非平衡磁控濺鍍製程中鍍膜厚度和鈦介層厚度對奈米晶氮化鈦薄膜之結構與性質之影響研究

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研究生：	歐陽汎怡 Fan-Yi Ou Yang
論文名稱：	非平衡磁控濺鍍製程中鍍膜厚度和鈦介層厚度對奈米晶氮化鈦薄膜之結構與性質之影響研究 Effect of film thickness and Ti interlayer thickness on the structure and properties of nanocrystalline TiN thin film deposited by unbalanced magnetron (UBM) sputtering
指導教授：	黃嘉宏 Jia-Hong Huang 喻冀平 Ge-Ping Yu
口試委員:
學位類別：	碩士 Master
系所名稱：	原子科學院 - 工程與系統科學系 Department of Engineering and System Science
論文出版年：	2004
畢業學年度：	92
語文別：	英文
論文頁數：	101
中文關鍵詞：	氮化鈦、鍍膜厚度、鈦介層、非平衡磁控濺鍍、奈米晶
外文關鍵詞：	TiN, Film thickness, Ti interlayer, UBMS, nanocrystal
相關次數：	點閱：4 下載：0
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本論文目的在研究非平衡磁控濺鍍系統中，鍍膜厚度和鈦介層厚度對於奈米晶氮化鈦薄膜成分、結構、機械性質與腐蝕抗性的影響。奈米晶氮化鈦薄膜分別鍍著於單晶矽晶片與AISI D2鋼上。結果顯示，不論基材為矽晶片或是D2鋼，氮化鈦薄膜都呈現 (111) 的優選方向，跟鍍膜厚度並無明顯關係。鍍膜厚度對於氮化鈦薄膜的氮鈦比例、表面粗糙度與晶粒大小也只有輕微的關係。薄膜堆積因子則是隨著鍍膜厚度變化而幾乎維持固定，其中最薄的試片的堆積因子已高達0.8。奈米硬度儀的實驗結果顯示氮化鈦薄膜硬度分布從22GPa至29GPa並指出薄膜硬度跟薄膜織構與鍍膜厚度並無相關性。氮化鈦薄膜呈現壓縮的殘留應力，並且在基材為D2鋼時，殘留應力隨著鍍膜厚度增加而下降。從殘留應力而來的介面剪應力隨著鍍膜厚度增加而增加，然而殘留應力未必隨著鍍膜厚度增加而上升。在氮化鈦/鈦之雙層鍍膜中，有一個臨界鈦介層厚度可有效的降低氮化鈦薄膜熱應力和殘留應力。在硫酸與鹽水的動態極化掃描結果指出堆積因子對於防蝕效果比鍍膜厚度有效。此外，如果薄膜堆積因子夠高，增加鍍膜厚度或是加入一個鈦介層皆可以保護基材，避免腐蝕。

Nanocrystalline TiN thin films were successfully deposited on Si (100) and D2 steel substrates using unbalanced magnetron sputtering (UBMS) system. The objective of this study was to investigate the effect of film thickness and Ti interlayer thickness on the composition, structures, mechanical properties, and corrosion resistance of TiN film. The results showed that (111) was the dominant preferred orientation in the TiN films. The effects of the film thickness were only slightly varied on the N/Ti ratio, roughness, and grain size. The packing factor was almost constant with film thickness and the thinnest specimen reached a quite high packing factor of 0.8. Nanoindentation data, ranging from 22~29 GPa, indicated that hardness of the films was not related to the film texture and film thickness. The residual stresses of all TiN films were compressive, and mostly decreased with increasing film thickness in TiN/D2 specimens. Interfacial shear stress induced from the residual stress was increased with film thickness, whereas the residual stress was not necessarily increased with film thickness. In the bi-layer TiN/Ti coating, there was a critical Ti interlayer thickness (120~150nm) to effectively reduce the thermal stress and residual stress in the TiN coating. The results of potentiodynamic polarization scan in both 5% NaCl and 0.5M H2SO4 + 0.05M KSCN solutions indicated that packing factor was more effective than film thickness to the corrosion resistance for the coating. Furthermore, increasing film thickness or adding a Ti interlayer could effectively protect the substrate from the corrosive medium, if the packing factor was sufficiently high.

Table of Contents
Table of Contents …..…..…..…..…..…..…..…………………………    i
List of Figures …………………………………………………………    ix
List of Tables …….…...……………………………………………….    xi

Chapter 1 Introduction ……….……………………………………...    1

Chapter 2 Literature Review
1 Unbalanced Magnetron Sputtering (UBMS)……...…..……………………...    3
2 Characteristics of TiN………………………………………………………...    4
3 Effect of Film Thickness on the Preferred Orientation of Nitride Thin Films.    7
4 Residual Stress……………..…….…………………………………………...    10
5 Effect of Ti interlayer…………………………………………………………    11
6 Corrosion Resistance…………………………………………………………    13

Chapter 3 Experimental Details
1 Preparation of Substrate Material and Coating Process……….......................    16
2 Characterization Methods…………………………………….........................    17
2.1 XRD………………..……………….……………………......................    17
2.2 Rutherford Backscattering Spectroscopy…….………………………...    21
2.3 FEG-SEM……….……..……………………….………………………    22
2.4 Secondary Ion mass Spectroscopy (SIMS)……..………………………    22
2.5 Atomic Force Microscopy (AFM).……………………………………..    23
2.6 X-Ray Photoelectron Spectrometer (XPS)…………... ………………..    23
2.5 Auger Electron Spectrometer (AES)…………………….......................    24
3 Properties Measurements…………………………………….……………….    24
3.1 Electrical Resistivity………………..……………….………………….    24
3.2 Hardness………………………………..…….………………………...    26
3.3 Residual Stress………………………………………………………….    26
4 Corrosion Resistance…………………..……………………………………..    27
5.1 Potentiodynamic polarization……….………………………………….    27
5.2 Salt spray test…………………………………………………………...    30

Chapter 4 Results
1 Scanning Electron Microscopy (SEM)……………………………………….    31
2 The Total Energy and Momentum……………………………………………    31
3 X-ray Diffraction (XRD)……………………………………………………..    38
4 Glancing Incident X-ray Diffraction (GIXRD)………………………………    46
5 N/Zr ratios and Packing Factor……………………………………………….    46
6 Electrical Resistivity………………………………………………………….    54
7 Roughness…………….………………………………………………………    56
8 Hardness…………….…………………………….…….................................    56
9 Residual Stress…..…………….…………..………………………………….    62
10 Saturated Bond Ratios………………………………..……………………..    62
11 Compositional Depth Profiles.……..…………….………………………….    62
12 Potentiodynamic Polarization……………………………………………….    66
12.1 0.5M H2SO4 + 0.05M KSCN …………………………………………    66
12.2 5%NaCl………………………………………………………………..    72
13 Salt Spray Test…………….………………………………………………...    72

Chapter 5 Discussion
1 Energy and Momentum...…………………………………….........................    75
2 Structure………………………………………………………………………    76
3 Hardness……………………………………………………………………...    77
4 Resistivity…………………………………………………………………….    78
5 Residual Stress………………………………………………………………..    79
5.1 Effect of Film Thickness………………..……………….……………...    79
5.2 Effect of Ti Interlayer………………..…….…………………………...    86
5.3 Substrate Effect…….……..……………………….……………………    88
5 Corrosion Resistance………………………………………………………..    90
Conclusions……...………………...…………………………...    93

References ……………………………………………………………..    95

                                

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