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系統識別號 U0026-0208201816355500
論文名稱(中文) 不同介電奈米粒子修飾於銀空心奈米球體陣列表面以強化SERS效應並應用於Ampicillin之檢測
論文名稱(英文) Silver Hollow Nanosphere Arrays Surface-modified with Dielectric Nanoparticles to Improve the Effect of SERS and Apply for Ampicillin Detection
校院名稱 成功大學
系所名稱(中) 材料科學及工程學系
系所名稱(英) Department of Materials Science and Engineering
學年度 106
學期 2
出版年 107
研究生(中文) 楊家瑋
研究生(英文) Jia-Wei Yang
學號 N56051302
學位類別 碩士
語文別 英文
論文頁數 83頁
口試委員 指導教授-廖峻德
共同指導教授-劉浩志
共同指導教授-王士豪
口試委員-傅尉恩
中文關鍵字 SERS  介電材料  LSPR效應  氨芐西林  殘留檢測 
英文關鍵字 SERS  dielectric material  LSPR effect  Ampicillin  residue detection 
學科別分類
中文摘要 殘留抗生素檢測在現今非常重要,而表面增顯拉曼散射技術(SERS)提供了高機率去檢測出微量檢測分子,使該技術獲得了更多的關注。而使用自組裝單層聚苯乙烯(PS)奈米球作為犧牲輔助模板,再用各種介電奈米粒子(HfO2,TiO2和Al2O3)去修飾的銀空心奈米球體(HNS)陣列,被證明其做為SERS活性基板的潛力。透過電子束蒸鍍沉積銀空心奈米球體和介電奈米顆粒(NP),此製造方法具有簡易,大規模生產和易於尺寸調整的優點。掃描式電子顯微鏡(SEM)圖像顯示其結構呈現六方最密排列,而原子力顯微鏡(AFM)則顯示沉積的銀外殼薄膜其表面形態和粗糙度呈現均勻分佈。源自於銀空心奈米球體間和金屬/介電界面的局部表面電漿共振(LSPR)效應,使介電奈米顆粒修飾的銀空心奈米球體系統表現出優於單獨銀空心奈米球體陣列的拉曼散射增顯效應。本研究對選用的介電材料其對SERS增顯提升效果進行了詳細的比較,在實驗結果中進行了分析及解釋,並且使用羅丹明紅(R6G)作為探測分子驗證SERS效應,證明本研究的SERS活性基板適用於拉曼散射增顯檢測。在三者基板中,以Al2O3奈米顆粒修飾的銀空心奈米球體系統顯示出最佳的增強因子(EF)為6.2×107。最後,SERS活性基板用於氨芐西林的拉曼訊號檢測,其可檢測的最低濃度為0.01ppm,符合最低法規標準,證明本研究之SERS活性基板為一具有前瞻性的微量抗生素檢測工具。
英文摘要 The detection of residual antibiotics is of great importance nowadays. Surface enhanced Raman scattering (SERS) provides a high chance in detecting trace molecules, so this technique gains more attention. The use of silver hollow nanosphere (HNS) arrays decorated with various dielectric nanoparticles (HfO2, TiO2, and Al2O3) using self-assembled monolayer polystyrene (PS) nanospheres as the sacrificial template is an attempt to demonstrate their potential as SERS-active substrates. Silver HNS and dielectric nanoparticles (NP) were deposited by E-beam evaporation. This fabrication method has the advantages of simplicity, large scale production, and easy size adjustment. Scanning electron microscopy (SEM) images show that the hybrid structures are hexagonally arranged, and Atomic force microscopy (AFM) shows that the surface morphology and the thickness of the deposited silver films are uniform. The dielectric NP modified silver HNS system exhibits superior Raman scattering enhancements than silver HNS alone due to the local surface plasmon resonance (LSPR) effect which originated from the silver HNSs and metal/semiconductor interface. The SERS enhancement with various dielectric materials was thoroughly compared and explained in experimental results. SERS application was verified using Rhodamine 6G (R6G) as a probe molecule, and the fabricated substrate was proven to be an effective SERS template for Raman signal detection. Al2O3 nanoparticles decorated on silver HNS exhibited the optimized enhancement factor (EF) value, which was found to be 6.2 x 107. Finally, the SERS-active substrate was used for Raman detection of Ampicillin, and the lowest concentration it can detect was 0.01 ppm, meeting the minimum legal standards, and showing that the SERS-active substrate is a promising tool for trace detection of antibiotics.
論文目次 摘要 I
Abstract II
誌謝 III
Chapter 1 Introduction 1
1.1 Introduction 1
1.2 Motivation 5
1.3 Objective 5
Chapter 2 Literature survey and Theoretical basis 7
2.1 Vibrational spectroscopy and Raman spectroscopy theory 7
2.1.1 Vibrational spectroscopy 7
2.1.2 Raman spectroscopy theory 10
2.2 Surface enhanced Raman scattering spectroscopy 12
2.2.1 The development of SERS spectroscopy 12
2.2.2 SERS mechanism with the surface of nanostructures 12
2.2.3 Surface plasmon 14
2.2.4 Electromagnetic effect 16
2.2.5 Chemical effect 18
2.3 SERS-active substrate 20
2.3.1 Metal/semiconductor plasmonic system 20
2.3.2 Hollow nanosphere structure 26
2.4 SERS technique in antibiotics detection 27
2.5 Summary 30
Chapter 3 Materials and methods 31
3.1 Experimental materials and methods 32
3.1.1 Substrate cleaning 32
3.1.2 Solution preparation 32
3.1.3 Substrate fabrication 34
3.2 Raman detection 36
3.2.1 Raman detection methods 36
3.2.2 Raman spectroscopy correction 37
3.2.3 Signal processing 39
3.2.4 Enhancement factor evaluation and calculation 39
3.3 Process equipment 40
3.3.1 E-beam evaporator 40
3.4 Analytical Instruments 41
3.4.1 Scanning electron microscopy 41
3.4.2 Atomic Force Microscopy 43
3.4.3 Raman spectrometer 44
Chapter 4 SERS-active substrate characteristics analysis 47
4.1 PS monolayer assisted-template analysis 47
4.2 Ag HNS substrate analysis 49
4.2.1 Surface morphology 49
4.2.2 Internal structure analysis 51
4.2.3 Raman spectra analysis and excitation laser wavelength optimization 52
4.3 SERS-active substrate analysis 54
4.3.1 SERS-active substrate Ag/Hf analysis 55
4.3.2 SERS-active substrate Ag/Ti analysis 55
4.3.3 SERS-active substrate Ag/Al analysis 56
4.4 The evaluation of SERS-active substrate enhancement 57
4.4.1 SERS spectra analysis 57
4.4.2 SERS spectra enhancement factor evaluation 58
4.4.3 SERS mechanism discussion 60
4.5 Summary 62
Chapter 5 SERS-active substrate in application of residue antibiotics detection 64
5.1 Detection limits of SERS-active substrates on Ampicillin 64
5.1.1 Ampicillin 64
5.1.2 Raman spectrum analysis of various concentrations on Ag/Hf water sample 65
5.1.3 Raman spectrum analysis of various concentrations on Ag/Al water sample 66
5.1.4 Raman spectrum analysis of various concentrations on Ag/Ti water sample 68
5.1.5 The evaluation of SERS-active substrate enhancement 71
5.2 Simulation of SERS-active substrates in milk detection 72
5.3 Summary 75
Conclusion 76
References 77

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