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研究生： 侯斯揚
Hou, Szu-Yang
論文名稱： 金奈米粒子沉積於介電材料成為具增顯拉曼散射活化基材應用於微量農藥檢測
Gold Nanoparticles Deposited on Dielectric Materials as SERS-active Substrates for Trace Detection of Pesticides
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： 2020
畢業學年度： 108
語文別： 中文
論文頁數： 73
中文關鍵詞： 表面增顯拉曼散射 、介電材料 、奈米金顆粒 、溶膠凝膠法 、電子束蒸鍍
外文關鍵詞： SERS, dielectric material, sol-gel, e-beam evaporation, gold nanoparticles
相關次數： 點閱：107  下載：0 
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    • 本研究將會利用模板輔助法的方式來製備SERS活性基板，利用溶膠凝膠法合成三種介電材料(ZrO2、TiO2、Al2O3)的奈米微結構，並透過調整前驅溶液濃度以變化三種試片的表面形貌，獲得具有奈米等級粗糙度的表面以及相近的矽基板覆蓋率，再結合電子束蒸鍍法(E-beam evaporator)沉積金奈米顆粒於試片表面以製備為SERS活性基板，觀察三種介電材料在相近的基板覆蓋率之下，對SERS增顯效果的貢獻。
    於介電材料試片的製備研究中，藉由調整前驅液液濃度以評估其對於表面結構的影響，其結果顯示:氧化鋯在低濃度時所得到的表面形貌為平坦的薄膜，0.3 M時獲得奈米纖維結構；二氧化鈦在低濃度下有些許顆粒產生，0.3 M時觀察到類似珊瑚礁狀的微結構；氧化鋁於0.1 M時出現細小顆粒，濃度提升到0.3 M時顆粒逐漸相連形成迷宮狀的微結構。在R6G檢測方面，三種材料的活性基板都在0.3 M時得到最佳的增顯效果，增顯因子由Au/Z_0.3、Au/T_0.3以及Au/A_0.3依序為1.13107、4.8106 以及2.5106，並且發現介電材料的堆疊結構相較於薄膜結構，所得到的拉曼訊號強度可以提升至7倍。
    而於微量農藥檢測的研究中，選用兩種農藥作為檢測物質：(1)賽滅寧、(2)巴拉松，檢測結果顯示，三個材料最佳試片均可以檢測出10-6 M的賽滅寧，符合我國所訂定之農藥殘留極限標準。巴拉松的檢測極限濃度依Au/Z_0.3, Au/T_0.3和Au/A_0.3順序分別為10-7 M, 10-6 M和10-5 M。
    綜合以上的研究成果顯示：利用溶膠凝膠法製備氧化鋯、二氧化鈦以及氧化鋁試片，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，於微量農藥檢測中有高靈敏度的表現；此外，其製備流程簡易且適用於大範圍面積的製備，適合應用於SERS技術於商品化發展的新趨勢。

    Trace detection of bio-chemical substances such as pathogenic microorganisms, polycyclic aromatic hydrocarbons and pesticides is necessary, given the potential health risk to consumers, thus a simple, straightforward, and effective analytical method is required. One of the sensitive and rapid detection methods that has been developed for a long while is surface-enhanced Raman scattering (SERS) since it requires minimal to no sample pretreatment. In this study, gold nanoparticles deposited onto three different dielectric materials templates (ZrO2, TiO2, Al2O3) prepared by the sol-gel spin-coated method were used as SERS-active substrates to observe the contribution of three dielectric materials to the enhancement effect of SERS under similar substrate coverage rate. With an optimized substrate-laser wavelength combination and Rhodamine 6G (R6G) as the probe molecular, the highest enhancement factor (EF) of 1.13 x 107 was obtained from sample Au/Z_0.3. Furthermore, the optimized SERS-active substrates Au/Z_0.3 were competent to detect two types of pesticides, including cypermethrin and parathion. The limit of detection were 10-6 M for cypermethrin, 10-7 M for parathion. The presence of hot spots in Au-Au interparticle gaps and the formation of electromagnetic fields on the Au-dielectric materials interfaces due to charge transfer between Au and ZrO2, TiO2, and Al2O3 are major factors that contribute to the SERS effect; in addition, the stacked nanostructures allowed the incident light to scatter repeatedly. The results show that the sample Au/Z_0.3 is a promising tool for trace detection of pesticides.

    目錄 摘要 I 第一章 緒論 1 1.1 前言 1 1.2 研究動機 4 第二章 文獻回顧與理論基礎 5 2.1 振動光譜 5 2.2 拉曼光譜基本理論 7 2.2.1. 拉曼散射原理 7 2.2.2. 拉曼光譜之極化誘發理論 8 2.3 表面增顯拉曼散射光譜 10 2.3.1. 表面增顯拉曼散射光譜於奈米結構表面機制 10 2.3.2. 表面電漿(surface plasmon) 12 2.3.3. 電磁效應(electromagnetic effect) 14 2.3.4. 化學效應(chemical effect) 16 2.4 表面增顯拉曼散射用於微量農藥檢測 19 2.5 表面增顯拉曼活性基板的製備 20 2.6 溶膠凝膠法(Sol-gel Method) 23 2.7 介電材料特性 24 2.7.1. 氧化鋯特性 24 2.7.2. 二氧化鈦特性 25 2.7.3. 氧化鋁特性 26 2.8 研究目的 27 第三章 材料與方法 29 3.1 實驗架構與流程 29 3.2 實驗材料與方法 30 3.2.1. 基板清洗 30 3.2.2. 溶液製備 30 3.2.3. 基板製作 31 3.2.4. 拉曼檢測 32 3.2.5. 拉曼光譜分析之校正 33 3.2.6. 訊號處理 34 3.2.7. 增顯因子之評估計算 34 3.3 製程儀器 35 3.4 分析儀器 36 3.4.1. 場發射掃描式電子顯微鏡 ( SEM ) 36 3.4.2. 場發射高解析電子微探儀 ( EPMA ) 36 3.4.3. X射線繞射分析儀 ( XRD ) 37 3.4.4. 顯微拉曼光譜儀 ( Raman spectrometer ) 38 第四章 SERS活性基板之評估 40 4.1 試片特性分析 40 4.1.1. 組成成分分析 40 4.1.2. 表面形貌分析 42 4.2 活性基板之表面形貌與元素分析 45 4.3 綜合討論 47 第五章 SERS活性基板應用於分子探針與微量農藥 48 5.1 SERS活性基板增顯效益之評估 48 5.1.1. 濃度與激發雷射波長之最佳化 48 5.1.2. 表面增顯拉曼散射光譜之分析 51 5.2 SERS活性基板應用於農藥樣品之檢測極限 52 5.2.1. 賽滅寧(Cypermethrin) 52 5.2.2. 巴拉松(Parathion) 55 5.3 SERS機制之探討 58 5.4 綜合討論 63 結論 64 未來展望 65 參考文獻 References 66   表目錄 Table 2-1: The comparison between infrared spectroscopy and Raman spectroscopy. 6 Table 3-1: The parameters of samples. 32 Table 3-2: The parameters of SERS-active substrates. 32 Table 4-1: XRD patterns of zirconia and the corresponding miller index. 41 Table 4-2: XRD patterns of titanium dioxide and the corresponding miller index. 42 Table 4-3: The diameter and coverage rate of ZrO2 nanofibers on various samples. 44 Table 4-4: The diameter and coverage rate of TiO2 nanoparticles on various samples. 44 Table 4-5: The spacing of Au nanoparticles on different samples, which was evaluated by software image J. 47 Table 5-1 : The EFs of samples with laser wavelength of 633 and 785 nm. 52 Table 5-2: Different conditions of each sample has, samples which have most conditions will get higher enhancement factor. 62   圖目錄 Fig. 2-1: Different types of vibrational modes. 5 Fig. 2-2: The comparison of energy level between Rayleigh and Raman scattering. 8 Fig. 2-3: Raman spectrum of CCl4 with 488 nm laser. It shows the relationship about three different kinds of light scattering[41]. 8 Fig. 2-4: The comparison of Raman intensity between (a) normal Raman scattering and (b) surface-enhanced Raman scattering. 12 Fig. 2-5: Raman spectra of MB cast from an aqueous solution on:(a) a layer of PMMA nanofibers and (b) on a spin-coated PMMA film. 12 Fig. 2-6: Illustration of surface plasmon oscillation. 13 Fig. 2-7: The dispersion relation of the plasmon between air-Ag interface, (1) the plane wave in vacuum and (2) the surface plasmon wave. 14 Fig. 2-8: Simple schematic diagram for the concept of LSPR and EM effects. 16 Fig. 2-9: Simple schematic diagram for the concept of hot spot. 16 Fig. 2-10: Simple schematic diagram for the concept of chemical effect. 17 Fig. 2-11: Energy diagram for photo induced vertical electron transfer from Ag(111) to the physisorbed vinyl chloride. 18 Fig. 2-12: (a) Raman spectrum of 4-ATP measured with (і) 532 nm and (іі) 633 nm; (b) SERS spectrum of 4-ATP (1) adsorbed on Au and (2) deposited on PVP spacer layer over Au film. 19 Fig. 2-13: SERS substrates applied for in situ pesticide detection. (a) AuNPs, (b) Ag NPs (fabricated in situ), (c) Au@SiO2 NPs, (d) Au@Ag NPs,and (e) Au NPs grafted on dendritic α-Fe2O3[8]. 19 Fig. 2-14: SERS spectra (a) from the pesticide containing aple peels in comparison with (b) a standard solution[64]. 20 Fig. 2-15: Schematics of tilted nanorods formation through the process of oblique angle deposition (OAD)[21]. 21 Fig. 2-16: Patterned nanoaggregates through electron beam lithography. By using this method, the nanoaggregates could be reproduced [17]. 22 Fig. 2-17: Steps for preparing Au NPs/ZrO2 nanofibers[64]. 23 Fig. 2-18: Phase diagram of yttria-stabilized zirconia[73]. 25 Fig. 2-19: Stripping voltammograms of (a) bare gold electrode and (b) ZrO2/Au electrode after 2-min adsorption in stirring 0.1 M of KCl solution containing 200 ng/mL methyl parathion. Potential scanning potential. -0.4 to +0.3 V[75]. 25 Fig. 2-20: Phase diagram of TiO2[76]. 26 Fig. 2-21: SERS spectra of pyridine on the Ti- and Al-based hybrid materials.[77] 27 Fig. 3-1: Scheme of fabrication process of substrates: (a) Spin coating precursor solutions onto Si wafer. (b) Heat treatment of precursor solutions onto Si substrate. (c) Deposition of gold nanoparticles. (d) Optimizing of SERS substrates. 29 Fig. 3-2: The molecular structure of R6G. 31 Fig. 3-3: Raman spectra of standard silicon wafer. 34 Fig. 3-4: The standard Raman spectrum of R6G. 34 Fig. 3-5: Schematic diagram of e-beam evaporation[80]. 36 Fig. 3-6: The structure of an EPMA device. 37 Fig. 3-7: Schematic diagram of Raman spectrometer[81]. 39 Fig. 4-1: grazing XRD patterns of (a) ZrO2, (b) TiO2 and (c) Al2O3. 41 Fig. 4-2: FE-SEM images of zirconia samples obtained from precursor concentration of (a) 0.05, (b) 0.1, (c) 0.3 M. 43 Fig. 4-3: FE-SEM images of Titania samples obtained from precursor concentration of (a) 0.05, (b) 0.1, (c) 0.3 M. 43 Fig. 4-4: FE-SEM images of alumina samples obtained from precursor concentration of (a) 0.05, (b) 0.1, (c) 0.3 M. 43 Fig. 4-5: AFM images of sample (a)Au/Z_0.3, (b)Au/T_0.3 and (c)Au/A_0.3. 44 Fig. 4-6: FE-SEM images of sample (a)Au/Z_0.3 and (b)Au/T_0.3. Uniform gold nanoparticles were deposited onto zirconia nanofibers and Titania nanoparticles. 46 Fig. 4-7: EMPA mapping patterns of sample Au/Z_0.3, figures from left to right represent to Au/Z_0.3 SEI, zirconium signal mapping pattern and Au signal mapping pattern. 46 Fig. 4-8: EMPA mapping patterns of sample Au/T_0.3, figures from left to right represent to Au/T_0.3 SEI, titanium signal mapping pattern and Au signal mapping pattern. 46 Fig. 4-9: The size distribution histogram of Au nanoparticles on sample (a)Au/Z_0.3 and (b)Au/T_0.3. Random 200 particles on Fig. 4-6(a) and Fig. 4-6 (b) were used to calculate the size. 47 Fig. 5-1: SERS spectra of 10-3 M R6G adsorbed on (a) Au/ZrO2, (b) Au/TiO2 and (c) Au/Al2O3 examined by 633 nm laser. 100% coverage of dielectric material, bare gold on Si wafer, bare dielectric material and normal Raman were used as the control group. 49 Fig. 5-2: SERS spectra of 10-3 M R6G adsorbed on various samples examined by (a) 633 nm laser and (b) 785 nm laser. Bare gold on Si wafer was used as the control group. 50 Fig. 5-3: Raman intensity at 1361 cm-1 collected from various samples. The laser wavelengths of 633 and 785 nm were varied. 50 Fig. 5-4: SERS spectra of cypermethrin standard solutions of various concentrations detected by sample (a) Au/Z_0.3, (b) Au/T_0.3 and (c) Au/A_0.3；the molecular structure of cypermethrin is also shown. 53 Fig. 5-5: Linear calibration plot for cypermethrin at 1002 cm-1 peak from (a) Au/Z_0.1, (b) Au/T_0.3, (c) Au/A_0.3 in Fig. 5-4. (d) Put the three linear calibration graphs together for comparison；the error bars represent the relatives errors taken from five independent measurements. 54 Fig. 5-6: Relative Raman intensities of 10-5 M cypermethrin at the 1002 cm-1 peak taken using the Au/Z_0.3, Au/T_0.3 and Au/A_0.3 samples at 633 nm excitation wavelength. 55 Fig. 5-7: SERS spectra of parathion standard solutions of various concentrations detected by sample (a) Au/Z_0.3, (b) Au/T_0.3 and (c) Au/A_0.3；the molecular structure of parathion is also shown. 56 Fig. 5-8: Linear calibration plot for parathion at 1345 cm-1 peak from (a) Au/Z_0.1, (b) Au/T_0.3, (c) Au/A_0.3 in Fig. 5-7. (d) Put the three linear calibration graphs together for comparison；the error bars represent the relative errors taken from five independent measurements. 57 Fig. 5-9: Relative Raman intensities of 10-5 M parathion at the 1002 cm-1 peak taken using the Au/Z_0.3, Au/T_0.3 and Au/A_0.3 samples at 633 nm excitation wavelength. 58 Fig. 5-10: Schematics depicting the interaction of light with (a) flat TiO2 film, (b) ZrO2 nanofibers and with (c) TiO2 nano-coral reef. The arrows schematize the incident laser. The direction of the light is almost unchanged in flat film, while scattering by nanofibers or nano coral deviates the light from their original direction, increasing the probability of interaction with adsorbates. 59 Fig. 5-11: (a) SERS spectrum of 10-3 M R6G detected by sample Au/Z_0.3 and control groups, (b) intensity histogram of 10-3 M R6G at peak 1361 cm-1 from plot (a). 59 Fig. 5-12: (a) SERS spectrum of 10-3 M R6G detected by sample Au/T_0.3 and control groups, (b) intensity histogram of 10-3 M R6G at peak 1361 cm-1 from plot (a). 60 Fig. 5-13: Two mechanism of SERS (i) LSPR effect or hot spot effect, (ii) Interface SPR effect or charge transfer. 61 Fig. 5-14: Conditions of gold on samples (1) Au NPs at short distance (2) Au NPs at longer distance but smaller than 40 nm (3) Au NPs on Si wafer (4) Au NPs couple, one on dielectric material and another on Si wafer. 62

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