钴钯铂的表面增强喇曼散射效应研究

利用天线共振子模型对钴钯铂的表面增强喇曼散射特性进行了计算和分析, 计算结果表明钴钯铂的增强分别为1、≤4、2～4, 实验测量的最大增强分别为≤5、105和140, 在考虑化学增强的情况下, 理论同实验是一致的; 在经氧化还原过程处理的钴钯铂片上做了核酸碱基胞嘧啶的SERS谱, 结果反映三种衬底上的SERS谱强弱不同, 以铂最大, 钴最小, 而且, 三种衬底对于胞嘧啶各振动模式的增强基本一致.     

表面增强拉曼散射(SERS)衬底的研究及应用

表面增强拉曼散射(surface enhanced Raman scattering,SERS)是通过吸附在粗糙金属表面或金属纳米结构上的分子与金属表面发生的等离子共振(SPR)相互作用而引起的拉曼散射增强现象,是一种高灵敏的探测界面特性和分子间相互作用的光谱手段。文章归纳总结了近年来常用的SERS衬底的制备方法(溶液中的金属溶胶(MNPs in suspension)、 金属纳米粒子的自组装(self-assembly)、 模板法(Template method)和纳米光刻法(Nanolithographic)等;综述了这些衬底的表面增强拉曼特性;着重介绍了SERS增强在环境监测和生物医学应用上的最新国内外研究动态。目前已经能够实现增强因子高、 可靠性好、 重现性强的SERS衬底的可控制备,表明SERS可以作为一种高性能的分析探测工具,充分实现其潜在应用价值。     

1,4-苯二硫醇分子的表面增强共振拉曼散射的化学增强

利用密度泛函和含时密度泛函理论方法研究了1,4-苯二硫醇分子在两个金团簇之间的表面增强拉曼散射及表面增强共振拉曼散射光谱. 采用对应四种不同形式的电荷转移激发态能量的入射光,计算了表面增强共振拉曼光谱. 结果显示,光谱增强的效果与电荷转移的形式密切相关. 不同的电荷转移形式对增强因子的贡献是有差异的.     

锌的表面增强喇曼散射效应

本文从莫育俊等人提出的天线共振子模型理论出发,计算了金属锌的SERS增强特性。天线共振子模型预言,在可见光区,锌的增强因子最大为10,而在红外则会达到很大的增强(10⁵以上).同时,我们通过实验分析了金属锌的SERS增强特性,得到了在可见光区锌的增强因子约为230.在考虑化学增强的情况下,理论计算结果同实验基本一致。     

制作高性能表面增强拉曼散射衬底

采取真空热蒸发镀膜的方法在普通玻璃、毛玻璃、硅片等衬底上镀银膜,并用扫描电子显微镜观察了镀银毛玻璃的表面形貌,通过激光散射实验得出毛玻璃的粗糙度.实验结果表明,镀银毛玻璃衬底具有很好的表面增强拉曼散射活性,所能探测罗丹明6G的最低浓度为10-10 mol/L.     

金属基底上光学偶极纳米天线的自发辐射宽带增强:表面等离激元直观模型

本文提出一种具有宽波段自发辐射增强性能的金属基底上光学偶极纳米天线,实现的总辐射速率与远场辐射速率增强因子分别达到5454和1041,在近红外波段,自发辐射增强(Purcell因子超过1000)波长范围达到260 nm,并且能够实现远场定向辐射.为了阐明天线性能背后的物理机制,本文考虑天线臂上表面等离激元激发和多重散射的直观物理过程,基于Maxwell方程组第一性原理,建立了一个半解析模型,能够全面复现天线的辐射特性,包括总辐射速率、远场辐射速率、远场辐射方向图等.该模型提供了一个直观的物理图像,即在模型导出的两个相位匹配条件下,表面等离激元在天线臂上形成了一对Fabry-Perot共振获得增强,然后传播到纳米间隙内点辐射源位置和散射到自由空间,由此分别提高了总辐射速率和远场辐射速率.并且,这一对Fabry-Perot共振产生了一对相互靠近的谐振峰,由此形成了宽波段自发辐射增强.本文提出的偶极纳米天线可以应用于荧光增强、拉曼散射增强及高速、高亮度纳米光源等领域,所提出的模型可用于光学天线的物理理解和直观设计.     

用天线共振子模型研究银镜的紫外可见吸收光谱

我们研究了具有不同表面粗糙度银镜的紫外可见吸收光谱,实验结果表明随着表面粗糙度的增加,银粒子的共振吸收峰发生红移。根据天线共振子模型,进行了吸收光谱的理论计算,计算结果与实验相当吻合。     

金属光栅表面增强拉曼散射的偏振依赖性研究

表面增强拉曼散射的机理主要来源于金属表面等离子体共振所产生的电磁场增强,因而基底的电磁特性决定了其增强的性能。本文以干涉光刻方法制作的大面积均匀性一维纳米光栅为增强基底,从实验和理论上探究其表面增强拉曼散射的偏振依赖特性。本文使用苯硫酚作为探针分子,并采用633nm和785nm两种波长作为激发光源,开展了等离子体共振与非共振状态下金属光栅表面增强拉曼光谱的偏振依赖特性实验研究,并通过时域有限差分法对光栅电磁特性进行分析。研究发现,光栅表面的电场无论是否激发表面等离子体共振,其电场随入射光偏振方向都会呈现出sin函数的规律性变化,拉曼光谱的峰值强度则呈sin2函数的变化规律;此外,表面等离子体共振会进一步加大拉曼光谱的偏振依赖性。     

Surface Enhanced Raman Scattering on Self-assembled Nano Silver Film Prepared by Electrolysis Method

用一种廉价的电解方法制备了纳米银膜,并详细研究了在这种银膜上的表面增强拉曼散射效果．结晶紫为本实验的检测性分子．通过实验发现,这种银膜用便携式拉曼光谱仪测试并计算出的表面增强拉曼散射的增强因子为603,并对结晶紫的最小检出限为0.1 nmol/L     

纳米Ag材料表面等离子体激元引起的表面增强拉曼散射光谱研究

用热蒸发的方法制备了纳米Ag材料,并用扫描电子显微镜对纳米粒子进行了形貌的表征,通过紫外—可见分光光度计得到Ag纳米粒子的透过谱,得到了Ag纳米粒子的表面等离子体共振的峰值位置.以罗丹明6G为探针分子测定Ag纳米粒子衬底的表面增强拉曼散射效应,通过拉曼散射光谱与透过谱研究了由表面等离子体激元的强极化场引起的表面增强拉曼散射效应,结合透过谱与拉曼增益因子提出了一种描述表面等离子体光学和电学特性的方法,并结合扫描电镜的结果给出了不同结构的纳米Ag材料对表面等离子体激元强度的影响. 关键词： 热蒸发 纳米Ag材料 表面等离子体 表面增强拉曼散射     

膜结构对金纳米线阵列表面增强拉曼散射的影响

金纳米线阵列作为表面增强拉曼散射的基底能够产生有效的增强效应,金纳米线阵列通过金线之间的电场耦合产生增强的拉曼信号。在实验中,制备出金纳米线阵列与金纳米刷,两种样品结构不同,金纳米刷的一面带有金膜。用巯基吡啶作为探针分子,金纳米刷的SERS实验显示出很好的增强效应,增强因子为106,不同位点的SERS谱具有区域不均一的特征。而相同实验条件下的金纳米线阵列的增强因子只有102。光学吸收谱表明这两种结构均发生了共振吸收增强电场,对其结构的分析表明,这两种结构具有不同的电场局域化分布,同时金纳米刷中金线上端强烈的电场耦合,这是其具有更好的增强效用的原因。同时,4-MP的表面增强拉曼谱的变化特征体现了化学增强效应的影响。     

Enhancement of Secondary Radiation of Chromophores Adsorbed on the Rough Surface of Thin Silver Films under Conditions of Resonance Excitation

The spectra of giant Raman scattering of light and surfaceenhanced fluorescence of certain chromophores absorbing light in the visible spectrum region are investigated. The factors that have an effect on the enhancement of secondary radiation of chromophores adsorbed on the surface of rough silver films under conditions of resonance excitation are determined. The spectra of mirror reflection of light by the substrates used are considered. The coefficients of diffuse and mirror reflection, absorption, and transmission of light by thin silver films at wavelengths of 488 and 633 nm are determined. The scheme of an experimental system for observation of the spectra of giant Raman scattering and surfaceenhanced fluorescence on the source side of a transparent substrate is proposed. Conclusions on the predominant contribution of the resonance excitation of surface plasmons to the enhancement of the signal of the giant Raman scattering and surfaceenhanced fluorescence of molecules adsorbed on the rough metal surface are drawn.     

Optical Properties of Plasmon Resonances with Ag/SiO2/Ag Multi-Layer Composite Nanoparticles

Optical properties of plasmon resonance with Ag/SiO2/Ag multi-layer nanoparticles are studied by numerical simulation based on Green＇s function theory. The results show that compared with single-layer Ag nanoparticles, the multi-layer nanoparticles exhibit several distinctive optical properties, e.g. with increasing the numbers of the multi-layer nanoparticles, the scattering efficiency red shiRs, and the intensity of scattering enhances accordingly. It is interesting to find out that slicing an Ag-layer into multi-layers leads to stronger scattering intensity and more ＂hot spots＂ or regions of stronger field enhancement. This property of plasmon resonance of surface Raman scattering has greatly broadened the application scope of Raman spectroscopy. The study of metal surface plasmon resonance characteristics is critical to the further understanding of surface enhanced Raman scattering as well as its applications.     

Raman effect in the x-ray region

This paper presents a brief review of x-ray Raman scattering and some of our calculations on Raman scattered line shapes from light elements. We summarise the history of the Raman process in the x-ray region and present a detailed theory of the Raman scattering from an atomic many-electron system. Actual calculations of the Raman cross-section using this theory in single-particle approximation are given. The process of internal resonance Raman scattering is also discussed in the same formulation. The Raman cross-section is compared with the cross-sections of other x-ray scattering processes.     

Sers investigation on the homologeous series of a cyanine dye adsorbed on silver colloidal particles

The Surface Enhanced Raman Scattering (SERS) on the first three representatives of the homologeous series of 3,3′-diethyl-2,2′-benzthiacyanines adsorbed on silver colloids was investigated in the blue-green excitation region. In spite of their different absorption wave lengths, i.e. different resonance Raman scattering (RRS) -conditions, the dyes showed very similar scattering intensities in SERS-experiments. This can be explained by a balancing superposition of RRS and a surface enhancement where the latter will be smaller under RRS-conditions than in the case of a more “normal” RS of the adsorbed dye.     

Surface-enhanced Raman scattering properties of highly ordered self-assemblies of gold nanorods with different aspect ratios

Gold nanorods with aspect ratios of from 1 (particles) to 31.6 were synthesized by the seed-mediated method and packed in a highly ordered structure on a large scale on silicon substrates through capillary force induced self-assembly behaviour during solvent evaporation.The gold nanorod surface exhibits a strong enhancing effect on Raman scattering spectroscopy.The enhancement of Raman scattering for two model molecules (2-naphthalenethiol and rhodamine 6G) is about 5-6 orders of magnitude.By changing the aspect ratio of the Au nanorods,we found that the enhancement factors decreased with the increase of aspect ratios.The observed Raman scattering enhancement is strong and should be ascribed to the surface plasmon coupling between closely packed nanorods,which may result in huge local electromagnetic field enhancements in those confined junctions.     

A comparison of Raman scattering,resonance Raman scattering,and fluorescence from molecules adsorbed on silver island films

The enhancement of Raman scattering (RS), resonance Raman scattering (RRS), and fluorescence from molecules adsorbed on silver-island films is reported. A heirarchy of enhancements is found: 10⁵ for RS, 10³ for RRS, and 0.1–10 for fluorescence, depending on the quantum yield of the free molecule. Using the framework of the electromagnetic theory of surface-enhanced Raman scattering, generalized to treat molecular resonance phenomena, we develop a unified picture of the role of the surface plasmon resonances, and the surface-induced damping, in the light scattering processes. The observed heirarchy of enhancements is shown to have important spectroscopic consequences.     

Two-magnon Raman scattering in a spin density wave antiferromagnet

We present the results for a model calculation of resonant two-magnon Raman scattering in a spin density wave (SDW) antiferromagnet. The resonant enhancement of the two-magnon intensity is obtained from a microscopic analysis of the photon-magnon coupling vertex. By combining magnon-magnon interactions with ‘triple resonance’ phenomena in the vertex function the resulting intensity line shape is found to closely resemble the measured two-magnon Raman signal in antiferromagnetic cuprates. Both, resonant and non-resonant Raman scattering are discussed for the SDW antiferromagnet and a comparison is made to the conventional Loudon-Fleury theory of two-magnon light scattering.     

密度泛函理论研究黄曲霉素B1的表面增强拉曼散射效应

用密度泛函理论B3LYP方法和6-311G(d,p)/Lanl2DZ优化得到黄曲霉素B₁(AFB₁)分子及其复合物AFB₁-Ag的稳定结构,并计算了复合物的表面增强拉曼光谱和预共振拉曼光谱. 结果表明,AFB₁分子的拉曼光谱很大程度依赖于吸附位点以及入射光的激发波长. 与分子的常规拉曼光谱相比,复合物表面增强拉曼光谱中C=O伸缩振动模的增强因子约为10²～10³复合物的极化率增强而导致的静态化学增强,并分析了振动模式的振动方向与其拉曼强度的关系．选择复合物最大吸收峰附近激发光266和482 nm以及远离共振吸收波长785和1064 nm作为入射光,计算得到不同入射光激发下复合物的预共振拉曼光谱．结果表明其增强因子最大达到10⁴量级,主要是由电荷转移产生的共振增强引起的．