表面等离子激元非线性表面增强拉曼散射效应

本文采用热蒸发法制备得到纳米Ag颗粒作为增强拉曼衬底, 利用入射光子与纳米颗粒表面价电子的相互作用机理, 激发出高能表面等离子激元, 其表面等离子形成的高能"热点"起到表面增强拉曼散射效果. 通过比较不同入射光强下的拉曼峰强, 指出纳米Ag颗粒的增强拉曼散射效果可以实现低探测光强下的高散射强度, 即纳米Ag颗粒的表面等离子激元具有非线性的表面增强拉曼散射效果, 可降低对样品的光、热损伤, 以利于拓展拉曼散射光谱的应用范围. 同时比较不同纳米Ag颗粒衬底的表面增强拉曼散射效果表明, 采用的热蒸发工艺具有较大的工艺域度, 具有较强的工艺兼容性.     

单个银纳米聚合体的偶极表面等离子体共振灵敏表面增强拉曼散射(英文)

pacc:5240F,7830Weinvestigatedpolarizationdependencesof surfaceenhancedresonanceRamanscattering(SERRS)andsurfaceplasmonresonance(SPR)toidentifytheSERRSyieldingSPRbands.We alsostudiedSERRSexcitationspectraforsingle Agnano-aggregateswiththeSPRbandstoex plore…     

基于“热点”效应的表面增强拉曼散射光谱研究

本文利用罗丹明6G在银胶体粒子聚集点上的表面增强拉曼光谱的强度变化,采用逐点扫描获得拉曼光谱的"Mapping"方法,获得了不同的银胶体粒子聚集点对吸附的R6G表面增强拉曼光谱强度的影响。分析了"热点"对拉曼散射的增强的作用,表明"热点"的增强强度和纳米粒子的聚集程度有关。     

表面等离子体共振与表面增强拉曼散射相关性研究

本实验利用实验室搭建的SPR-SERS显微拉曼光谱仪同时检测了吸附在40 nm银膜上的4-amin-othiophenol(4-ATP)自组装膜的表面等离子体共振(Surface Plasmon Resonance,简称SPR)消光谱及表面增强拉曼散射(Surface-Enhanced Raman Scattering,简称SERS)光谱,研究了两者之间的相关性。实验发现随着SPR吸收的增强,SERS强度也急剧增强,在SPR共振角附近SERS强度是远离共振角处的20多倍。因此在共振角附近能够极大的提高SERS的检测灵敏度并扩展SERS的应用。     

表面增强拉曼散射光谱的应用进展

表面增强拉曼光谱是一种非常有效的探测界面特性和分子间相互作用、表征表面分子吸附行为和分子结构的工具。已成为灵敏度最高的研究界面效应的技术之一,最大范围地应用于研究吸附分子在表面的取向及吸附行为、吸附界面表面状态、生物大分子的界面取向及构型、构象和结构分析;SERS技术也逐渐成为表面科学和电化学领域有力的研究手段,并已在痕量分析乃至单分子检测、化学及工业、环境科学、生物医学体系、纳米材料以及传感器等方面的研究中得到了广泛应用,甚至出现了拉曼技术与其他技术的联用。文章综述了近几年来表面增强拉曼散射作为一种光谱技术在这些应用领域的研究进展以及潜在应用价值;并简单介绍了作者所在实验室的相关工作,特别是富勒烯和碳纳米管材料等领域的一些探讨与研究。     

纳米结构Si表面增强拉曼散射特性研究

为了实现低成本高灵敏度的表面增强拉曼散射效应,制备了一种基于硅表面纳米结构的表面增强拉曼散射效应（SERS）衬底。首先利用低能反应离子注入的方法对单晶硅进行表面处理,制作高陡值度的墙壁结构。然后采用电子束蒸发的方式在硅片表面蒸镀银膜,高密度的银纳米点阵列出现在侧壁表面,形成大量的热点。实验采用罗丹明6G（R6G）作为探针分子进行表征,发现获得最强拉曼信号的银膜厚度为40 nm,R6G的探测极限能达到10^-14 mol/L;同时分析衬底的重复性和稳定性,发现在614 cm^-1和1 650 cm^-1处的拉曼信号特征峰的相对标准偏差分别达到12.3%和14.3%,保存一个月的衬底测得的拉曼信号强度保持不变。本研究提供了一种操作简单、成本低的制备高灵敏度增强拉曼效应衬底的方法,制备的衬底具有高信号可重复性和高稳定性的优点。     

Au纳米粒子增强丙酮受激拉曼散射研究

受激拉曼散射(stimulated Raman scattering,SRS)具有激光的特性,并且容易获取不同波长的激光,从而成为调谐激光频率的重要途径之一。然而,由于其转化效率低,限制了它的实际应用。金属纳米粒子具有很强的表面增强效应,曾被广泛地用于增强拉曼散射而获得良好的效果。本文提出将金属纳米粒子的这种性质用于增强SRS。把Au纳米粒子混合于拉曼介质丙酮中,以532nm的纳秒脉冲激光作为激发光,研究了Au纳米粒子在丙酮中的浓度对丙酮SRS一阶Stokes光强的影响,并通过仿真计算对实验结果进行了解释和分析。     

活血化瘀汤药队的表面增强拉曼散射光谱研究

在中药治疗过程中,以方剂为载体,注重整体,采用辨证论治的方法。为揭示方剂的药队规律,根据药队协同效应设计法,将活血化瘀汤方剂拆分为“调和”、“化瘀生新”、“活血止痛”、“补气”四个药队方剂。由于银纳米粒子可与煎剂产生强交互作用,并极大地增强拉曼信号,获取活血化瘀汤、调和药队煎剂、化瘀生新药队煎剂、活血止痛药队煎剂和补气药队煎剂五种方剂煎剂的表面增强拉曼散射(SERS)光谱,并对所有SERS谱峰进行归属。主要针对各煎剂中的18个拉曼信号(523,538,622,647,732,959,977,1 003,1 048,1 077,1 145,1 245,1 326,1 402,1 456,1 470,1 518和1 605 cm-1)进行讨论。活血化瘀汤SERS光谱中保留了药队煎剂的某些拉曼峰,如：538,622,647,732,959,1 003,1 048,1 326,1 402,1 456,1 470,1 518和1 605 cm-1。药队煎剂SERS光谱的某些拉曼峰并未在活血化瘀汤中出现,如：1 077,1 145和1 245 cm-1。在活血化瘀汤SERS光谱中,出现了新的拉曼峰,如：523和977 cm-1。新的拉曼峰出现说明新物质的产生。实验结果表明,活血化瘀汤所包含的药物成分并非是各药队煎剂所含药物成分的简单相加,SERS光谱可为方剂药队规律研究提供一优异、有效和准确的检测方法。     

聚甲基丙烯酸甲酯间隔的金纳米立方体与金膜复合结构的表面增强拉曼散射研究

金属纳米颗粒与金属薄膜的复合结构由于其局域表面等离子体和传播表面等离子体间的强共振耦合作用,可作为表面增强拉曼散射(SERS)基底,显著增强吸附分子的拉曼信号.本文提出了一种聚甲基丙烯酸甲酯(PMMA)间隔的90 nm金纳米立方体与50 nm金膜复合结构的SERS基底,通过有限元方法数值模拟,得到PMMA的最优化厚度为15 nm.实验制备了PMMA间隔层厚度为14 nm的复合结构,利用罗丹明6G (R6G)为拉曼探针分子, 633 nm的氦氖激光器作为激发光源,研究了复合结构和单一金纳米立方体的SERS效应,发现复合结构可以使探针分子产生比单一结构更强的拉曼信号.在此基础上,研究了不同浓度金纳米立方体水溶液条件下复合结构中R6G的拉曼光谱.结果表明,当金纳米立方体水溶液浓度为5.625μg/mL的条件下复合结构中R6G的拉曼信号最强,且可测量R6G的最低浓度达10~(–11) mol/L.     

Al2O3薄膜/纳米Ag颗粒复合结构的光吸收谱及增强Raman散射光谱研究

Al₂O₃介质薄膜与纳米Ag颗粒构成的复合结构,被应用于表面增强Raman散射探测实验中,其中Al₂O₃介质薄膜对纳米Ag颗粒的吸收谱及增强Raman散射光谱的影响被特别关注.该复合结构的光学特性表征出纳米Ag颗粒的偶极振荡特性.从光吸收谱中可以看到,其共振吸收谱随Al₂O₃介质薄膜厚度增加而在整个谱域上发生红移,表明纳米Ag颗粒的周围介电常数随Al₂O₃介质薄膜厚度的增加而增大.采用罗丹明6G作为探针原子,6个Raman特征峰的平均增益值作为表征表面增强Raman散射衬底增益程度的量度.实验结果表明,Al₂O₃介质薄膜层的引入提高了纳米Ag颗粒的衬底介电常数,并引起了散射共振的增强,从而使表面增强Raman散射强度提高.     

Al2O3薄膜/纳米Ag颗粒复合结构的光吸收谱及增强Raman散射光谱研究

Al₂O₃介质薄膜与纳米Ag颗粒构成的复合结构,被应用于表面增强Raman散射探测实验中,其中Al₂O₃介质薄膜对纳米Ag颗粒的吸收谱及增强Raman散射光谱的影响被特别关注.该复合结构的光学特性表征出纳米Ag颗粒的偶极振荡特性.从光吸收谱中可以看到,其共振吸收谱随Al₂O₃介质薄膜厚度增加而在整个谱域上发生红移,表明纳米Ag颗粒的周围介电常数随Al₂O₃介质薄膜厚度的增加而增大.采用罗丹明6G作为探针原子,6个Raman特征峰的平均增益值作为表征表面增强Raman散射衬底增益程度的量度.实验结果表明,Al₂O₃介质薄膜层的引入提高了纳米Ag颗粒的衬底介电常数,并引起了散射共振的增强,从而使表面增强Raman散射强度提高. 关键词： 纳米Ag薄膜 共振吸收 表面增强Raman散射 介电常数     

TiO_2/Ag composite nanowires for a recyclable surface enhanced Raman scattering substrate

Multifunctional TiO2/Ag composite nanowires are fabricated with a hydrothermal method by precipitating Ag nanoparticles （NPs） on the surfaces of TiO2 nanowires. This hierarchical one-dimensional （1D） nanostructure can be used as a surface enhanced Raman scattering （SERS） substrate with high sensitivity, for detecting the rhodamine 6G （R6G） in a wide range of low concentrations （from 1 × 10 6 M to 1 × 10-12 M）. In addition, the substrate can be self-cleaned under the irradiation of ultraviolet （UV） light due to the superior photocatalytic capacity of the TiO2/Ag composite nanostructure, making the recycled use of SERS substrates closer to reality. With both the evident SERS performance and high efficiency of photocatalytic capacity, such TiOz/Ag composite nanowires demonstrate considerable potential in the chemical sensing of organic pollutants.     

非水体系中哌啶在银电极表面的表面增强喇曼散射

本文测定了哌啶在甲醇溶液中吸附在银电极表面的表面增强喇曼散射(SERS)光谱,及其随电位的变化,同时还测定了电极经不同氧化-还原循环(ORC)预处理时的SERS谱,对所得结果进行了分析比较,并进一步研究了非水体系和水体系SERS谱之间的关系.实验结果表明:哌啶在甲醇体系中比在水体系中SERS谱的增强因子要小,并且它们的SERS谱线随电位的变化也有一定的差别.     

Raman scattering of L‐tryptophan enhanced by surface plasmon of silver nanoparticles: vibrational assignment and structural determination

Vibrational bands of L ‐tryptophan which was adsorbed on Ag nanoparticles (∼10 nm in diameter) have been investigated in the spectral range of 200–1700 cm⁻¹ using surface‐enhanced Raman scattering (SERS) spectroscopy. Compared with the normal Raman scattering (NRS) of L ‐tryptophan in either 0.5 M aqueous solution (NRS‐AS) or solid powder (NRS‐SP), the intensified signals by SERS have made the SERS investigation at a lower molecular concentration (5 × 10⁻⁴ M ) possible. Ab initio calculations at the B3LYP/6‐311G level have been carried out to predict the optimal structure and vibrational wavenumbers for the zwitterionic form of L ‐tryptophan. Facilitated with the theoretical prediction, the observed vibrational modes of L ‐tryptophan in the NRS‐AS, NRS‐SP, and SERS spectra have been analyzed. In the spectroscopic observations, there are no significant changes for the vibrational bands of the indole ring in either NRS‐AS, NRS‐SP, or SERS. In contrast, spectral intensities involving the vibrations of carboxylate and amino groups are weak in NRS‐AS and NRS‐SP, but strong in SERS. The intensity enhancement in the SERS spectrum can reach 10³–10⁴‐fold magnification. On the basis of spectroscopic analysis, the carboxylate and amino groups of L ‐tryptophan are determined to be the preferential terminal groups to attach onto the surfaces of Ag nanoparticles in the SERS measurement. Copyright © 2008 John Wiley & Sons, Ltd.     

Deposition of Ag nanoparticles on porous anodic alumina for surface enhanced Raman scattering substrate

Ag nanoparticles were exclusively deposited inside the pores of the porous anodic alumina (PAA) template through the deposition cycle including the incubation and the subsequent reduction of Ag(NH₃) . Both the density and size of the produced Ag nanoparticles increased as the deposition cycle number increased. A field‐emission scanning electron microscopeand an ultraviolet‐visible spectrometer were applied, respectively, to study the morphology and the extinction spectra of the Ag nanoparticles. The optimum deposition number was found from the scanning electron microscope (SEM) analysis. Surface enhanced Raman scattering (SERS) spectra of p‐aminothiophenol recorded on the Ag–PAA substrates prepared under increasing number of deposition cycles, manifested an enlarging trend of peak intensity. A point‐by‐point SERS mapping of p‐aminothiophenol on the Ag–PAA substrate was acquired to characterise the homogeneity of the substrate. Copyright © 2008 John Wiley & Sons, Ltd.     

Deep‐UV tip‐enhanced Raman scattering

We report for the first time the tip‐enhancement of resonance Raman scattering using deep ultraviolet (DUV) excitation wavelength. The tip‐enhancement was successfully demonstrated with an aluminum‐coated silicon tip that acts as a plasmonic material in DUV wavelengths. Both the crystal violet and adenine molecules, which were used as test samples, show electronic resonance at the 266‐nm excitation used in the experiments. With results demonstrated here, molecular analysis and imaging with nanoscale spatial resolution in DUV resonance Raman spectroscopy can be realized using the tip‐enhancement effect. Copyright © 2009 John Wiley & Sons, Ltd.     

Hole arrayed metal-insulator-metal structure for surface enhanced Raman scattering by self-assembling polystyrene spheres

A fabrication process based on the self-assembling polystyrene spheres is proposed to obtain hole arrayed metal-insulator-metal （HA-MIM） structure for surface enhanced Raman scattering （SERS）. The localized field enhancement aroused by the gap resonance in the HA-MIM structure is analyzed by finite-different time domain （FDTD） method. With reference to the theory result, the structure is experimentally fabricated and the Raman scattering spectrum of rhodamine 6G （R6G） is measured by a miniaturized Raman spectrometer. The results shows that the enhancement factor is 3.85 times higher than the control sample with single layered metal hole array. The fabrication process to obtain the HA-MIM SERS substrate is reproducible, fast, large area and low cost.     

Plasmon‐enhanced Raman scattering by suspended carbon nanotubes

We report plasmon‐enhanced Raman scattering of the order of 10³ by a metallic carbon nanotube partially suspended inside a near‐field cavity. The tube is part of a small bundle, and is interfaced with an Au nanodisc dimer using a recently developed assembly scheme based on dielectrophoretic deposition. Spatially resolved Raman measurements with two excitation wavelengths and two orthogonal polarizations confirm that the enhancement arises from a 65 nm long suspended tube segment. We show that the orientation of the tube inside the cavity can be as effective for generating enhancement as placing the nanotube precisely in a plasmonic hotspot. Position and shape of the G‐peak show that the suspended part of the tube is free of strain and doped with a Fermi energy shift ≤40 meV. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)