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研究生： 張志宇
Chang, Chih-Yu
論文名稱： 於金奈米柱陣列附著金屬奈米粒子做為雙接面表面增顯拉曼散射基板對第一型膠原蛋白之量測
Metal Nanoclusters on Focused ion beam Fabricated Au Nanorod Array as a Double junction SERS-active substrate for Collagen Type-I Detection
指導教授： 廖峻德
Liao, Jiunn-Der
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： 2014
畢業學年度： 102
語文別： 中文
論文頁數： 67
中文關鍵詞： 表面增顯拉曼散射 、雙接面 、4-氨基苯硫酚 、第一型膠原蛋白
外文關鍵詞： SERS, double junction, 4- aminobenzenethiol, collagen type-I
相關次數： 點閱：114  下載：7 
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    • 金或銀奈米簇藉由電子束蒸鍍機蒸鍍於聚焦離子束製作之金奈米柱陣列上(fibAu_gNC與fibAu_sNC)以增加表面拉曼增顯散射(SERS)效果。利用結晶紫(crystal violet, CV)做為分子探針來評估增顯效果後發現與奈米簇之厚度有關。金與銀奈米簇層的蒸鍍厚度因而被選擇並蒸鍍於奈米柱表面上。之後選用4-氨基苯硫酚(4-ABT)與第一型膠原蛋白(collagen type-I)做為目標物，在與金或銀奈米粒子混合後置於fibAu_sNC基板上後使用拉曼光譜儀量測，結果顯示這種由奈米簇於奈米柱上和奈米粒子所形成之雙接面基板結構，將會產生強大的電磁增顯效果。藉由這種奈米結構複合基板，將可以達到單分子量測等級；而對第一型膠原蛋白來說，膠原蛋白中的胺基酸亦可被偵測。由這些初步的結果，我們推測基板中的奈米簇與奈米柱間的許多微小縫隙將會使電磁增顯效應提升，而目標物與奈米粒子混合後置於fibAu_sNC上將可進一步提昇對於SERS量測的靈敏度與選擇性。

    Au or Ag nanoclusters (NCs) were sputtered on focused-ion-beam (FIB) fabricated Au nanorod (NR) array (fibAu_gNC and fibAu_sNC) to promote the effect of surface enhanced Raman scattering (SERS). The effect was estimated by crystal violet (CV) as the probe molecule and found to rely on the agglomerated thickness of NCs. A thin-layer deposition of Au or Ag on the top and side surfaces of NR was thereafter chosen. Furthermore examinations on 4-aminobenzenethiol and collagen type-I, mixing with AuNPs or AgNPs upon fibAu_sNC, showed that a strong electromagnetic field effect is presumably generated at the two hot-spot junctions, namely, NPs with NCs and NCs with NRs. Through this hybrid nanostructure system, trace detection at the single molecule level can be reached. In particular for the collagen type-I target, the quality of amino acids can also be detected. Based upon this preliminary study, a small gap at the NCs on NR interface may increase the localized EM field, while target species mixed with NPs place upon fibAu_sNC additionally increase the sensitivity and selectivity of SERS-active detection.

    摘要 I Extended Abstract II 誌謝 VIII 表目錄 XII 圖目錄 XIII 第一章 導論 1 1.1 研究背景 1 1.2 研究動機 2 1.3 文獻回顧 3 1.3.1 金奈米柱陣列基版的製作與效果 3 1.3.2 奈米簇結構在拉曼增顯活性基版的控制與應用 4 1.3.3 拉曼光譜對4-ABT的量測應用 6 1.3.4 拉曼光譜對第一型膠原蛋白的量測應用 7 1.4 研究目的 8 第二章 理論基礎 10 2.1振動光譜 10 2.2 拉曼光譜基本理論 12 2.2.1 拉曼散射原理 12 2.2.2 拉曼光譜之極化誘發理論 13 2.3 表面增顯拉曼散射光譜 15 2.3.1 表面電漿(surface plasmon) 16 2.3.2 電磁效應在奈米柱上的作用 18 2.4 第一型膠原蛋白與基質金屬蛋白酶-9 20 第三章 材料與方法 21 3.1 實驗設計 21 3.2 實驗流程 21 3.3 實驗材料與製備 22 3.3.1 鍍金基板製作 22 3.3.2 金奈米柱SERS活性基板製作 23 3.3.3 分子探針溶液與奈米粒子製備 24 3.3.4 拉曼檢測與訊號處理 25 3.3.5增顯因子(enhancement factor, EF)之評估 26 3.4 製程儀器 27 3.4.1 電子束蒸鍍機 27 3.4.2 雙束型聚焦離子束 28 3.5 分析儀器 29 3.5.1 掃描式電子顯微鏡 29 3.5.2 顯微拉曼光譜儀 30 3.5.3 原子力顯微鏡 31 3.5.4 穿透式電子顯微鏡 32 第四章 結合奈米簇與奈米柱陣列SERS活性基板之效能評估 34 4.1 奈米簇與奈米柱陣列基板之結合與分析 34 4.1.1 奈米簇與奈米柱陣列基板之結合與分析 34 4.1.2 奈米簇之表面形貌與粗糙度分析 35 4.1.3 蒸鍍奈米簇於奈米柱陣列之表面形貌與基板成分分析 38 4.2 不同奈米簇蒸度厚度之誘發SERS效應分析 42 第五章 4-氨基苯硫酚與裂解第一型膠原蛋白之拉曼光譜分析 46 5.1 4-氨基苯硫酚之拉曼光譜分析 46 5.1.1 金、銀奈米粒子之合成及與4-氨基苯硫酚混合結果 46 5.1.2 4-氨基苯硫酚於雙接面結構基板之檢測應用 48 5.2 第一型膠原蛋白之拉曼光譜分析 51 5.2.1金、銀奈米粒子與第一型膠原蛋白混合與量測 51 5.2.2 第一型膠原蛋白與基質金屬蛋白酶-9作用檢測與分析 54 5.3 拉曼增顯之可能機制討論 58 結論 60 未來展望 61 參考文獻 62

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