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研究生: 黃珮瑜
Huang,Pei-Yu
論文名稱: 化學鍍法製備銅奈米島狀薄膜及其螢光增強特性分析
Preparation of Copper Nano-Island Films by Electroless Plating and Their Fluorescence Enhancement Characteristics
指導教授: 陳家俊
Chen, Chia-Chun
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2020
畢業學年度: 108
語文別: 中文
論文頁數: 49
中文關鍵詞: 金屬螢光增強局部表面電漿共振銅奈米粒子賈凡尼置換反應
英文關鍵詞: Metal Enhanced Fluorescence (MEF), Local Surface Plasmon Resonance (LSPR), Copper nanoparticles, Galvanic replacement
DOI URL: http://doi.org/10.6345/NTNU202000786
論文種類: 學術論文
相關次數: 點閱:220下載:18
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金屬奈米粒子具有金屬螢光增強( Metal Enhanced Fluorescence, MEF )之特性,鄰近於金屬奈米粒子的螢光分子(距離小於20nm),會受到金屬奈米粒子表面增強電場的影響,進而增強或減弱螢光分子的螢光強度。目前關於金屬螢光增強的研究文獻大多著重於金與銀的奈米粒子,而銅奈米粒子由於其表面相對的容易氧化,故銅的表面電漿共振( Localized Surface Plasmon Resonance, LSPR )相關的研究和應用並未受到太大的重視。本實驗室先前利用金的晶種修飾於玻璃基板後,順利的製備出銅奈米薄膜,但金的晶種增加了實驗成本,因此本研究改善了銅奈米島狀薄膜的製備方法,在不使用金的條件下先於玻璃基板上長出銅晶種,再以少量的銀離子進行賈凡尼置換反應( Galvanic replacement ),形成銅銀核殼晶種( Cu@Ag Seed ),最後以甲醛作為還原劑,順利成長出銅奈米島狀薄膜。為了解決銅奈米島狀薄膜氧化的問題,我們在薄膜上修飾硫醇,並利用碳酸氫鈉緩衝溶液抑制銅的氧化。為了進一步探討銅奈米島狀薄膜與螢光增強倍率的關係,本研究改變銅的生長時間並測試不同的硫醇表面修飾。結果發現銅薄膜的生長時間為4分鐘且以硫十一醇( 11-mercapto-1-undecanol,11-MUD )修飾薄膜表面時,能夠得到最高的螢光增強倍率達148倍。未來期許本實驗所備的銅奈米島狀薄膜能更進一步的應用到螢光增強的生物化學檢測技術中。

Metal nanoparticles have the characteristics of Metal Enhanced Fluorescence (MEF). The fluorescent molecules adjacent to the metal nanoparticles (with a distance of less than 20 nm) are affected by the enhanced electric field on the surface of the metal nanoparticles, thereby enhancing or reducing the fluorescence intensity of fluorescent molecules. Currently, most of the research on MEF focuses on gold and silver nanoparticles, while copper nanoparticles are relatively easily oxidized on the surface. Therefore, researches on Local Surface Plasmon Resonance (LSPR) of copper haven’t been attracted. Previously, the laboratory used gold seeds to modify the glass substrate and successfully prepared copper nano-films, but gold seeds increased the experimental cost, so this study improved the preparation method of copper nano-island films. In the absence of gold, copper seeds were grown on a glass substrate, and then a small amount of silver ions were used to perform the Galvanic replacement to form copper silver core-shell seed. Finally, formaldehyde was used as a reducing agent to grow a copper nano island film. To prevent oxidation of copper, we modified the thiol on the films and used sodium bicarbonate buffer solution to inhibit copper oxidation. In order to explore the relationship between the copper nano-island films and the fluorescence enhancement magnification, we changed the copper growth time and different thiol surface modifications. From the results, the growth time of the copper film was 4 minutes as the surface of the film was modified with 11-mercapto-1-undecanol,then the highest fluorescence enhancement factor was 148 times. This experiment expects that the prepared copper nano-island film can be further applied to fluorescence enhanced biochemical detection technology.

第一章 緒論 1 1-1生物傳感器(Biosensor)的簡介 1 1-2 生物傳感器的換能器種類 3 1-2-1 電化學生物傳感器 4 1-2-2 光學生物傳感器 5 1-3 奈米材料 7 1-3-1 奈米材料的特性 7 1-3-2 金屬奈米材料 8 第二章 文獻回顧 9 2-1 SPR與LSPR特性 9 2-1-1 表面電漿共振( Surface Plasmon Resonance, SPR ) 9 2-1-2 局部表面電漿共振( Localized Surface Plasmon Resonance, LSPR ) 9 2-2 金屬螢光增強 (Metal-Enhanced fluorescence, MEF) 10 2-3 銅奈米薄膜的螢光增強研究 13 2-4 研究目的 15 第三章 實驗藥品與步驟 16 3-1 實驗藥品 16 3-2 實驗儀器介紹 18 3-2-1 往返式振盪恆溫水槽 18 3-2-2 低溫循環水槽 18 3-2-3 酸鹼度測定儀與電極 19 3-2-4 玻片迷你微量離心機 19 3-2-5 迴轉式振盪器 20 3-2-6 紫外光-可見光吸收光譜儀 20 3-2-7 紫外光-可見光-近紅外光分光光譜儀 21 3-2-8 掃描式電子顯微鏡 21 3-2-9 X光能量分散光譜儀 22 3-2-10 X射線光電子能譜儀 23 3-2-11 微陣列螢光掃描儀 23 3-3 實驗步驟 24 3-3-1 前置作業 : 玻片清洗與Succinic anhydride修飾 24 3-3-2 晶種奈米薄膜的製備 24 3-3-3 Cu奈米島狀薄膜的製備 25 3-3-4 Cu奈米島狀薄膜的表面修飾 25 3-3-5 修飾螢光物質 26 第四章 研究過程與結果與討論 28 4-1 晶種薄膜( seed films )的製備與分析鑑定 28 4-2 Cu奈米島狀薄膜的製備與分析鑑定 33 4-2-1 Cu奈米島狀薄膜的製備 33 4-2-2 反應時間對Cu奈米島狀薄膜的影響 33 4-2-3 Cu奈米島狀薄膜的表面分析 37 4-3 Cu奈米島狀薄膜的表面修飾 38 4-3-1 Cu奈米島狀薄膜的表面修飾流程 38 4-3-2 硫醇修飾對Cu奈米島狀薄膜的影響 39 4-4 Cu奈米島狀薄膜的螢光增強測試 41 4-4-1 不同緩衝溶液對Cu奈米島狀薄膜的影響 41 4-4-2 修飾上不同的硫醇對螢光增強的影響 42 4-4-3 Cu奈米島狀薄膜之不同成長時間對螢光增強的影響 43 第五章 結論與未來展望 45 參考文獻 46

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