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研究生： 侯昱全
Hou, Yu-Cyuan
論文名稱： 螯合劑補助之非導電溶液局部陽極氧化法於鋁基板製備摻雜氮(N)或鈦(Ti)Al2O3薄膜
Fabrication of selective-area (N or Ti)-doped Al2O3 films on Al substrates through chelating-agent-assisted local anodization processes using non-conducting solutions
指導教授： 張高碩
Chang, Kao-Shuo
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2023
畢業學年度： 111
語文別： 英文
論文頁數： 156
中文關鍵詞： （N 或 Ti）摻雜的 Al2O3 薄膜 、非導電溶液 、局部陽極氧化和螯合效應
外文關鍵詞： (N or Ti)-doped Al2O3 film, non-conducting solution, local anodization, and chelating effect
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    • 非導電溶液中局部電化學反應的發展具有重要的研究價值，傳統的氧化膜合成方法成本高、程序複雜，且需使用商業化的設備進行製備，相比之下，我們提出的水溶液陽極氧化法具有眾多優勢。首先，這個方法能夠在室溫、常壓下進行氧化膜製備，這一簡化過程降低了氧化膜合成的複雜性。其次，非導電的螯合劑能形成穩定的螯合基團與金屬離子結合，防止金屬離子與水反應並產生水化合物沉澱。第三，高電壓作為能量來源誘導電化學反應，觸發基板的局部陽極氧化，控制氧化膜在非導電溶液中的形成速率和結構，也通過添加適當的前驅物實現對摻雜元素含量的調控。
    通過光學顯微鏡（OM）、掃描電子顯微鏡（SEM）、SEM 能量分散 X 射線光譜（EDS）和 X 射線光電子能譜（XPS）等觀察方法，我們觀察到在基板上形成的氧化膜不僅具有理想的尺寸和形態，還能夠將螯合基團的金屬元素納入其中，表明在高電壓之下，非導電的螯合基團有效地參與電化學反應，成功製備帶有和不帶有摻雜元素的氧化膜。
    通過高電壓作用，我們成功獲得了 N 摻雜的 Al2O3薄膜，其使尿素釋放出帶有負電荷的氮離子，氮離子參與 Al 基板表面的電化學反應，並納入到 Al2O3 薄膜中。製備 Ti 摻雜的 Al2O3 薄膜時，鈦酸異丙酯和乙二醇之間的螯合效應在強電場區域起主導作用，從而製備了含有 Ti 元素的 Al2O3薄膜。

    The development of local electrochemical reaction through non-conducting solutions holds significant research values. Traditional methods for the synthesis of oxide films suffer from limitations such as high cost, complex processes, and equipment requirements. By contrast, our proposed aqueous solution-based approach offers numerous advantages. Firstly, the process enables the film deposition at room temperature and under ambient atmospheric
    conditions, this simplifies the process and reduces complexity of oxide film synthesis. Secondly, non-conductive chelating agents form stable chelation groups with metal ions, preventing their reaction with water and subsequent hydrolysis to form precipitates. Thirdly, high voltage as an energy source was applied to induce electrochemical reactions, allows us to control the formation rate and structure of oxide films in non-conducting solutions, trigger localized anodic oxidation reactions directly on substrates, and the tuning of the amounts of dopants by adding appropriate doping element precursors.
    Through optical microscopy (OM), scanning electron microscopy (SEM), SEM energydispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS), we observed that the resulting oxide films on substrates not only exhibited the desirable size and morphology but also incorporated the metal elements from the chelating groups. This indicates the effective electrochemical involvement of non-conductive chelating groups by the assistance of high voltage, thus accomplishing the goal of film deposition with and without dopants.
    The N-doped Al2O3 film was obtained using high voltage, which enabled urea to release negatively charged nitrogen ions. These ions were participated in the electrochemical reactions on Al substrate surface and became incorporated into the resulting Al2O3 film. For the fabrication of Ti-doped Al2O3 film, the chelating effect between titanium isopropoxide and ethylene glycol is predominant in the regions with strong electric fields, which triggers the formation of the Al2O3 film simultaneously incorporated with Ti elements.

    摘要 Ⅰ Abstract Ⅱ 致謝 Ⅳ Contents Ⅵ Figure Contents Ⅻ Table Contents ⅩⅩⅡ Introduction 1 1.1 Conventional Approach Through Electrolyte Solution 1 1.1.1 Electrochemical Method Without Plasma 1 1.1.1.1 Electrochemical cells and reactions 1 1.1.1.2 Factors Affecting Electrode Reaction Rate and Current 5 1.1.1.2.1 Rate Determining Step 5 1.1.1.2.2 Capacitance and Charge of an Electrode 9 1.1.1.2.3 Electrical Double Layer 10 1.1.1.3 Application- Electrochemical Cell 11 1.1.1.3.1 Electrolyzer Cell 12 1.1.1.3.2 Galvanic Cell 14 1.1.2 Solution Plasma Process 16 1.1.2.1 Introduction of Solution Plasma Process 16 1.1.2.2 Solution Plasma Generation Method 20 1.1.2.3 Pin to pin distance Effect 22 1.1.2.4 Electrolyte Concentration Effect 23 1.1.2.5 Possible Mechanism of Solution Plasma 26 1.1.2.5.1 Electronic Mechanism 27 1.1.2.5.2 Bubble Mechanism 30 1.1.2.6 Solution Plasma Application 34 1.1.2.6.1 Plasma Electrolysis Oxidation 34 1.1.2.6.2 Nanomaterials Synthesis 38 1.1.2.6.3 Water treatment 43 1.1.2.6.4 Agricultural Development 47 1.2 Novel approach: Localized Oxidation in solutions 49 1.2.1 AFM-tip Induced Local Anodization Oxidation 49 1.2.1.1 Introduction and Experimental Setup 49 1.2.1.2 Factors Influencing the Water Bridge Size and Oxide Deposition 52 1.2.1.3 Application – Nano Writing 59 1.2.2 Pechini Solution Process & Polymer Matrix 61 1.3 Tungsten Tip Fabrication Process 62 Chapter 2 Experimental methods 64 2.1 Material 64 2.2 Experiment Procedure 66 2.2.1 Substrate preparation 66 2.2.2 Substrate cleaning 67 2.2.3 Fabrication and cleaning of tungsten tip 68 2.2.4 Experimental Setup 73 2.2.5 Plasma test experiment 76 2.2.6 Silicon substrate localized anodization oxidation experiment 77 2.2.7 Aluminum substrate anodization oxidation experiment 80 2.3 Characterization 83 2.3.1 X-ray diffraction (XRD) analysis 83 2.3.2 Optical microscope analysis 84 2.3.3 X-ray photoelectron spectroscopy (XPS) 85 2.3.4 Scanning electron microscopy (SEM) 86 2.3.5 Optical emission spectrum (OES) 87 2.3.6 Alpha-step profilometer 88 Chapter 3 Results and discussion 89 3.1 Solution optical emission spectrum 89 3.1.1 Electrolyte solution optical emission spectrum 90 3.1.2 Non-conductive solution optical emission spectrum test 91 3.2 Different non-conductive solutions for localized anodization on substrates 92 3.3 Commercial and home-made tungsten tips 94 3.4 Tungsten tip condition under electrochemical reaction 95 3.5 SiO2 film 99 3.5.1 Effect of W tip–substrate distance 99 3.5.2 Effect of current and anodization time 103 3.5.2.1 Current effect 103 3.5.2.1.1 OM image of SiO2 under various current 103 3.5.2.1.2 SEM image of SiO2 under various current 106 3.5.2.2 Various anodization times 108 3.5.2.2.1 OM image of SiO2 with different anodization time 108 3.5.2.2.2 Kinetics of the SiO2 film anodization 111 3.5.3 Zirconium (Zr) doped-SiO2 film 114 3.5.3.1 SEM analysis of Zr-doped SiO2 116 3.5.3.2 XPS analysis of Zr-doped SiO2 119 3.5.3.3 XRD analysis of Zr-doped SiO2 124 3.6 Localized anodization oxidation of Al2O3 film 125 3.6.1 Various anodization times of Al2O3 film 125 3.6.1.1 OM image 125 3.6.1.2 SEM image 128 3.6.1.3 Kinetics of the Al2O3 film anodization 130 3.6.1.4 XRD analysis 131 3.6.1.5 XPS analysis 132 3.6.2 Nitrogen (N)-doped Al2O3 film 134 3.6.2.1 XPS analysis 134 3.6.2.2 SEM analysis 138 3.6.3 Titanium(Ti)-doped Al2O3 film 141 3.6.3.1 XPS analysis 141 3.6.3.2 SEM analysis 146 Chapter 4 Conclusion & Future Work 149 4.1 Conclusion 149 4.2 Future work 150 Chapter 5 References 151

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