臺灣博碩士論文加值系統

本研究將以模板輔助型的方式來製備SERS活性基板，利用溶膠凝膠法合成氧化鋯奈米纖維，透過調整前驅溶液濃度以變化氧化鋯試片的表面形貌，並結合電子束蒸鍍法沉積金奈米顆粒於氧化鋯試片表面以製備為SERS活性基板，氧化鋯對於有機磷劑具有強親和性的特性，能縮短有機磷劑與表面結構的距離，使其落於熱點區域的機率提升，進而增強SERS效應。
於氧化鋯試片的製備研究中，藉由調整前驅溶液濃度以評估其對於表面結構的影響，其結果顯示：於低濃度的試片中，其表面形貌為平坦表面，隨著濃度的提升，奈米纖維的結構逐漸生成，而於濃度0.5 M的試片中以可觀察到部分區域因奈米纖維的生成密集而團聚為塊狀；於SERS活性基板增顯效應的評估中，以R6G作為分子探針，其結果顯示：使用雷射波長633 nm可激發較強的表面電漿共振，而藉由增顯因子的計算，得知以濃度0.3 M所製備的SERS活性基板具有最佳的增顯效應，其增顯因子達2.1 × 107，可應用於單分子的檢測，而其它基板的增顯因子也皆有106。
而於微量農藥檢測的研究中，選用四種農藥作為檢測物質：(1)益滅松、(2)加保利、(3)百滅寧與(4)賽滅寧，其結果顯示本研究之最佳SERS活性基板於賽滅寧的檢測極限濃度達10-6 M，加保利與百滅寧為10-7 M，而益滅松更高達10-8 M，表示本研究之最佳SERS活性基板於微量農藥檢測中具有高靈敏度的表現，此外，混合農藥的檢測分析中，更證實了氧化鋯可提升有機磷劑其增顯效益。
綜合以上的研究成果顯示：利用溶膠凝膠法製備氧化鋯試片，並以電子束蒸鍍沉積奈米金顆粒以製備為SERS活性基板的製程方式，不但於微量農藥檢測中有高靈敏度的表現，且對於有機磷劑有較高的選擇性表現，此外，其製備流程簡易且適用於大範圍面積的製備，正適合應用於SERS技術於商品化發展的新趨勢。

Trace detection of pesticide residues is necessary to assure food safety, given the potential health risks the pesticide residues may pose to consumers, thus a simple, rapid and effective analytical method is required. Surface-enhanced Raman scattering (SERS) has been well developed for detecting target species. Herein, gold nanoparticles deposited onto a template zirconia nanofibers prepared by the spin-coated sol-gel method were used as SERS-active substrates. The morphologies of zirconia samples were easily controlled by adjusting the precursor concentrations. The SERS effects of samples were firstly evaluated by different laser wavelengths using rhodamine 6G (R6G) as the probe molecule. The sample Au/Z_0.3 exhibited the highest enhancement factor of 2.1 × 107. Furthermore, the optimized SERS-active substrates Au/Z_0.3 were competent to detect four types of pesticides, including phosmet, carbaryl, permethrin and cypermethrin. The limits of detection were 10-6 M for cypermethrin, 10-7 M for carbaryl and permethrin, and 10-8 M for phosmet. In the Raman analysis of mixed pesticides, the substrates showed high selectivity to organophosphates. Finally, the characteristic peaks of each pesticide could be still identified in the simulation of detecting pesticides on fruits. The results show that the sample Au/Z_0.3 is a promising tool for trace detection of pesticides on fruits.

摘要 I
Extended Abstract II
誌謝 XI
目錄 XIII
表目錄 XV
圖目錄 XVI
第一章 緒論 1
1.1 前言 1
1.2 研究動機 6
1.3 研究目的 7
第二章 文獻回顧與理論基礎 8
2.1 振動光譜 8
2.2 拉曼光譜基本理論 10
2.2.1 拉曼散射原理 10
2.2.2 拉曼光譜之極化誘發理論 12
2.3 表面增顯拉曼散射光譜 13
2.3.1 表面增顯拉曼散射光譜之發展與簡述 13
2.3.2 表面增顯拉曼散射光譜於奈米結構表面之機制 13
2.3.3 表面電漿(surface plasmon) 15
2.3.4 電磁效應(electromagnetic effect) 17
2.3.5 化學效應(chemical effect) 19
2.4 表面增顯拉曼散射光譜應用於微量農藥檢測 22
2.5 表面增顯拉曼活性基板製備 27
2.5.1 減去法(top-down fabrication) 27
2.5.2 加成法(bottom-up assembly) 29
2.5.3 複合型(combination technique) 29
2.5.4 模板輔助型(template-assisted fabrication) 30
2.6 氧化鋯特性與其製備 31
2.6.1 氧化鋯特性 31
2.6.2 以溶膠凝膠法製備氧化鋯試片 34
第三章 材料與方法 37
3.1 實驗設計與流程 37
3.2 實驗材料與方法 38
3.2.1 基板清洗 38
3.2.2 溶液製備 39
3.2.3 基板製作 40
3.2.4 拉曼檢測 41
3.2.5 拉曼光譜分析之校正 42
3.2.6 訊號處理 43
3.2.7 增顯因子之評估計算 44
3.3 製程儀器 46
3.3.1 電子束蒸鍍機 46
3.4 分析儀器 47
3.4.1 掃描式電子顯微鏡(SEM) 47
3.4.2 X射線繞射分析儀(XRD) 48
3.4.3 顯微拉曼光譜儀(Raman spectrometer) 51
第四章 SERS活性基板應用於分子探針之研究 53
4.1 氧化鋯試片特性分析 53
4.1.1 組成成分分析 53
4.1.2 表面形貌分析 55
4.2 SERS活性基板之表面形貌與元素分析 56
4.3 SERS活性基板之效益評估 58
4.3.1 激發雷射波長之最佳化 58
4.3.2 表面增顯拉曼散射光譜之分析 61
4.3.3 SERS機制之探討 62
第五章 SERS活性基板應用於微量農藥檢測之研究 65
5.1 SERS活性基板於農藥樣品之檢測極限分析 65
5.1.1 益滅松(phosmet) 65
5.1.2 加保利(carbaryl) 66
5.1.3 百滅寧(permethrin) 67
5.1.4 賽滅寧(cypermethrin) 68
5.2 SERS活性基板於多重農藥之應用 69
5.2.1 SERS活性基板於單次多重農藥之檢測 69
5.2.2 SERS活性基板於有機磷劑之親和性分析 71
5.3 SERS活性基板於水果實體之模擬檢測 72
結論 75
未來展望 76
參考文獻 77

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