本研究的目的在於探討金屬介層之設計對於雙層硬膜應力釋放的影響。我們提出以能量觀點的物理模式去探究金屬介層如何釋放硬膜中的應力。此模式的概念是金屬介層所作之塑變功，等於在鍍層內和藉由基材曲率緩解而釋放的儲存能。在模式中我們提出有效變形厚度用來評估特定種類介層之設計對於鍍層能量釋放的效果。本研究選擇具有鈦，鈦鋯和鈦鋯/鈦介層的氮化鈦鋯鍍層作為模型系統，並使用非平衡磁控濺鍍沉積鍍層在矽基板上。整個試片的應力和氮化鈦鋯鍍層內的應力分別由曲率法和結合奈米壓痕的平均X光應變法來量測。實驗結果顯示介層的塑性變形並不會在其整個厚度發生，只會在靠近氮化鈦鋯/介層的介面附近有變形。也就是說介層的有效變形厚度不會隨著介層厚度增加而增加，因而增加金屬介層厚度並不能有效地提高鍍層的應力釋放量。此外，由於高強度係數(k)的金屬塑性變形較困難，使用高強度係數且相同厚度的金屬介層，將會降低鍍層內的能量釋放。然而使用適當的介層厚度，高強度係數介層可以作為傳遞應力到矽基材之渠道。因此，使用適當鈦鋯/鈦比例厚度組合的介層，就可以將鍍層內的應力通過鈦鋯傳遞到鈦，可顯著增加鈦的有效變形厚度，因而降低更多鍍層內的能量。

The purpose of the study was to investigate the effect of metal interlayer design on the stress relief of bilayer hard coatings. We proposed an energy-based physical model to explore the stress relief in hard coating by metal interlayer. The model was based on the concept that the stored energy relief from the coating (ΔGf) and the relaxation of substrate curvature (ΔGSi) was equal to the plastic work undertaken by the metal interlayer. A parameter named effective deformation thickness (EDT) was used to evaluate the energy relief with a specific type of interlayer for different interlayer design. TiZrN coatings with Ti, TiZr and TiZr/Ti interlayers were selected as the model system. The specimens with 200 and 400 nm interlayers were deposited on Si substrate using unbalanced magnetron sputtering. The overall stress of the specimen and layer stress of TiZrN were measured by wafer curvature method and average X-ray strain combined with nanoindentation methods, respectively. The experimental results showed that increasing the metal interlayer thickness may not be an effective way on increasing stress relief efficiency in the coating. Since plastic deformation of the interlayer cannot occur in the entire thickness but only in part of the interlayer near the TiZrN/interlayer interface, defined as EDT, the EDT does not substantially increase with the interlayer thickness. In addition, plastic deformation of metal interlayer with high strength coefficient (k) is more difficult to occur by the stress transferred from the coating. Therefore, ΔGf may decrease by using high-k interlayer with the same thickness. However, the high-k interlayer can act as a channel to convey the stress to the Si substrate, if proper interlayer thickness is used. By using TiZr/Ti composite interlayer with proper thickness combination, significant amount of stress can be transmitted through TiZr to Ti, thereby increasing the EDT in Ti, and hence larger ΔGf can be attained compared with that using Ti interlayer with the same thickness.

致謝 i
摘要 ii
Contents iv
List of Figures vi
List of Tables vii
Chapter 1 Introduction 1
Chapter 2 Literature Review 3
2.1 The Origin of Stress in Thin Film 3
2.2 Effect of Metal Interlayer on the Stress Relief of Thin Films 3
2.3 Characteristics of TiZrN 6
2.3.1 Structure of TiZrN 6
2.3.2 Properties of TiZrN 6
2.4 Nondestructive Residual Stress Measurement in Thin Films 7
2.4.1 Wafer Curvature Method (WCM) 7
2.4.2 Grazing Incidence XRD cos2αsin2ψ Method 8
2.4.3 Average X-ray Strain (AXS) Method 11
2.5 The Stored Elastic Energy in Hard Coatings 11
Chapter 3 Theoretical Basis 13
3.1 Relief of Stored Elastic Energy in Coating and Si 13
3.2 Yield Strength and Plastic Work of a Metal Interlayer under Equi-biaxial Stress State 14
Chapter 4 Experimental details 18
4.1 Substrate Preparation and Sample Deposition 18
4.2 Characterization for Compositions and Structure 23
4.2.1 Compositions 23
4.2.2 Crystal Structure 23
4.2.3 Cross-sectional and Surface Morphology 24
4.2.4 Surface Roughness 24
4.3 Characterization for Properties 24
4.3.1 Hardness and Young’s Modulus 25
4.3.2 Residual Stress 25
4.3.2.1 Laser Curvature Measurement 25
4.3.2.2 XRD cos2αsin2ψ Method 26
Chapter 5 Results 28
5.1 Chemical Compositions and Structure 31
5.1.1 Chemical Compositions 31
5.1.2 Crystal Structure 31
5.1.3 Microstructure 34
5.1.4 Roughness 34
5.2 Properties 37
5.2.1 Hardness and Young’s Modulus 37
5.2.2 Residual Stress 37
Chapter 6 Discussion 42
6.1 Energy Relief and Stress Relief 42
6.2 Effect of Interlayer Thickness on Energy Relief 45
6.3 Effect of Strength Coefficient (k) of Interlayer on Energy Relief 46
6.4 Effect of Composite Interlayer (TiZr/Ti) on Energy Relief 48
6.5 Effective Deformation Thickness of Coating (EDTf) and Si (EDTSi) 50
Chapter 7 Conclusions 53
Reference 54
Appendix A AXS Linear Regression Fitting 60

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