以嵌段共聚物模板製備金納米結構藉由SERS光譜進行分子傳感

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蓓達(Belda Amelia Junisu) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

以嵌段共聚物模板製備金納米結構藉由SERS光譜進行分子傳感
(Block-Copolymer Templated Gold Nanostructures for Molecular Sensing through SERS Spectroscopy)

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摘要(中)

兩性高分子的自組裝奈米結構近來在奈米科學界上引起了相當程度的關注。將具有自組裝行為的高分子摻混金屬作為奈米結構模板有很廣的應用層面，例如表面增強拉曼散射(SERS)。表面增強拉曼散射(SERS)是一個偵測、追蹤許多無機及有機材料的重要工具。高分子的自組裝行為可以避免金奈米粒子發生團聚現象，此團聚現象在某種程度上會降低表面增強拉曼散射(SERS)的表現。有鑑於此，在此研究中，透過表面重組方法，以聚-2-乙烯基吡啶奈米微胞多層結構為材料(SR-PS-b-P2VP)，利用嵌段高分子自組裝行為製備奈米多孔網狀結構。透過在氮氣氣氛下照紫外光的方法，使高分子模板穩定，減少金離子並且在高分子模板上形成金的晶種(GS-PS-b-P2VP)。並且利用後續成長方式製備金奈米結構。結果上來說，我們成功利用晶種成長方法透過軟質模板製備出相互交連的金骨架結構。以羅丹明6G分子在金基材為例，在1µM R6G濃度的情況下，表面增強拉曼散射(SERS)的增強因子大約為106；而10µM濃度的R6G，表面增強拉曼散射(SERS)的增強因子可以達到大約108。此結果證明，利用本實驗簡單且低成本的方式所製備出的金奈米結構，在表面增強拉曼散射(SERS)的相關應用上有優異的表現。

摘要(英)

Self-assembled nanostructures from amphiphilic block copolymers have received interests in nanoscience and nanotechnology. Incorporating metals within self-assembled block-copolymer nanodomains as a template could form versatile and robust nanostructures with a broad range of applications, including surface-enhanced Raman scattering (SERS) enhancement. SERS is an important tool for the analytical, trace detection of many inorganic and organic materials. Self-assembly can avoid aggregation of gold nanostructures which could decrease its performance in some way. Hence, in this study, self-assembly of BCP was used to form nanoporous networks through surface reconstruction of micellar films of multilayer thickness (SR-PS-b-P2VP). UV irradiation in nitrogen (UVIN) was used to stabilize the template and to reduce the gold ions to form gold seeds (GS-PS-b-P2VP). Gold nanostructure (GN-PS-b-P2VP) were further formed through the growth approach. As a result, a straightforward seed-growth method allows the formation of gold interconnected frameworks through templating of the soft template. The corresponding enhancement factor of gold substrates using R6G as the model molecule are ~108 and ~106 folds for 10 µM and 1 µM R6G, respectively. Such results prove the excellent performance of gold nanostructure fabricated from a relatively simple and cost-effective method for high potential in SERS-related applications.

關鍵字(中)

★ Surface reconstruction
★ Self-assembly
★ PS-b-P2VP
★ Gold interconnected frameworks
★ SERS enhancement

關鍵字(英)

論文目次

Table of Contents
Chinese Abstract i
Abstract ii
Acknowledgement iii
Table of Contents iv
List of Figures vi
List of Tables xii
CHAPTER I 1
INTRODUCTION 1
CHAPTER II 5
LITERATURE REVIEW 5
2.1 Gold Nanostructure 5
2.1.1 Fabrication Methods of Gold Porous Nanostructures 6
2.1.2 Optical Properties of Gold Nanostructures 15
2.2 Raman Spectroscopy 19
2.2.1 Surface Enhanced Raman Scattering (SERS) 23
2.2.2 Surface Plasmon Resonance (SPR) 25
2.2.3 SERS Enhancement Factor 27
2.2.4 Possible SERS Substrates (Metallic Substrates) 30
2.2.5 Development of Au Metallic Substrates in SERS Applications 31
2.3 Self-Assembly Block Copolymer (BCP) 37
2.3.1 Micelle Formation in Bulk and Solution System 38
2.3.2 BCP as a Template on The Growth of Metal Nanostructure 40
2.3.3 The Development of BCP-Templated Gold Nanostructure 42
CHAPTER III 45
EXPERIMENTAL METHODS 45
3.1 Materials 45
3.2 Instruments 46
3.3 Experimental Section 47
3.4 Instrumental Analysis 50
3.4.1 Field Emission Scanning Electron Microscope (FE-SEM) 50
3.4.2 X-Ray Diffraction (XRD) 52
3.4.3 X-Ray Photoelectron Spectroscopy (XPS) 53
3.4.4 UV-Visible (UV-Vis) Spectroscopy 54
3.4.5 Transmission Electron Microscopy (TEM) 55
3.4.6 Atomic Force Microscopy 57
3.4.7 Surface Enhanced Raman Spectroscopy 58
CHAPTER IV 60
RESULTS AND DISCUSSION 60
4.1 Fabrication and Characterization of Polymer Template 61
4.2 Fabrication and Characterization of Gold Seeds 67
4.3 Growth and Characterization of Gold Nanostructure 75
4.4 SERS Performance of Dye Molecules Absorbed on Gold Nanostructures 86
CHAPTER V 97
CONCLUSION 97
REFERENCES 98

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指導教授

孫亞賢(Ya-Sen Sun)

審核日期

2019-7-9

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