表面增強拉曼散射( SERS )是一個非常重要的分析技術，且廣泛應用在化學、生物及環境的領域上。而如何製備出一個高增強效應、再現性佳及高穩定度的SERS基材是相當熱門的。本篇透過自組裝的方法來製備SERS活性基材，我們利用APS、APTES以及Poly-L-Lysine來進行分子自組裝修飾，FT-IR及XPS鑑定薄膜的形成，AFM觀察表面形貌並測量表面粗糙度，發現APTES易產生聚集現象，使表面粗糙度大增，而APS及Poly-L-Lysine則形成平滑無聚集的薄膜。藉由薄膜上的胺基( -NH2 )與金奈米粒子間的高親和力，將金奈米粒子固定於固態基板上，並用AFM觀察表面奈米結構。而在SERS實驗部分，使用4-MBA為探測分子，偵測極限可達到10-6 M。此外，所製備之SERS活性基板也有很好的再現性及穩定度。過去二十年來，利用金奈米粒子進行的非勻相催化反應引起科學家廣大的興趣。因此，我們將所製備之SERS活性基材，應用於監控金奈米粒子所催化之化學反應，以4-NTP還原為4-ATP的反應作為研究對象，成功觀察到SERS光譜的形貌隨時間產生變化，藉由動力學之分析，顯示此反應為一級反應，而UV-Vis光譜之結果也證實了金奈米粒子具催化活性。

Surface-enhanced Raman scattering ( SERS ) has become an important analytical tool, and it has broad applications in the fields of chemistry, biology and environmental science. However, how to prepare a SERS-active substrate with high enhancement, good reproducibility and stability is a big challenge. In this study, we prepared the SERS-active substrate through self-assembly method. We used APS, APTES and Poly-L-Lysine for surface modification, and the films were characterized by FT-IR and XPS. AFM was use to characterize the surface morphology and measure the surface roughness. It was found that APTES was prone to forming molecular aggregates on the surface, leading to the increase in surface roughness. In contrast, APS and Poly-L-Lysine created a smooth and aggregate-free film. Then, the gold nanoparticles could be immobilized on solid supports by its high affinity to amine groups, and the nanostructure of the surface was investigated by AFM and UV-Vis spectroscopy. In SERS measurements, 4-MBA was chosen as a probe molecule to test the performance of the substrate, and the detection limit is 10-6 M. Furthermore, the substrate showed excellent reproducibility of the gold nanostructure and good stability over time. In the past two decades, heterogeneous catalysis with gold nanoparticle has received a great deal of attention. Therefore, we employed the SERS-active substrate for monitoring the Au-catalyzed reduction of 4-NTP to 4-ATP, and it was observed successfully that the feature of the SERS spectra changed over different reaction times. Kinetic study indicates that this reaction follows first-order kinetics, and the result of UV-Vis spectroscopy also demonstrated that gold nanoparticle exhibit catalytic activity.

摘要 i
Abstract ii
目錄 iii
圖次 vii
表次 xi
第一章 緒論 1
1-1 拉曼散射 ( Raman Scattering ) 1
1-1-1 簡介 1
1-1-2 拉曼散射機制 2
1-1-3 拉曼散射理論 4
1-2 表面增強拉曼散射 ( Surface Enhanced Raman Scattering, SERS ) 7
1-2-1 簡介 7
1-2-2 電磁場增強效應 ( electromagnetic enhancement ) 8
1-2-3 化學增強效應 ( chemical enhancement ) 9
1-3 研究動機 12
第二章 儀器介紹 13
2-1 原子力顯微鏡 ( Atomic Force Microscopy, AFM ) 13
2-1-1 簡介 13
2-1-2 原理 14
2-1-3 工作模式 16
2-1-4 使用儀器及參數設定 18
2-2 傅立葉轉換紅外光譜儀 ( Fourier Transform Infrared Spectrometer, FT-IR ) 19
2-2-1 原理 19
2-2-2 使用儀器與參數設定 23
2-3 紫外/可見光光譜儀 ( Ultraviolet-Visible Spectrometer ) 24
2-3-1 比爾定律 ( Beer’s Law ) 24
2-3-2 紫外/可見光光譜 ( Ultraviolet-Visible Spectrometry, UV-Vis ) 25
2-3-3 使用儀器與參數設定 27
2-4 拉曼光譜儀 ( Raman Spectrometer ) 28
2-4-1 簡介 28
2-4-2 使用儀器與參數設定 28
2-5 接觸角量測儀 ( Contact Angle Meter ) 29
2-5-1 原理 29
2-5-2 使用儀器與參數設定 31
第三章 金奈米粒子組裝於固態基材上作為表面增強拉曼散射之平台 32
3-1 前言 32
3-2 文獻回顧 34
3-2-1 自組裝單分子薄膜 ( Self-assembled monolayer, SAM ) 34
3-2-2 金奈米粒子之特性與應用 37
3-3 實驗部分 38
3-3-1 實驗藥品 38
3-3-2 實驗材料 39
3-3-3 實驗流程 40
3-3-3-1 基板準備 40
3-3-3-2 SERS活性基板製備 40
3-3-3-3 FT-IR樣品製備 41
3-3-3-4 UV-Vis樣品製備 41
3-3-3-5 Contact angle樣品製備 42
3-3-3-6 XPS樣品製備 42
3-3-3-7 SERS實驗部分 42
3-3-3-8 實驗流程示意圖 42
3-4 結果與討論 44
3-4-1 自組裝單分子薄膜之表面分析與鑑定 45
3-4-1-1 AFM觀察表面形貌與表面粗糙度測量 45
3-4-1-2 FT-IR鑑定薄膜之形成 51
3-4-1-3 XPS鑑定薄膜之形成 52
3-4-1-4 Contact angle測量薄膜表面特性 54
3-4-2 金奈米結構之鑑定 56
3-4-2-1 UV-Vis光譜測量金奈米結構之光學特性 56
3-4-2-2 AFM鑑定金奈米結構 59
3-4-3 金奈米結構之SERS測試 62
3-4-3-1 偵測極限 63
3-4-3-2 靈敏度 66
3-4-3-3 再現性 68
3-4-3-4 穩定度 68
3-5 結論 70
第四章 表面增強拉曼散射應用於監控金奈米粒子催化之化學反應 71
4-1 前言 71
4-2 實驗部分 73
4-2-1 實驗藥品 73
4-2-2 實驗材料 74
4-2-3 實驗流程 74
4-3 結果與討論 75
4-3-1 SERS監控金奈米粒子催化4-NTP之還原反應 75
4-3-2 金奈米粒子具催化活性之證據 83
4-4 結論 89
第五章 結論 90
第六章 未來展望 91
參考文獻 92

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