化學鍍法製備銅奈米島狀薄膜及其螢光增強特性分析
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2020
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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.
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.
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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, Metal Enhanced Fluorescence (MEF), Local Surface Plasmon Resonance (LSPR), Copper nanoparticles, Galvanic replacement