多孔氧化鋁膜與貴金屬納米顆粒復(fù)合結(jié)構(gòu)的表面增強(qiáng)熒光效應(yīng)研究
發(fā)布時(shí)間：2019-05-24 13:40
【摘要】：具有納米結(jié)構(gòu)的金屬襯底,在外光場(chǎng)激發(fā)下,其表面所產(chǎn)生的表面等離激元會(huì)導(dǎo)致金屬襯底附近的局域電磁場(chǎng)分布發(fā)生改變。因此,位于襯底表面附近的熒光物種的熒光輻射將受到調(diào)制,相比自由態(tài)的熒光分子而言,其熒光輻射效率大幅提升的現(xiàn)象稱為表面增強(qiáng)熒光效應(yīng)。在實(shí)際應(yīng)用中,檢測(cè)環(huán)境對(duì)光譜測(cè)量技術(shù)的靈敏度的要求不斷提高,表面增強(qiáng)熒光效應(yīng)憑借其高靈敏度的特點(diǎn),受到越來(lái)越多的科研工作者青睞。且隨著納米技術(shù)的迅猛發(fā)展,人們從納米材料的性質(zhì)、襯底尺寸的調(diào)整、表面形貌的修飾等方面,對(duì)表面增強(qiáng)熒光效應(yīng)展開(kāi)研究。同時(shí),在理論研究方面,構(gòu)建了局域場(chǎng)增強(qiáng)理論、能量轉(zhuǎn)移理論、輻射衰減速率理論等三大理論模型,為表面增強(qiáng)熒光效應(yīng)的實(shí)驗(yàn)探究提供了理論支持。在表面增強(qiáng)熒光效應(yīng)的研究中,襯底制備的探究成為了研究人員關(guān)注的熱點(diǎn)之一。目前,納米線、納米球、納米棒、納米花等形貌的襯底結(jié)構(gòu),已被廣泛應(yīng)用到表面增強(qiáng)熒光效應(yīng)中。利用氧化還原法、磁控濺射法、熱蒸鍍法等制備得到銀島膜、球形金膠、三角銀膠、棒狀金膠等多種形貌的納米結(jié)構(gòu)襯底,為系統(tǒng)研究表面增強(qiáng)熒光效應(yīng)提供了良好的樣品平臺(tái)。然而,上述襯底在實(shí)現(xiàn)大面積、均勻性的增強(qiáng)襯底探索方面,具有一定的不足,從而限制其大規(guī)模推廣。眾所周知,多孔氧化鋁膜具有六角形蜂窩狀孔洞結(jié)構(gòu),孔徑大小可控,孔洞分布均勻,孔道取向性良好,與膜表面垂直等特點(diǎn)。在表面增強(qiáng)拉曼散射的研究領(lǐng)域,利用多孔氧化鋁膜制備高度有序的增強(qiáng)襯底,已經(jīng)取得了廣泛的應(yīng)用。但在表面增強(qiáng)熒光效應(yīng)研究中,基于多孔氧化鋁膜的襯底制備等研究卻鮮有報(bào)道。本論文利用多孔氧化鋁膜作為模板,綜合運(yùn)用電化學(xué)沉積法、離子濺射法等多種手段,制備出多孔氧化鋁膜與貴金屬納米顆粒復(fù)合結(jié)構(gòu)襯底,同時(shí)對(duì)其表面增強(qiáng)熒光效應(yīng)進(jìn)行了研究,獲得工藝簡(jiǎn)單、成本低廉、形貌易控、大面積均勻性好、熒光增強(qiáng)效果顯著的金屬納米顆粒復(fù)合結(jié)構(gòu)襯底。主要工作及結(jié)論如下：1、多孔氧化鋁膜的制備及熒光光譜測(cè)量通過(guò)二次氧化法制備得到含有均勻分布的六角形蜂窩狀孔洞網(wǎng)格的多孔氧化鋁膜襯底。采用場(chǎng)發(fā)射掃描電子顯微鏡進(jìn)行形貌表征。利用激光光譜學(xué)方法,研究擴(kuò)孔處理對(duì)多孔氧化鋁膜表面增強(qiáng)熒光效應(yīng)的影響規(guī)律。結(jié)果表明,未經(jīng)擴(kuò)孔處理的多孔氧化鋁膜具有較強(qiáng)的增強(qiáng)作用,相比于擴(kuò)孔處理的增強(qiáng)因子最大可達(dá)3.8。分析表明,未經(jīng)擴(kuò)孔處理的多孔氧化鋁膜具有獨(dú)特的三維表面形貌,其自身表面積增大,更有利于熒光效應(yīng)的增強(qiáng)。2、多孔氧化鋁模板調(diào)制金銀復(fù)合納米結(jié)構(gòu)的制備及其表面增強(qiáng)熒光效應(yīng)的研究應(yīng)用電化學(xué)沉積的方法,在多孔氧化鋁膜的孔洞之中依次沉積金、銀納米顆粒,制備得到一種受AAO調(diào)制的Au/Ag復(fù)合納米結(jié)構(gòu)襯底。實(shí)驗(yàn)中選取Rh6G分子作為熒光探針?lè)肿?在532nm激光激發(fā)下,對(duì)該新型襯底表面增強(qiáng)熒光效應(yīng)進(jìn)行了研究。結(jié)果表明,所制備襯底具有顯著的熒光增強(qiáng)效果,最大增強(qiáng)倍數(shù)約8.5倍,且隨著孔密度的減小,增強(qiáng)因子變大。從局域場(chǎng)增強(qiáng)理論、金／銀納米顆粒的電磁響應(yīng)特性等角度,對(duì)該復(fù)合襯底的表面增強(qiáng)熒光效應(yīng)進(jìn)行分析討論。3、金銀納米顆粒修飾的多孔氧化鋁膜復(fù)合結(jié)構(gòu)襯底的表面增強(qiáng)熒光效應(yīng)研究分別采用離子濺射和電化學(xué)沉積的方法,獲得了經(jīng)金銀納米顆粒修飾的多孔氧化鋁膜復(fù)合結(jié)構(gòu)襯底,研究了該襯底對(duì)Rh6G的熒光增強(qiáng)效應(yīng)。在532nm激光激發(fā)下,獲得了平均值為2.6倍的熒光增強(qiáng)因子。根據(jù)輻射衰減速率增加理論,對(duì)所觀察到的實(shí)驗(yàn)現(xiàn)象進(jìn)行了分析討論。
[Abstract]:The metal substrate with the nano structure, under the excitation of the external light field, the surface of the metal substrate and the like away from the exciting element can cause the local electromagnetic field distribution near the metal substrate to change. Thus, the fluorescence radiation of the fluorescent species located near the surface of the substrate will be modulated, and the phenomenon of a significant increase in the fluorescence radiation efficiency of the fluorescent molecule in the free state is called a surface-enhanced fluorescence effect. In the practical application, the requirement of the detection environment to the sensitivity of the spectral measurement technology is continuously improved, and the surface-enhanced fluorescence effect is favored by an increasing number of scientific researchers by virtue of its high sensitivity. And with the rapid development of the nano technology, the surface-enhanced fluorescence effect is studied from the aspects of the properties of the nano-materials, the adjustment of the size of the substrate, the modification of the surface morphology, and the like. At the same time, in the aspect of theory research, three theoretical models, such as the local field enhancement theory, energy transfer theory and radiation attenuation rate theory, are built, and the theoretical support is provided for the experimental investigation of the surface-enhanced fluorescence effect. In the study of the surface-enhanced fluorescence effect, the research on the preparation of the substrate has become one of the hot spots of the researchers' attention. At present, the substrate structure, such as nanowires, nanospheres, nanorods, nano-flowers, and the like, has been widely used in the surface-enhanced fluorescence effect. The nano-structure substrates such as the silver island film, the spherical gold glue, the triangular silver glue and the rod-shaped gold glue are prepared by using an oxidation reduction method, a magnetron sputtering method, a thermal evaporation method and the like to provide a good sample platform for the surface-enhanced fluorescence effect of the system. However, the above-mentioned substrate has a certain disadvantage in realizing large-area and uniform enhancement of substrate exploration, thereby limiting its large-scale popularization. It is well known that the porous aluminum oxide film has the characteristics of hexagonal honeycomb-shaped hole structure, controllable pore size, uniform pore distribution, good channel orientation, and perpendicular to the surface of the film. In the field of surface-enhanced Raman scattering, a highly ordered reinforced substrate was prepared by using a porous alumina film, and a wide range of applications has been achieved. However, in the study of the surface-enhanced fluorescence effect, the preparation of the substrate based on the porous alumina film is rarely reported. in this paper, a porous alumina film is used as a template, and a porous aluminum oxide film and a noble metal nanoparticle composite structure substrate are prepared by using a plurality of means such as an electrochemical deposition method and an ion sputtering method, The metal nanoparticle composite structure substrate has the advantages of low cost, easy control of appearance, good large area uniformity and remarkable fluorescence enhancement effect. The main work and conclusion are as follows:1, the preparation of the porous alumina film and the fluorescence spectrum measurement are prepared by a secondary oxidation method to obtain a porous aluminum oxide film substrate containing a hexagonal honeycomb-shaped hole mesh which is uniformly distributed. The morphology was characterized by a field emission scanning electron microscope. The effect of hole-enlarging treatment on the surface-enhanced fluorescence effect of porous alumina film was studied by means of laser spectroscopy. The results show that the porous alumina film without the hole-enlarging treatment has a strong reinforcing effect, and the enhancement factor of the pore-expanding treatment can reach 3.8. The analysis shows that the porous alumina film without the hole-enlarging treatment has a unique three-dimensional surface morphology, the surface area of the porous aluminum oxide film is increased, and the enhancement of the fluorescence effect is more favorable. The preparation of the porous alumina template and the preparation of the gold and silver composite nano structure and the application of the electrochemical deposition method in the study of the surface enhanced fluorescence effect are sequentially deposited in the holes of the porous aluminum oxide film to prepare the Au/ Ag composite nano-structure substrate which is prepared by the AAO modulation. In the experiment, Rh6G is used as a fluorescent probe molecule, and the fluorescence effect on the surface of the novel substrate is studied under the excitation of 532 nm laser. The results show that the prepared substrate has a significant fluorescence enhancement effect, the maximum enhancement factor is about 8.5 times, and the enhancement factor becomes larger with the decrease of the pore density. The surface-enhanced fluorescence effect of the composite substrate is analyzed and discussed from the aspects of the local field enhancement theory, the electromagnetic response characteristics of the gold/ silver nanoparticles, and the like. The surface-enhanced fluorescence effect of the porous aluminum oxide film composite structure substrate modified by the gold and silver nano-particles adopts the method of ion sputtering and electrochemical deposition respectively, and the porous aluminum oxide film composite structure substrate modified by the gold and silver nano-particles is obtained, The effect of the substrate on the fluorescence enhancement of Rh6G is studied. The fluorescence enhancement factor of 2.6 times the average was obtained under the excitation of 532 nm laser. Based on the theory of radiation decay rate, the observed experimental phenomena are analyzed and discussed.
【學(xué)位授予單位】：陜西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.1
本文編號(hào)：2484906
[Abstract]:The metal substrate with the nano structure, under the excitation of the external light field, the surface of the metal substrate and the like away from the exciting element can cause the local electromagnetic field distribution near the metal substrate to change. Thus, the fluorescence radiation of the fluorescent species located near the surface of the substrate will be modulated, and the phenomenon of a significant increase in the fluorescence radiation efficiency of the fluorescent molecule in the free state is called a surface-enhanced fluorescence effect. In the practical application, the requirement of the detection environment to the sensitivity of the spectral measurement technology is continuously improved, and the surface-enhanced fluorescence effect is favored by an increasing number of scientific researchers by virtue of its high sensitivity. And with the rapid development of the nano technology, the surface-enhanced fluorescence effect is studied from the aspects of the properties of the nano-materials, the adjustment of the size of the substrate, the modification of the surface morphology, and the like. At the same time, in the aspect of theory research, three theoretical models, such as the local field enhancement theory, energy transfer theory and radiation attenuation rate theory, are built, and the theoretical support is provided for the experimental investigation of the surface-enhanced fluorescence effect. In the study of the surface-enhanced fluorescence effect, the research on the preparation of the substrate has become one of the hot spots of the researchers' attention. At present, the substrate structure, such as nanowires, nanospheres, nanorods, nano-flowers, and the like, has been widely used in the surface-enhanced fluorescence effect. The nano-structure substrates such as the silver island film, the spherical gold glue, the triangular silver glue and the rod-shaped gold glue are prepared by using an oxidation reduction method, a magnetron sputtering method, a thermal evaporation method and the like to provide a good sample platform for the surface-enhanced fluorescence effect of the system. However, the above-mentioned substrate has a certain disadvantage in realizing large-area and uniform enhancement of substrate exploration, thereby limiting its large-scale popularization. It is well known that the porous aluminum oxide film has the characteristics of hexagonal honeycomb-shaped hole structure, controllable pore size, uniform pore distribution, good channel orientation, and perpendicular to the surface of the film. In the field of surface-enhanced Raman scattering, a highly ordered reinforced substrate was prepared by using a porous alumina film, and a wide range of applications has been achieved. However, in the study of the surface-enhanced fluorescence effect, the preparation of the substrate based on the porous alumina film is rarely reported. in this paper, a porous alumina film is used as a template, and a porous aluminum oxide film and a noble metal nanoparticle composite structure substrate are prepared by using a plurality of means such as an electrochemical deposition method and an ion sputtering method, The metal nanoparticle composite structure substrate has the advantages of low cost, easy control of appearance, good large area uniformity and remarkable fluorescence enhancement effect. The main work and conclusion are as follows:1, the preparation of the porous alumina film and the fluorescence spectrum measurement are prepared by a secondary oxidation method to obtain a porous aluminum oxide film substrate containing a hexagonal honeycomb-shaped hole mesh which is uniformly distributed. The morphology was characterized by a field emission scanning electron microscope. The effect of hole-enlarging treatment on the surface-enhanced fluorescence effect of porous alumina film was studied by means of laser spectroscopy. The results show that the porous alumina film without the hole-enlarging treatment has a strong reinforcing effect, and the enhancement factor of the pore-expanding treatment can reach 3.8. The analysis shows that the porous alumina film without the hole-enlarging treatment has a unique three-dimensional surface morphology, the surface area of the porous aluminum oxide film is increased, and the enhancement of the fluorescence effect is more favorable. The preparation of the porous alumina template and the preparation of the gold and silver composite nano structure and the application of the electrochemical deposition method in the study of the surface enhanced fluorescence effect are sequentially deposited in the holes of the porous aluminum oxide film to prepare the Au/ Ag composite nano-structure substrate which is prepared by the AAO modulation. In the experiment, Rh6G is used as a fluorescent probe molecule, and the fluorescence effect on the surface of the novel substrate is studied under the excitation of 532 nm laser. The results show that the prepared substrate has a significant fluorescence enhancement effect, the maximum enhancement factor is about 8.5 times, and the enhancement factor becomes larger with the decrease of the pore density. The surface-enhanced fluorescence effect of the composite substrate is analyzed and discussed from the aspects of the local field enhancement theory, the electromagnetic response characteristics of the gold/ silver nanoparticles, and the like. The surface-enhanced fluorescence effect of the porous aluminum oxide film composite structure substrate modified by the gold and silver nano-particles adopts the method of ion sputtering and electrochemical deposition respectively, and the porous aluminum oxide film composite structure substrate modified by the gold and silver nano-particles is obtained, The effect of the substrate on the fluorescence enhancement of Rh6G is studied. The fluorescence enhancement factor of 2.6 times the average was obtained under the excitation of 532 nm laser. Based on the theory of radiation decay rate, the observed experimental phenomena are analyzed and discussed.
【學(xué)位授予單位】：陜西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.1
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 呂鳳婷;鄭海榮;房喻;;表面增強(qiáng)熒光研究進(jìn)展[J];化學(xué)進(jìn)展;2007年Z1期
2 ;Surface enhanced fluorescence by porous alumina with nanohole arrays[J];Science China(Physics,Mechanics & Astronomy);2012年05期
相關(guān)碩士學(xué)位論文 前2條
1 敖昕;AAO模板制備的基礎(chǔ)理論及其超薄化制備方法研究[D];中國(guó)海洋大學(xué);2011年
2 閻曉慶;多孔陣列調(diào)制的貴金屬納米顆粒組裝結(jié)構(gòu)的表面增強(qiáng)熒光效應(yīng)研究[D];陜西師范大學(xué);2012年
，本文編號(hào)：2484906
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