臺灣博碩士論文加值系統

Ti-Si-N films were deposited on P-type (100) Si wafers using unbalanced magnetron sputtering (UBMS) at different deposition durations. The purposes of this study were to investigate the mechanical properties of Ti-Si-N films with different thickness, especially the hardness and residual stress, and to prepare Ti-Si-N films with high hardness and large thickness suitable for industrial applications. The thickness of the thin films increased with increasing deposition time ranging from 281 to 2044 nm. The structure of the nanocomposite coatings characterized by X-ray diffraction (XRD) showed that the crystalline phase was TiN with (200) or (111) preferred orientation depending on thickness. The results of X-ray photoelectron spectroscopy (XPS) indicated the existence of Si3N4 bonding in the nanocomposites. Therefore, the Ti-Si-N films were TiN/SiNx nanocomposite. Nanocomposite specimen with a good combination of hardness and thickness was obtained, where the hardness was 37 GPa with a thickness of 2 mm. Optical laser curvature method and modified XRD sin2ψ method were used to measure the average residual stress and stress of TiN phase in the nanocomposite, respectively. The results indicated that the amorphous SiNx in the TiN/SiNx nanocomposite could significantly relieve the average residual stress ranging from 19 to 68%. The degree of stress relief increased with increasing film thickness, which may be the reason that the thickness of nanocomposite can reach 2 mm. From the calculation of fracture mechanics, the critical residual stress leading to delamination for each specimen decreases as the film thickness increases. When measured stress reaches critical stress, the film starts to delaminate.

本實驗利用非平衡磁控濺鍍系統(UBMS)，於P 型(100)矽晶片上改變鍍膜時間以
製備鈦-矽-氮薄膜。此篇論文的目的為研究不同厚度下鈦-矽-氮薄膜的機械性質，特
別著重在殘留應力和硬度的部份，並且製備高硬度與高厚度的鈦-矽-氮薄膜以適合工
業應用。薄膜厚度隨著鍍膜時間的增加而上升，從281 nm 上升至 2044 nm。結構上藉
由X 光繞射 (XRD) 的測定得知，氮化鈦的優選方向為(111)方向或是(200)方向是取決
於厚度。而藉由X 光光電子儀 (XPS) 的測定得知在此複合材料裡有氮化矽的鍵結存
在。因此，在此實驗中的鈦-矽-氮薄膜為氮化鈦/氮化矽奈米複合材料。這些奈米複合
材料試片的硬度和膜厚達成了一個很好的結合，在硬度上達到37 GPa，而膜厚也達到
了2 μm。 利用雷射光學曲率及X 光繞射之改良式 sin2ψ 的方法可個別量測薄膜的平
均殘留應力，及氮化鈦相的應力。在氮化鈦/氮化矽奈米複合材料裡的非晶氮化矽可以
有效的釋放平均殘留應力，其範圍分別從19% 到68%。釋放殘留應力的程度隨著厚度
的上升而提高，此現象可能是奈米複合材料厚度可以到達2 μm 以上的主因。經由破裂
力學計算得知，薄膜可承受之臨界應力隨著膜厚增加而下降。當量測之真實應力達到
臨界應力計算值時，薄膜會開始剝落。

Contents
誌謝 ..i
摘要 iii
Abstract iv
Contents v
List of Figures vii
List of Tables viii
Chapter 1 Introduction 1
Chapter 2 Literature Review 3
2.1 Deposition Methods 3
2.2 Characteristics of TiN/Si3N4 Nanocomposites 4
2.2.1 TiN 4
2.2.2 Si3N4 4
2.2.3 TiN/Si3N4 Nanocomposites 4
2.3 The Origin of High Hardness of TiN/Si3N4 Nanocomposites 5
2.3.1 The Hardening Mechanism 6
2.3.2 The Roles of Interfacial Si3N4 Phase and Si Content 6
2.3.3 Influence of Impurity 7
2.4. The Applications of TiN/Si3N4 Nanocomposites 8
Chapter 3 Experimental Details 15
3.1 Specimen Preparation and Coating Process 15
3.2 Characterization Methods for Structure and Compositions 18
3.2.1 Field-Emission Gun Scanning Electron Microscopy (FEG-SEM) 18
3.2.2 X-Ray Diffraction (XRD) and Grazing Incidence XRD (GIXRD) 18
3.2.3 X-Ray Photoelectron Spectroscopy (XPS) 19
3.2.4 Auger Electron Spectroscopy (AES) 20
3.2.5 Rutherford Backscattering Spectroscopy (RBS) 20
3.3 Characterization Methods for Properties 20
3.3.1 Hardness and Roughness 20
3.3.2 Electrical Resistivity 21
3.3.3 Coloration and Reflectance 23
3.3.4 Residual Stress 25
3.3.4.1 Optical Method 25
3.3.4.2 Modified XRD sin2ψ Method 27
Chapter 4 Results 28
4.1 Compositions 28
4.1.1 XPS 28
4.1.2 Rutherford Backscattering Spectroscopy (RBS) 29
4.2 Structure 40
4.2.1 SEM microstructure 40
4.2.2 X-ray diffraction (XRD) 40
4.2.3 Grazing Incidence XRD (GIXRD) 41
4.2.4 Auger Electron Spectroscopy (AES) 41
4.3 Properties 49
4.3.1 Hardness 49
4.3.2 Roughness 49
4.3.3 Residual stress 51
4.3.4 Color and Reflectance 51
4.3.5 Electrical Resistivity 52
Chapter 5 Discussion 58
5.1 Hardness 58
5.2 Effect of Texture in TiN Phase on Hardness 61
5.3 Residual stress 62
References 70
Appendix A XPS deconvolution 75
Appendix B Surface morphology 84

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