在本研究，我們提出一個標準流程用平均X光應變方法去測量多晶氮化鈦鋯薄膜的殘餘應力。本研究目的是降低應力量測誤差到十百分比，並找出X光繞射及奈米壓印法的厚度限制。此外，成分對氮化鈦鋯薄膜之殘餘應力的影響也會被探討。八組不同成分及厚度的氮化鈦鋯藉由非平衡磁控濺鍍系統鍍在矽基材(100)上。薄膜的應變被cos2αsin2ψ X光繞射在眾多旋轉角中量測。奈米壓印法測量氮化鈦鋯薄膜的楊氏係數。從應變和cos2αsin2ψ作圖得到的斜率，我們可以得到平均X光應變。為了驗證測量的應力，合併平均X光應變及奈米壓印法得到的應力和光學曲率應力比較並算出誤差。實驗結果顯示壓縮應力範圍在2.69到5.10GPa，在鋯/(鋯+鈦)為0.75到達最大值。在鋯/(鋯+鈦)=0.5的壓縮應力可能會因為晶格缺陷減少隨厚度增加而下降。不同的成分在氮化鈦鋯中會導致殘餘應力的不對稱變化。殘餘應力的不對稱行為可能是因為鈦在氮化鋯晶格以及鋯在氮化鈦晶格的原子大小差異所造成。在本研究，X光繞射應力量測誤差成功地降低到九點二百分比。氮化鈦鋯(鈦:鋯:氮=1:1:2)平均X光應變厚度限制在兩百奈米以下，而奈米壓印法的厚度限制在六百奈米左右。合併平均X光應變及光學曲率應力可以決定膜厚在兩百奈米以上的平均有效X光彈性係數(AEXEC)。

In this study, we proposed a standard procedure to measure the stress of polycrystalline Ti1-xZrxN thin films by using average X-ray strain (AXS) method. The objective was to narrow down the deviation of stress measurement to 10%, and to find the thickness limit in X-ray diffraction (XRD) and nanoindentation measurement. In addition, the effect of composition on the residual stress of Ti1-xZrxN thin films was also investigated. Eight Ti1-xZrxN thin film specimens with different compositions (x=0.25, 0.50, 0.75) and thicknesses were deposited on Si(100) by unbalanced magnetron sputtering. The strain of the thin films was measured by cos2αsin2ψ XRD method at multiple rotational angles (). The Young’s modulus of Ti1-xZrxN thin films was determined by nanoindentation. The AXS can be obtained from the slope of strain vs. cos2αsin2ψ plot. To verify stress of the thin films, the stress measured by combining AXS and nanoindentation was compared with the stress measured by laser curvature method and the deviation was assessed. The results showed that the compressive stress ranged from 2.69 to 5.10 GPa, and reached a maximum for Ti0.25Zr0.75N. The compressive stress of the Ti0.5Zr0.5N specimens decreased with increasing thickness probably due to the decrease of lattice defects. The different compositions in Ti1-xZrxN induce the asymmetrical variation of residual stress. The asymmetrical behavior in residual stress may be due to the difference in atomic size between Ti atoms in ZrN lattice and Zr atoms in TiN lattice. In this study, the deviation of XRD stress measurement was successfully decreased to 9.2%. The thickness limit of AXS measurement in Ti0.5Zr0.5N thin films was smaller than 200 nm, and the thickness limit of nanoindentation was about 600nm. By combining AXS and stress obtained by laser curvature method, the average effective X-ray elastic constant (AEXEC) could be determined for film thickness down to 200 nm.

致謝 I
摘要 III
Abstract IV
Content V
List of Figures VII
List of Tables X
Chapter 1 Introduction 1
Chapter 2 Literature Review 2
2.1 Characteristics of TiN and ZrN 2
2.2 Characteristics of TiZrN 5
2.2.1 Structure of TiZrN 5
2.2.2 Properties of TiZrN 8
2.3 Young’s Modulus and Stress Measurement in TiZrN 9
Chapter 3 Theoretical Basis 13
3.1 cos2αsin2ψ methods 13
3.2 Average X-Ray Strain (AXS) 16
3.3 Stress Verification Method 19
Chapter 4 Experimental Details 20
4.1 Specimen Preparation and Deposition Process 20
4.2 Characteristics for Structure and Compositions 23
4.2.1 X-Ray Diffraction (XRD) and Glancing Incident X-Ray Diffraction (GIXRD) 23
4.2.2 X-Ray Photoelectron Spectroscopy (XPS) 24
4.2.3 Field-Emission Gun Scanning Electron Microscopy (FEG-SEM) 25
4.2.4 Atomic Force Microscopy (AFM) 25
4.3 Properties Measurement 26
4.3.1 Nanoindentation (NIP) 26
4.3.2 Measurement of Residual Stress 27
4.3.2.1 Laser Curvature Method (LCM) 27
4.3.2.2 XRD cos2αsin2ψ Method 29
4.3.4 Four-Point Probe 30
Chapter 5 Results 32
5.1 Composition 32
5.2 Crystal Structure 37
5.3 Microstructure 42
5.4 Surface Morphology 42
5.5 Hardness and Young’s Modulus 45
5.6 Average X-ray Strain(AXS), XEC and AEXEC 46
5.7 Stress measurement 48
5.8 Resistivity 49
Chapter 6 Discussions 50
6.1 Residual Stress Variation of Ti1-xZrxN Thin Films 50
6.1.1 Composition Effect 50
6.1.2 Asymmetry of Compressive stress 52
6.1.3 Thickness Effect 52
6.2 Stress Verification 56
6.3 The Limit of AXS and NIP 61
6.4 Advantage and Shortcomings 62
Chapter 7 Conclusions 64
References 65
Appendix A Deconvoluted Spectra of XPS 70
Appendix B SEM 77
Appendix C XRD cos2αsin2ψ 79
Appendix D Standard Procedures of Stress Measurement 89

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