy conditions with low temperature and low substrate bias.
The microstructure of VN thin films and mechanical properties were divided into two regions according to texture coefficient. The film microstructure in region I belongs to zone T structure with dense columnar structure and smooth surface, while that in region II has zone I structure with loose columnar structure and rough surface. The film hardness of in region I is about 30 GPa and weakly texture-dependent, while that in region II is quite low and texture dependent ranging from 5.7 to 11.4 GPa. The residual stress of films in region I decreases from -5.66 to -2.66 GPa with increasing (111) texture coefficient, while that in region II is mostly relieved due to loose microstructure, ranging from -0.44 to 0.45 GPa. The electrical resistivity of the understoichiometric samples is higher than that of stoichiometric samples except for the sample with (111)-dominant texture. In addition, loose-packed microstructure also causes higher electrical resistivity.

摘要 i
Abstract ii
Content iii
List of Figures vi
List of Tables viii
Chapter 1 Introduction 1
Chapter 2 Literature Review 3
2.1 Deposition Method 3
2.2 Structure Zone Models 3
2.3 Characteristics of VN Thin Films 8
2.4 Superior Properties of VN 10
2.4.1 Self-lubricant Property of VN for High Temperature Wear Applications 10
2.4.2 Toughness Enhancement of VN-based Nitride 11
2.5 Theories of Texture Evolution 13
2.5.1 Overall Energy Model 13
2.5.2 Competitive Growth Theory 13
2.6 Effects of Process Parameters on Texture and Crystal Structure of VN Thin Films 15
2.7 Effect of Texture on Mechanical Properties 17
2.7.1 Hardness 17
2.7.2 Residual Stress 18
Chapter 3 Experimental Details 20
3.1 Specimen Preparation and Deposition Process 20
3.2 Characterization of Composition and Film Structure 24
3.2.1 Chemical Composition 24
3.2.2 Crystal Structure and Preferred Orientation 25
3.2.3 Cross-sectional Microstructure and Top-View Morphology 27
3.2.4 Surface Roughness and Morphology 27
3.3 Characterization of Film Properties 28
3.3.1 Hardness and Young’s Modulus 28
3.3.2 Residual Stress 28
3.3.3 Electrical Resistivity 30
3.3.4 Coloration 32
Chapter 4 Results 33
4.1 Chemical Compositions and Structure 33
4.1.1 Chemical Compositions 33
4.1.2 Cross-Sectional and Surface Morphology 35
4.1.3 Crystal Structure and Texture 37
4.1.4 Surface Roughness 40
4.2 Properties 42
4.2.1 Hardness and Young’s Modulus 42
4.2.2 Residual Stress 45
4.2.3 Electrical Resistivity 45
4.2.4 Coloration 46
Chapter 5 Discussion 48
5.1 Texture Evolution of VN Thin Films 48
5.1.1 The Formation of VN(200) Texture 48
5.1.2 The Formation of VN(111) Texture 52
5.2 Microstructure and Surface Morphology 53
5.3 Effect of Texture on Mechanical Properties 54
5.3.1 Effect of Texture on Hardness 54
5.3.2 Effect of Texture on Residual Stress 55
5.4 Electrical Resistivity 56
Chapter 6 Conclusions 58
Reference 59
Appendix A Deconvolution Results of XPS Spectra 67
Appendix B SEM Images 75
Appendix C AFM Images 77

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