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研究生： 張翊程
Chang, Yi-Cheng
論文名稱： 利用電紡絲製程與電漿蝕刻製備銅銀奈米纖維
Fabrications of Copper-Silver Nanofibers via Electrospinning and Plasma Etching
指導教授： 郭昌恕
Kuo, Chang-Shu
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： 2020
畢業學年度： 108
語文別： 英文
論文頁數： 139
中文關鍵詞： 電紡絲 、電漿 、銅銀奈米纖維 、銅銀奈米纖維的結構 、抗氧化 、電極
外文關鍵詞： electrospinning, plasma, copper-silver nanofibers, structure of Cu-Ag nanofibers, resistance to oxidation, electrodes
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    • 本研究透過電紡絲技術和電漿蝕刻製程成功製備出銅銀和銀奈米纖維。電紡絲溶液之高分子使用易受電漿蝕刻的聚環氧乙烷以及少量的聚丙烯酸，加入銅及銀前驅物，並使用環境友善的醋酸水溶液所組成。電紡絲製程完成後，再分別採用常壓電漿以及低壓氬氣電漿給于高分子適度的蝕刻，同時裂解銅和銀的前驅物形成金屬銅銀。在電漿蝕刻製程中，金屬銅銀會逐漸累積在纖維表面並形成連續導電相，優勢是不需要使用化學還原劑。透過穿透式電子顯微鏡之線掃描分析以及化學分析電子光譜儀的表面分析驗證常壓電漿製備的銅銀奈米纖維具有銀殼層包住內核銅銀之結構，展現良好的導電性以及抗氧化的能力。銅銀電紡絲在低壓電漿製程之收縮裂開之行為也被研究，並且透過調整配方中金屬對高分子之含量比來解決。低壓氬氣電漿製程製備的銅銀電紡絲具有銅在表面濃度高於銀的結構，但仍展現良好的抵抗氧化能力。無序沉積的電紡銅銀之導電網路由於具有良好的導電性，本質導電度可達106 (S/m)， 具有應用於電極的潛力。

    Copper-silver nanofibers were fabricated successfully via electrospinning technique and plasma etching. The plasma-vulnerable polymer, poly(ethylene oxide), poly(acrylic acid), and silver nitrate, copper nitrate trihydrate as metal precursor were fully dissolved in acetic acid aqueous solution which was friendly to environment. The atmospheric pressure plasma and low pressure argon plasma were employed to provide moderate etching to the polymer, as well as to decompose the silver and copper precursor that formed metallic copper and silver. During the plasma etching, the metallic copper and silver were formed and gradually accumulated to the fiber surface, forming the continuous conductive domain. The advantage was without utilizing the chemical reagent. The TEM-EDS linescan and ESCA demonstrated that the structure of Cu-Ag nanofibers synthesized via atmospheric pressure plasma was silver sheath covered the core of Cu-Ag, performing excellent conductivity and resistance to oxidation. The shrinkage and crack formation of Cu-Ag nanofibers synthesized via low pressure argon plasma were investigated. The adequate adjustment to weight ratio of metal/polymer in recipe could prevent the crack formation. The Cu-Ag nanofibers synthesized via argon plasma had higher concentration of Cu on nanofibers surface, but still performed fine resistance to oxidation. Randomly-deposited electrospun nanofibers and resultant copper-silver nanofibers revealed the excellent electrical conductivity (106 S/m), having potential in the application of electrodes.

    中文摘要 I Abstract II 致謝 III Table of Contents IV List of Tables VIII List of Illustrations X Chapter 1 Introduction 1 1.1 Electrode 1 1.1.1 Metal thin film based electrode 1 1.1.2 Metal oxides based electrodes 2 1.1.3 Polymer based electrodes 2 1.1.4 Graphene based electrodes 3 1.1.5 Conductive thin electrode with networks structure 3 1.2 Introduction to electrospinning technique 4 1.2.1 The principle of electrospinning 6 1.2.2 The component of electrospinning 7 1.2.3 The conductive network via electrospinning 11 1.2.4 The electrospun polymer/metal composite nanofibers 13 1.3 Introduction to Plasma 14 1.3.1 Atmospheric pressure plasma 15 1.3.2 Low pressure plasma 15 1.3.3 The application of cold plasma 16 1.4 Bi-metallic alloy 18 Chapter 2 Motivation 19 Chapter 3 Experiments 20 3.1 Materials and instruments for experiment 20 3.1.1 Chemical reagent and materials 20 3.1.2 Instruments for experiments 21 3.2 Fabrication of electrospun nanofibers 22 3.2.1 The electrospinning solution 22 3.2.2 Electrospinning process via basic setup 24 3.2.3 Electrospinning process via electrospinning machine 25 3.2.4 Wet compression 26 3.3 Plasma treatment 28 3.3.1 Atmospheric pressure plasma 29 3.3.2 The parameters of atmospheric pressure plasma 29 3.3.3 Argon low pressure plasma 32 3.4 Washing process 34 3.5 Properties investigation 35 3.5.1 Morphologies and diameters of nanofibers 35 3.5.2 The quantification of Cu to Ag inside Cu-Ag nanofibers 37 3.5.3 The distribution of Cu and Ag inside the Cu-Ag nanofibers 37 3.5.4 The Surface analysis of ESCA(XPS) 38 3.3.5 Thermogravimetric analysis of Cu-Ag nanofibers 40 3.5.6 The electrical property of Cu-Ag networks 41 Chapter 4 Results and discussion 42 4.1 The recipes for electrospun polymer with silver precursor /silver precursor and copper precursor 42 4.1.1 The difficulty in fabrication of Cu nanofibers and successful fabrication of Cu-Ag nanofibers 42 4.1.2 The adding of PAA to improve the thermal resistance of as-spun nanofibers 46 4.1.3 The ratio of CH3COOH to H2O in recipes of single-nozzle electrospun Ag and Cu-Ag nanofibers 55 4.1.4 The feeding weight ratio of metal/polymer corresponded to crack 58 4.1.5 The optimal recipes for the fabrication of Ag and Cu-Ag nanofibers synthesized by atmospheric pressure plasma and low pressure argon plasma 60 4.2 Electrospinning of polymer nanofibers with silver and copper precursor 64 4.2.1 The electrospinning process via basic instruments. 64 4.3 The Cu-Ag nanofibers synthesized via atmospheric pressure plasma 69 4.3.1 The morphology of Cu-Ag nanofibers synthesized by atmospheric pressure plasma 69 4.3.2 The SEM-EDS to analyze the ratio of Cu to Ag 74 4.3.3 The XPS(ESCA) analysis to Cu-Ag nanofibers 76 4.3.4 The relative concentration of Cu to Ag on the surface and the whole nanofibers 89 4.3.5 TEM-EDS linescan for investigating the distribution of Cu and Ag 92 4.3.6 The thermogravimetric analysis of Cu-Ag nanofibers 98 4.3.7 The electrical property of Cu-Ag networks 99 4.3.8 The resistance to oxidation 101 4.3.9 The mechanism of Ag on the nanofibers surface 103 4.4 The Ag and Cu-Ag nanofiber synthesized via low pressure argon plasma 104 4.4.1 The shrinkage of Cu-Ag nanofibers under argon plasma treatment 105 4.4.2 The reduction in volume results in the shrinkage of Cu-Ag nanofibers 106 4.4.3 The effect of adhesion 108 4.4.4 The morphology and diameters of Ag and Cu-Ag nanofibers synthesized by low pressure argon plasma 109 4.4.5 SEM-EDS to quantify the ratio of Cu-Ag nanofibers 113 4.4.6 The XPS(ESCA) analysis to Cu-Ag nanofibers 114 4.4.7 The relative concentration of Cu to Ag on the surface and the whole nanofibers 122 4.4.8 TEM-EDS linescan of Cu-Ag nanofibers synthesized via argon plasma 124 4.4.9 The resistance to oxidation 129 4.4.10 The electrical property of Cu-Ag networks synthesized via low pressure argon plasma 131 4.4.11 The reduction mechanism of Cu-Ag nanofibers synthesized via argon plasma 134 Chapter 5 Conclusion 135 Chapter 6 Reference 136

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