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研究生:汪孟涵
論文名稱:氮氣流量對非平衡磁控濺鍍奈米晶氮化鋯薄膜之結構和性質的影響
論文名稱(外文):Effects of Nitrogen Flow Rate on the Structure and Properties of Nanocrystalline ZrN Thin Film deposited by Unbalanced Magnetron Sputtering
指導教授:喩冀平黃嘉宏黃嘉宏引用關係
學位類別:碩士
校院名稱:國立清華大學
系所名稱:工程與系統科學系
學門:工程學門
學類:核子工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:英文
論文頁數:103
中文關鍵詞:氮氣流量濺鍍氮化鋯
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本研究成功的利用非平衡式磁控濺鍍法鍍著奈米晶氮化鋯薄膜於(100)矽晶片和304不�袗�上。在研究中,主要探討改變氮氣流量對氮化鋯薄膜之組成、結構、性質以及腐蝕抗性的研究。氮氣流量改變的範圍從0.25至1.75 sccm。以X光繞射法來決定薄膜的晶粒大小,其結果小於15 nm。從AFM和SEM的結果也顯示氮化鋯薄膜晶粒為奈米級。薄膜氮鋯的比率(N/Zr ratio)隨氮氣流量從0.2改變至1。氮化鋯薄膜以(111)為主要的優選方向。改變氮氣分壓對其硬度並沒有太大的改變,除了在Zr 和ZrN的混合相,因為Zr是金屬其硬度相對較軟。ZrN膜的表面粗糙度會隨著氮氣流量的增加而減少。氮化鈦薄膜的電阻率隨著堆積因子的上升而下降和ZrN飽和鍵的增加而下降,而晶粒大小並不是影響電阻率變化的主要因素。在腐蝕抗性實驗方面,5%實驗水以及0.5M H2SO4 + 0.05M KSCN 溶液中的極化掃描實驗和鹽水噴霧實驗結果發現,若奈米晶氮化鋯薄膜厚大於220nm,則氮化鋯薄膜可以有效的防止腐蝕物質穿透而侵蝕到基板。對於極化掃描實驗而言,影響抗腐蝕優劣的重要因子包跨堆積程度、結晶程度和飽和鍵的多寡。對於鹽水噴霧實驗而言,膜表面的粗糙度就是一個關鍵性的指標
Abstract

Nano-crystalline ZrN films were successfully deposited on Si (100) and AISI 304 stainless steel substrates using unbalanced magnetron sputtering (UBM) system. The effect of nitrogen flow rate was investigated on the composition, structures, properties, and corrosion resistance of the ZrN film. The N/Zr ratio increases with increasing nitrogen flow rate. The preferred orientation (111) peak is dominant for all specimens. The roughness decreases with increasing the nitrogen flow rate for all samples. The electrical resistivity of ZrN films decreases from 271.6 to 34.6 then increases to 56.3 μΩ-cm. The residual stress of the ZrN film deposited on Si is lower than that on AISI 304 stainless steel. This may be due to the difference in thermal stress and conductivity of the substrate. The results of potentiodynamic polarization dynamics scan in both 5% NaCl and 0.5M H2SO4 + 0.05M KSCN solutions indicate that packing factor is more effective than film thickness to the corrosion resistance for the coating. However in the 5% NaCl solution, crystallinity and saturated bond ratio are more important than packing factor. For salt spray test, the corrosion area increases with the films roughness. The more saturated bonds exist in the ZrN thin films, the less defects in the film structure, the less corrosion area is observed. If a nano-crystalline ZrN film is thicker than 220 nm, it could effectively protect the substrate from the corrosive medium. High packing factor is good for corrosion resistance. Better crystallinity also improves the corrosion resistance of nano-crystal thin film.
Contents…………………………………………………………….… I
List of Figures………………………………………………………… IV
List of Tables .………………………………………………………… XI
Abstract………………………………………………………………... XIII
摘要……………………………………………………………………. XIV

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

Chapter 2 Literature Review……………………………………... 4
2.1 Unbalanced Magnetron Sputtering……………………….. 4
2.2 Characteristics of ZrN..…….…..………………………….. 7
2.3 Properties of ZrN Films….…..……………………………. 8
2.3.1 Hardness……………………………………………... 8
2.3.2 Resistivity of ZrN Film……………………………… 9
2.3.3 Residual Stress ……………………………………… 11
2.4 Effect of Nitrogen Flow Rate on the Deposition Rate ……. 14

Chapter 3 Experimental Details………………………………….. 15
3.1 Specimen Preparation and Coating process……………… 15
3.2 Methods of Characterization………………………………. 17
3.2.1 X-Ray Diffraction (XRD) ……………………………. 17
3.2.1.1 θ/2θ Scan ……………………………………….. 17
3.2.1.2 Glancing incidence X-ray diffraction (GIXRD)... 18
3.2.2 Field Emission Scanning Electron Microscopy (FEG-SEM)………………………………………….. 18
3.3 Composition Characterization ………...………………….. 18
3.3.1 Rutherford Backscattering Spectrometer (RBS)……… 18
3.3.2 Electron Spectroscopy For Chemical Analysis (ESCA) 19
3.3.3 Auger Electron Spectrometer (AES)……………....…. 20
3.4 Properties Characterization ……………………………….. 20
3.4.1 Electrical Resistivity……………………………….…. 20
3.4.2 Hardness……………………..………………………... 20
3.4.3 Residual Stress …………………..…...…………….… 21
3.4.4 Atomic Force Microscopy (AFM)………………….… 21
3.6 Corrosion Resistivity ………………….………………….. 21
3.6.1 Potentiodynamic Polarization Test …………………... 21
3.6.2 Salt Spray Test……………………………….…….…. 22

Chapter 4 Results and Discuss ………………..…………………… 23
4.1 Substrate Ion Current Density………………………..……. 26
4.2 Energy and Momentum …….………………………..……. 28
4.3 Structure……….…………….…………………………….. 34
4.3.1 Scanning Electron Microscopy (SEM)……………….. 34
4.3.2 Auger Electron Spectrometer (AES) ………………… 36
4.3.3 N/Zr Ratios and Packing Factor (RBS) ………..….…. 38
4.3.4 X-Ray Diffraction (XRD)……………………………. 44
4.3.5 Glancing Incident X-Ray Diffraction (GIXRD)……… 49
4.3.6 Roughness (AFM)……………………………….……. 52
4.3.6 Composition (ESCA) .………………………….……. 53
4.4 Properties………………………………………………... 56
4.4.1 Electrical Resistivity……………….………………… 56
4.4.2 Residual Stress………………………………………. 57
4.4.3 Hardness……………………………………………… 59
4.5 Corrosion Resistivity ……………………………………... 61
4.5.1 Potentiodynamic Polarization Scan ...………….. …… 61
4.5.1.1 1N H2SO4 + 0.05M KSCN ……………………. 61
4.5.1.2 5%NaCl ………………………………………… 64
4.5.2 Salt Spray Test ………………..…. ...………….. …… 66
Chapter 5 Discussion………………………………………………. 67
5.1 Deposition Rate……………………………………..……. 69
5.2 Nanocomposite…………………………………………… 74
5.3 Grain Size……………………………………….……..… 74
5.4 Hardness.............................................................................. 76
5.5 Resistivity………………………………………………… 81
5.6 Roughness…………………………………………………. 84
5.7 Residual Stress…………………………………………….. 87
5.8 Corrosion Resistance…………………………………..….. 90
5.8.1 Potentiodynamic polarization scan test………………. 90
5.8.2 Salt spray teat………………………………………… 95

Chapter 6 Conclusions…………………………………………….. 96

Chapter 7 Reference……………………………………..….……... 98
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