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標題: 探討無電極置換法製備銀奈米材修飾鋅板之效果及其表面增強拉曼散射效應
Electroless Deposition Method in Preparation of Silver Nanomaterials on Zinc Substrates for Surface Enhanced Raman Scattering Measurement
作者: 陳俊瑋
Chen, Chun-Wei
關鍵字: Raman scattering;拉曼散射;Surface enhanced Raman scattering;SERS;Electroless deposition;Zinc substrates;Amino additve;表面增強拉曼散射;無電極置換;鋅基材;氨類添加劑
出版社: 化學系所
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本研究以鋅金屬做為基板, 利用無電極置換法(Electroless
deposition)製備奈米銀材於基板上,做為表面增強拉曼散射(Surface enhanced Raman Scattering, SERS)基材,透過感測硝基硫苯酚的拉曼訊號、最佳化反應條件,達到提升SERS 訊號之目的。為瞭解反應條件對形成銀材形態之影響,以及瞭解SERS 訊號與形態的關係,本研究透過使用掃描式電子顯微鏡(Scanning electron microscope, SEM)取得各種條件下製備出之奈米銀材的形態,並與SERS 訊號作相關性探討,為有效控制奈米銀材之形態,本研究透過使用胺類化合物之添加達到有效製備結合SERS 量測之奈米銀材。
為瞭解反應機制與最佳化反應條件,研究分為兩部份:其一為單一胺類添加劑對SERS 基板製備之影響。其二為混合式胺類添加劑對SERS 基板製備之影響。在單一胺類添加劑影響之研究中,舉凡反應時間、反應溫度、添加劑濃度與物種皆詳加討論。實驗結果顯示10 mM 硝酸銀與550 mM ethylamine 反應50 分鐘之鋅基板其效果最好,增強倍率可達到10的6次方倍。胺類添加劑之濃度提高有助於降低反應速率,以便製備出奈米銀材具有較高之晶性,SERS 訊號也相對提高,反應溫度之降低亦與高濃度添加劑之效果相同,亦即有助於SERS 訊號之提升,以胺類物種而言,具較短碳鍵之一級胺類分子對基材之製備有正面之效果尤其ethylamine 之效果最佳。在混合式胺類添加劑使用效果的探討上,實驗以ethylamine 為主要物種經添加第二種胺類分子後,觀察形態的變化結果。當使用長鏈分子作為第二添加劑時,隨著鏈長和濃度的提高銀材呈現樹叢狀的晶性結構。由當使用直鏈雙胺分子作為第二添加劑時,短鏈雙胺分子會製備出球狀結構,長鏈雙胺分子則會使反應受到抑制而製備出聚集銀層。

In this study, methods to prepare substrates for Surface-Enhanced Raman Scattering (SERS) measurements were proposed and examined.Zinc plates were used as base plates to have further modifications of a thin layer of nanostructural silver materials using electroless deposition method. In general, the prepared substrates offer an enhancement factor larger than 106 in SERS measurements. To understand the mechanism in formation of nanostructural silver materials and to optimize the reaction conditions, factors that affect the reactions were examined. These factors included the concentration of silver nitrate, the reaction time and temperatures, and the concentration and species of amino additives.Results indicated that the formation of the structural silver materials having large enhancement factors is strongly depending upon the reaction speed in the electroless deposition processes. Basically, the slower of the reaction rate, the produced silver materials tend to have crystal structures to provide better SERS signals. Therefore, the increase of reaction temperature and concentration of silver nitrates decreased the SERS signals due to formation of less crystalline structures. Amino compounds were selected to form complexes with silver ions and the zinc ions. The addition of amino compounds indeed largely reduced the reaction rate and with an enough concentration of amino compounds, the formed structural silver materials provided strong SERS effect, especially when short alkyl chain amino compounds were used. The optimal condition was found as the reaction was performed under ice-water bath with the reaction solution containing 550 mM ethylamine and 10 mM of silver nitrate. The enhancement factor found in the optimal reaction condition could be larger than 106.To further examine the role of the amino additive and to further improve the enhancement factors, amino additives were composed with two amino compounds to tune the reaction conditions to match the SERS effects. In this study, ethylamine was selected as the first amino compound due to better performance among the examined amino compounds. Second amino compounds were designed to have different alkyl chain length and second functional groups. These second amino compounds included diamino compounds and alkyl amines with different chain length. The mechanism to form the nanostructural silver materials followed the behaviors when only one amino additive was used. In general, the formed structural silver materials with two amino compounds as additive provided better performance than with one amino compound as additive. Also, the morphologies of the silver nanomaterials could be controlled more precisely to have higher precision in SERS signals when combined amino compounds were used as additive.
其他識別: U0005-1908200913514200
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