利用非平衡磁控濺鍍法製備鋯銅銀鋁金屬薄膜與其後熱處理之研究

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研究生：	陳培儂 Chen, Pei-Nung
論文名稱：	利用非平衡磁控濺鍍法製備鋯銅銀鋁金屬薄膜與其後熱處理之研究 Preparation and post-annealing of ZrCuAgAl thin films by unbalanced magnetron sputtering
指導教授：	黃嘉宏 Huang, Jia-Hong
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：	2010
畢業學年度：	99
語文別：	英文
論文頁數：	92
中文關鍵詞：	金屬玻璃、薄膜、腐蝕
外文關鍵詞：	metallic glass, thin film, corrosion
相關次數：	點閱：4 下載：0
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本實驗主要目的在於研究鍍膜後熱處理和鍍膜時基材偏壓對鋯-銅-銀-鋁金屬薄膜機械與腐蝕性質的影響。本研究之金屬薄膜使用非平衡磁控濺鍍系統，製備於p型(100)矽晶片和304不□鋼兩種不同基材上，金屬玻璃鍍膜溫度為室溫。成分分析顯示，金屬玻璃薄膜中的各種元素皆隨厚度均勻分布，然而薄膜中銀含量卻明顯低於靶材，其原因可能在於鍍膜過程中基材表面再濺射所致。金屬玻璃薄膜在真空環境中經250□C熱處理一小時後成為結晶結構，其結晶相經X光繞射分析發現主要為ZrO2、CuZrO3、Cu10Zr7、AlCu2Zr及Al3Zr5。
金屬薄膜性質的改變明顯的是由於熱處理促使非晶薄膜結晶所致。在機械性質方面，結晶薄膜之硬度較非晶薄膜高，同時金屬薄膜經熱處理後其堆積密度上升且電阻率下降。在殘留應力方面，非晶薄膜的殘留應力為壓應力並隨薄膜厚度的增加而減小；而熱處理後大部分試片之應力狀態則由壓應力轉為拉應力。本研究將試片置於1N H2SO4+ 0.05 M KSCN的試驗溶液中進行動態極化掃描，以評估鍍著金屬薄膜之304不□鋼的防蝕能力。結果顯示，非晶或結晶金屬薄膜皆能顯著提升不□鋼基材之防蝕性，而結晶薄膜由於熱處理所增生之表面氧化層，使其抗蝕能力更高於非晶薄膜。然而金屬薄膜的鹽霧測試結果卻不盡理想，無論是非晶或結晶薄膜皆受到氯離子的侵蝕而生成ZrClO.43和CrCl3，導致薄膜遭受破壞，使得鍍層和基材剝離。

The purpose of this study is to investigate the effect of post-annealing and substrate bias on the mechanical properties and corrosion behavior of Zr-Cu-Ag-Al metallic films. The metallic films were deposited on p-type (100) Si wafer and 304 stainless steel substrates using unbalanced magnetron sputtering. The Zr-Cu-Ag-Al metallic glass (MG) films were deposited at room temperature. The compositions of the MG thin films were uniformly distributed through thickness; however, Ag composition in the films was significantly lower than that in the sputtering target, which may be attributed to re-sputtering effect. The MG films were annealed in vacuum at 250□C for 1 hour, by which the metallic films were crystallized and the crystalline phases were characterized by X-ray diffraction, where the major phases included ZrO2, CuZrO3, Cu10Zr7, AlCu2Zr, and Al3Zr5.
The property changes were obviously due to crystallization by post-annealing. For the mechanical properties, the hardness of the crystalline films was higher than the as-deposited counterparts. In addition, the packing density of the MG films increased and electric resistivity decreased after annealing. The residual stress of the as-deposited films was compressive and decreased with thickness; after annealing the stress changed to tensile state for most of the samples. The potentiodynamic polarization scanning was performed in 1N H2SO4+ 0.05 M KSCN solutions to evaluate the corrosion resistance of the metallic film coated 304 stainless steel. The results showed that the corrosion resistance of MG coated-304 stainless steel, in both amorphous and crystalline phases, was significantly improved. The corrosion resistance of the crystalline coatings substantially increased, which was mainly contributed from the surface oxide layer. The salt spray test results of the MG films were not satisfactory. The deterioration of the MG coatings, both amorphous and crystalline structure, in the salt spray test is mainly due to the attack of chloride ions and the formation of ZrClO.43 and CrCl3 compounds, which leads to the spallation of the coatings.

摘要........................................................................................................................................... I
Abstract................................................................................................................................... II
誌謝.........................................................................................................................................III
Content....................................................................................................................................V
List of Figures....................................................................................................................... VII
List of Tables..........................................................................................................................IX
Chapter 1 Introduction.........................................................................................................1
Chapter 2 Literature Review ...............................................................................................3
1 History of Bulk Metallic Glass (BMG).....................................................................3
2 Physics and Criterion of BMG Formation ..............................................................6
3 Characteristics of BMGs ...........................................................................................7
3.1 Mechanical Properties and Plastic Deformation Mechanisms of BMGs...7
3.2 Electrical Properties .......................................................................................7
3.3 Corrosion Behavior.........................................................................................7
4 Methods to Fabricate Amorphous Alloys ..............................................................10
5 Characteristics of Thin Film Metallic Glasses (TFMGs) .....................................13
5.1 Mechanical Properties ..................................................................................13
5.2 Electrical Properties .....................................................................................13
5.3 Corrosion Behavior.......................................................................................14
6 Compositions Selection of Sputtering Target ........................................................14
Chapter 3 Experimental Details ........................................................................................16
1 Specimen Preparation and Deposition Process .....................................................16
2 Characterization Methods.......................................................................................21
2.1 X-Ray Diffraction (XRD) .............................................................................21
2.2 Field-Emission Gun Scanning Electron Microscopy (FEG-SEM) ...........21
2.3 Rutherford Backscattering Spectroscopy (RBS) .......................................21
2.4 Auger Electron Spectroscopy (AES)............................................................22
2.5 Electron Probe X-ray MicroAnalysis (EPMA)...........................................22
3 Property Measurement............................................................................................22
3.1 Electrical Resistivity .....................................................................................22
3.2 Hardness ........................................................................................................23
3.3 Residual Stress...............................................................................................23
3.4 Corrosion Resistance ....................................................................................26
Chapter 4 Results................................................................................................................28
1 Compositions ............................................................................................................28
1.1 EPMA and RBS.............................................................................................28
VI
1.2 AES Compositional Depth Profiles..............................................................35
2 Structure ...................................................................................................................40
2.1 XRD................................................................................................................40
2.2 SEM................................................................................................................45
3 Properties..................................................................................................................51
3.1 Packing Density.............................................................................................51
3.2 Hardness and Elastic Constant....................................................................54
3.3 Electrical Resistivity .....................................................................................58
3.4 Residual Stress...............................................................................................60
4 Corrosion Behavior..................................................................................................62
4.1 Potentiodynamic polarization scan .............................................................62
Chapter 5 Discussion ..........................................................................................................69
1 The effect of applied bias.........................................................................................69
1.1 Compositions and crystal structure ............................................................69
1.2 The relationship between applied bias and element contents...................69
1.3 Bias effect on the mechanical and corrosion properties............................70
2 Effects of post-annealing .........................................................................................73
2.1 Crystal structure and compositions ............................................................73
2.2 Mechanical properties ..................................................................................74
2.3 Corrosion resistance .....................................................................................76
Chapter 6 Conclusions........................................................................................................80
References..............................................................................................................................81
Appendix................................................................................................................................85

                                

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