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研究生： 葉忠憲
Yeh, Chung-Hsien
論文名稱： 掃描式熱探針技術合成並微影銀奈米粒子及其電漿子共振性質之研究
Plasmonic Resonances of Silver Nanoparticles Synthesized and Patterned by Scanning Thermal Lithography
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： 2012
畢業學年度： 100
語文別： 英文
論文頁數： 84
中文關鍵詞： 掃描熱探針微影技術 、定點熱分析 、微熱分析 、過氧化物 、電漿子共振 、銀奈米粒子
外文關鍵詞： Scanning Thermal Lithography, in-situ Thermal Analysis, Microthermal Analysis, Peroxide, Plasmon Resonance, Silver Nanoparticles
相關次數： 點閱：141  下載：0 
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    • 本篇論文以掃描熱探針微影技術在高分子薄膜內定點合成及成像銀奈米粒子。掃描熱探針技術是利用掃描探針顯微鏡搭配微米級的熱探針，此設備不但能提供定點加熱而且也能同時作為溫度感應器。將光學級的聚對苯二甲酸乙二醇酯和銀的前趨物-三氟醋酸銀溶液，利用旋轉塗布的方式在玻片上成膜。藉由在室溫下的溶劑退火，使得聚對苯二甲酸乙二醇酯薄膜的軟化溫度提升。此外，異苯過氧化氫為一種過氧化物的高能物質，能在較低的溫度下產生熱裂解，此特性在掃描熱微影過程中能提供額外的熱源，並且在熱探針所加熱的區域加速產生所需的物理和化學反應。實驗結果顯示，高能物質輔助掃描熱探針微影技術成能將聚對苯二甲酸乙二酯醇薄膜內的銀奈米粒子還原溫度降低至200 oC。由暗視野光學顯微鏡研究掃描熱探針顯微鏡微影的銀奈米陣列之表面電漿共振特性，散射光譜顯示隨著陣列間距的縮小，峰值呈現藍位移，此特性是由於奈米粒子間產生耦合。

    Scanning thermal lithography (SThL) was demonstrated in this research work for the in-situ synthesis and patterning of silver nanoparticles in a polymer thin film. SThL technique involved the scanning probe microscope equipped with a micro-scale thermal probe that provided a localized heating mechanism and simultaneously acted as a temperature sensor. Robust and optically-transparent poly(ethylene terephthalate) (PET) was co-dissolved with silver trifluoroacetic acid, the nanoparticle precursor, and spin-coated on the slide. Solvent annealing process at room temperature successfully promotes the softening temperature of the spin-coated PET. In addition, a peroxide-based energetic, cumene hydroperoxide (CHP), was incorporated to provide the extra joule energy during the SThL process. Thermal decomposition of CHP took place at a relatively-low temperature. Its decomposition exothermic energy accelerated the desired chemical or physical reactions right under the SThL probe. As a result, the energetic-assisted SThL produced and patterned the silver nanoparticles in a PET thin film at the temperature as low as 200 oC. Obtained SThL-synthesized silver nanoparticles were examined by the dark-field microscope, and the surface plasmon resonance was found blue-shifted as closing the SThL array spacing. Desired SThL patterns and the plasmon coupling were demonstrated and investigated.

    中文摘要 I Abstract II 誌謝 III Table of Contents IV List of Tables VI List of Illustrations VII Chapter 1 Introduction 1 1.1 Introduction of Plasmonics 1 1.2 Introduction of scanning probe microscopy (SPM) 2 1.2.1 Scanning tunneling microscopy (STM) 2 1.2.2 Atomic force microscopy (AFM) 3 1.2.3 Scanning thermal microscopy (SThM) 5 1.3 Surface plasmon 8 1.3.1 Localized surface plasmon resonance (LSPR) 9 1.3.2 Factors for effecting LSPR 10 1.3.3 Plasmon coupling in periodic nanoparticle arrays 12 1.4 Fabrication of metal nanostructures 13 1.4.1 Templated method 13 1.4.2 Electron-beam lithography 13 1.4.3 Laser printing 14 1.5 Scanning probe lithography (SPL) 15 1.5.1 Dip-pen lithography (DPL) 15 1.5.2 Anodization lithography (ANL) 16 1.5.3 Mechanical force lithography (MFL) 16 1.5.4 Scanning thermal lithography (SThL) 17 1.6 Introduction of thermal probe, in-situ thermal analysis and SThM 20 1.6.1 Micro-scale thermal probe: Wollaston wire probe 20 1.6.2 Nano-scale thermal probe: nano-TATM probes 20 1.7 Theory of scanning thermal microscopy (SThM) 23 1.8 The principle of in-situ thermal analysis 25 1.9 Energy absorption by a sample from micro- or nano-probe 28 Chapter 2 Motivation of research 32 Chapter 3 Experiments 33 3.1 Materials and instruments 33 3.1.1 Materials 33 3.1.2 Instruments 35 3.2 Experiment process 36 3.2.1 PET film preparation 36 3.2.2 Pattering on PET/CF3COOAg/CHP films by SThL 38 3.2.3 Scattering spectra measurement 39 3.3 Analysis instrument 40 3.3.1 Scanning probe microscopy (SPM) 40 3.3.2 Dark-field optical microscopy 40 3.3.3 Spectrometer 42 Chapter 4 Result and Discussion 43 4.1 Preparing polymer/silver precursors/energetic films 43 4.1.1 Silver precursors 43 4.1.2 Preparation of PET/CF3COOAg films via solution dipping process 45 4.1.3 Preparation of PET/CF3COOAg films via spin-coating process 47 4.2 Investigations of spin-coated PET/CF3COOAg/energetics films 49 4.2.1 Thermal analysis of PET/CF3COOAg/energetics films 49 4.2.2 Optical properties of PET/CF3COOAg/energetics films 52 4.2.3 UV-vis spectra of PET/CF3COOAg/energetics films 57 4.2.4 Removal of unreacted CF3COOAg from PET films 59 4.3 Thermal analysis of CHP and PET/CHP films 61 4.3.1 In-situ thermal analysis of CHP 61 4.3.2 In-situ thermal analysis of PET/CHP films 63 4.4 Patterns fabricated by scanning thermal lithography (SThL) 66 4.4.1 The morphology of patterns fabricated by SThL 66 4.4.2 The dark-field optical microscopy images patterned by SThL 69 4.5 Fabrication of silver nanoparticles arrays by scanning thermal lithography 72 4.5.1 Effect of probe temperature 72 4.5.2 Effect of arrays patterns 75 Chapter 5 Conclusion 78 Chapter 6 Reference 79

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