P-thiocresol 吸附在银纳米粒子表面系统的表面增强拉曼散射和表面增强共振拉曼散射的增强研究

文中从实验和计算两方面报道了在514.5 nm激发光下P-Thiocresol吸附在银胶表面系统的表面增强拉曼散射(SERS).文中分析了它的增强机制,发现增强主要来自于电磁场增强.如果考虑距离为2nm的两个银纳米粒子的耦舍效应,两粒子之间的SERS的电磁场增强为7.16 × 107.静态化学增强亦起到部分增强作用,它的增强倍数为6.所以,总的SERS增强,包括静态化学增强和电磁场增强,是Gtotal=Gsc ×GEM=4.4×108.我们也理论地研究了此系统的表面增强共振拉曼散射(SERRS).当激发光与P-Thiocresol-Ag3系统的激发态共振时,电荷转移机制(化学增强)也将起到重要作用,最强的增强可迭106.我们使用电荷密度将激发光下p-Thlocresol和Ag团簇问的电荷转移结果可视化,这是电荷转移的直接理论证据.对于SERRS增强,包括电荷转移和电磁场增强机制,能达到1013.     

Direct visual evidence for the chemical mechanism of surface‐enhanced resonance Raman scattering via charge transfer: (II) Binding‐site and quantum‐size effects

We describe quantum‐size and binding‐site effects on the chemical and local field enhancement mechanisms of surface‐enhanced resonance Raman scattering (SERRS), in which the pyridine molecule is adsorbed on one of the vertices of the Ag₂₀ tetrahedron. We first investigated the influence of the binding site on normal Raman scattering (NRS) and excited state properties of optical absorption spectroscopy. Second, we investigated the quantum‐size effect on the electromagnetic (EM) and chemical mechanism from 300 to 1000 nm with charge difference density. It is found that the strong absorption at around 350 nm is mainly the charge transfer (CT) excitation (CT between the molecule and the silver cluster) for large clusters, which is the direct evidence for the chemical enhancement mechanism for SERRS; for a small cluster the strong absorption around 350 nm is mainly intracluster excitation, which is the direct evidence for the EM enhancement mechanism. This conclusion is further confirmed with the general Mie theory. The plasmon peak in EM enhancement will be red‐shifted with the increase of cluster size. The influence of the binding site and quantum‐size effects on NRS, as well as chemical and EM enhancement mechanisms on SERRS, is significant. Copyright © 2009 John Wiley & Sons, Ltd.     

Direct visual evidence for chemical mechanisms of SERRS via charge transfer in Au20–pyrazine–Au20 junction

The essence of the chemical mechanism for surface‐enhanced resonance Raman scattering (SERRS) is the charge transfer (CT) between the metal and the molecule at the resonant electronic transition, which results in the mode‐selective enhancement in the SERRS spectrum. The site‐orientated CT can directly interpret the mode‐selective chemical enhancement in SERRS. However, it is a great challenge to intutively visualize the orientation and site of the CT. In this paper, for the pyrazine–Au₂ complex, a three‐dimensional (3D) cubic representation is built to provide direct visual evidence for chemical mechanisms of SERRS via CT from the Au₂ cluster to pyrazine at the resonant electronic transition. The relationship between the mode‐selective enhancements in SERRS and the site‐orientated CT was clearly revealed. The intracluster excitation (analog of plasmon excitation in large naonoparticles) was also visualized by the 3D cubic presentation, which provided the direct evidence of local electromagnetic field enhancement of SERRS. To study the quantum size effect and the coupling effect of the nanoparticles, the photoexcitation mechanisms of the Au₂₀–pyrazine complex and the Au₂₀–pyrazine–Au₂₀ junction were also investigated. The tunneling charge transfer from one Au₂₀ cluster to another Au₂₀ cluster outside the pyrazine in Au₂₀–pyrazine–Au₂₀ junction was also revealed visually. The calculated normalized extinction spectra of Au nanoparticles using the generalized Mie theory reveal that the resonance peak is red‐shifted due to the coupling between particles. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical study on SERRS of rhodamine 6G adsorbed on Ag2 cluster: chemical mechanism via intermolecular or intramolecular charge transfer

The problem of the chemical enhancement of rhodamine 6G (R6G) adsorbed on silver cluster has been theoretically investigated by charge difference densities (CDDs) to show the direct charge transfer (CT) evidence. For surface‐enhanced resonance Raman scattering (SERRS) of R6G excited at 514.5 nm, the enhancements of v(151) and v(154) result from weak intermolecular (from Ag to R6G) CT and the strong intramolecular CT [similar to that of resonance Raman scattering (RRS) of R6G], respectively. The possibility of the SERRS of R6G contributed from pure intermolecular CT is also discussed, when the incident light is close to the new metal–R6G CT excited state at 1571.4 nm. Meanwhile compared with the absorption process the fluorescence yield of R6G is investigated by transition densities and CCDs. Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Mechanism of Surface-Enhanced Raman Scattering and Its Application to Highly Sensitive Protein Detection

Surface-enhanced resonance Raman scattering(SERRS)has recently attracted great interest in analytical science due toenormous enhancement factors that have decreased the detec-tionli mits of a wide variety of molecules to the single moleculelevel.The SERRS-electromagnetic(EM)model describessingle-molecule SERRS sensitivity     

Experimental and theoretical evidence for the chemical mechanism in SERRS of rhodamine 6G adsorbed on colloidal silver excited at 1064 nm

The evidence for the existence of a chemical mechanism in surface‐enhanced resonance Raman scattering (SERRS) of rhodamine 6G (R6G) adsorbed on colloidal silver excited at 1064 nm is reported on the basis of experimental and theoretical analyses. A weak absorption peak at around 1060 nm for R6G‐functionalized silver nanoparticles was observed, which is not present in the individual spectra of R6G or silver nanoparticles. Theoretically, the charge difference density reveals that this weak absorption is a metal‐to‐molecule charge transfer excited state. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of shape and interstice on surface enhanced Raman scattering (SERS) of molecules adsorbed on gold nanoparticles in the near‐dipole and quadrupole regions

Surface enhanced Raman scattering (SERS) of adsorbed molecule on colloidal gold nanoparticles of different shapes, namely nanospheres (NSs), nanorods (NRs), and nanoprisms (NPs) as well as the three NPs arrays of different interstice prepared by NS lithography, are studied with incident wavenumbers in the near‐dipole and near‐quadrpole regions of the nanoparticles. In the colloidal gold nanoparticles, the SERS enhancement is the largest for the sharp tip followed by the truncated tip NPs, then the NRs and least enhancement for the NSs. This decreasing order of enhancement occurs although the incident wavenumber was near the dipole resonance of NSs and the quadrupole resonance for the NPs. These varied enhancements are explained in part as due to the binding energies of the nanocrystal facets, but the larger contribution results from the plasmon electromagnetic fields. A parallel finite difference time domain (FDTD) calculations were carried out, which corporate the experimental results and show agreement with ratios of the SERS enhancement for the different shapes. The normalized SERS intensity for NPs of different interstice distances show a sharp rise with the decrease of the interstice distances because of interparticle dipolar and quadrupolar coupling as evidenced also by FDTD calculations. Furthermore, these calculations show that the enhancement is polarization independent for an incident wavelength near quadrupole resonance but polarization dependent for an incident wavelength near the plasmon dipole transition. In the last case, the enhancement is larger by an order of magnitude for a polarization parallel to the NPs bisector than for polarization normal to the bisector with no hot spots for the relatively large interstice dimensions used. Copyright © 2012 John Wiley & Sons, Ltd.     

Distinguishing chemical and electromagnetic enhancement in surface‐enhanced Raman spectra: The case of para‐nitrothiophenol

Surface‐enhanced Raman spectra are simulated using a combined classical electrodynamics/real‐time time‐dependent density functional theory approach and compared to experiments. Emphasis is put on discerning between chemical and electromagnetic enhancement. Therefore, three different calculation scenarios are investigated using para‐nitrothiophenol as a test molecule. In the first one, corresponding to electromagnetic enhancement, we simulate the molecule alone with ab initio computations incorporating the electromagnetic field emitted by a nanoparticle. Chemical enhancement is modeled in the second scenario, where we include not only the molecule into the quantum chemistry calculations but also metal atoms of the nanoparticle. Here, any modification of the electromagnetic field due to the nanoparticle is not considered. In the third scenario, the former two setups are combined and demanding simulations of the hybrid system containing the molecule and the metal atoms exposed to a strongly modified electromagnetic field due to the plasmonic properties of the metallic nanoparticles are considered. Results are compared to our experimentally measured spectra. Based on our analysis, we show here on rigorous grounds that the electromagnetic effect leads to increased absolute Raman scattering cross sections but no change of the relative intensities. In contrast, the chemical effect leads to changes in relative peak height and also to newly emerging bands in the spectrum. These findings will have major implications in any study that concerns the interaction of molecules with metallic nanostructures. Copyright © 2013 John Wiley & Sons, Ltd.     

分子激发中的表面等离激元增强效应

金属纳米粒子的表面等离激元增强效应是纳米科学领域的一个研究热点.针对染料分子与金属纳米粒子的耦合系统,应用偶极-偶极近似计算分子与金属纳米粒子的库仑相互作用,并应用密度矩阵理论描述在不同极化方向的电场作用下的电荷输运过程,分析了分子与金属纳米粒子在不同相对位置下分子激发态的动力学过程,发现表面等离激元的增强效应与分子和金属钠米粒子的相对位置以及等离激元的耗散系数有密切关系,详细讨论了分子与金属纳米粒子间的耦合强度、外场的极化方向、等离激元的寿命及共振激发条件对分子激发态及表面等离激元增强的影响,分析了分子-金属纳米粒子耦合系统中表面等离激元增强效应的物理本质.     

斜入射脉冲X射线产生电流实验

 针对斜入射脉冲X射线与金属的几种可能相互作用机制,设计了实验布局,测量了斜入射X射线在金属靶上产生的脉冲电流,建立了相应的理论模型。结果显示,当X射线入射强度低于10⁵ W/cm²时,以光电效应为主,高于此值时,以热电效应为主导。这表明,X射线加载强度较弱时,电子表现出个体行为,而增大X射线入射强度,电子表现出弱关联集体行为。由此可以预测,超强X射线辐照下,金属表面将出现宏观尺度的电荷密度调制,在退激发过程中,这种调制状态可能以较高的效率辐射定向的微波电磁脉冲。     

Surface‐enhanced Raman scattering study of Ag@PPy nanoparticles

Surface‐enhanced Raman scattering (SERS) spectra of Ag@polypyrrole (PPy) nanoparticles with both 488 and 1064 nm excitation were investigated. Experimental results as well as theoretical analysis demonstrated that electromagnetic (EM) enhancement and charge transfer (CT) both rebounded to the SERS effect of Ag@PPy nanoparticles. When near‐IR excitation (1064 nm) was used for the SERS measurements, the contribution from CT was amplified relative to that from EM because the energy of the near‐IR excitation is far from the surface plasmon resonance of the nanosized Ag particles. The increased doping level of PPy, leading to optimal energy matching between the Fermi levels of the Ag nanoparticles and the energy levels in PPy molecules, could obviouslyenhance the SERS signal. These results suggested that the SERStechnique wasan effective tool for investigating the doping effect and interface interaction in metal‐conductingpolymer composite nanoparticles. In particular, the SERS technique with near‐IR excitation could give more information regarding the contribution of the charge‐transfer mechanism to the spectral enhancement of this kind of system. Copyright © 2010 John Wiley & Sons, Ltd.     

光激发作用下分子与多金属纳米粒子间的电荷转移研究

金属纳米粒子在光激发作用下的增强作用是纳米科学领域的一个研究热点. 针对分子和多个不同位形下的金属纳米粒子在光激发下的相互作用展开了理论研究. 应用密度矩阵理论描述分子和金属纳米粒子同时激发产生表面等离激元后的电荷输运过程. 研究发现, 表面等离激元增强效应与分子和各个金属纳米粒子的相对位置有密切关系. 详细分析了金属纳米粒子间的耦合强度、分子和金属纳米粒子间的耦合强度、表面等离激元能级杂化、分子激发能和外场频率对表面等离激元增强效应的影响.     

基于石墨烯基底的光催化特性

金属纳米结构中传导电子的集体振荡所产生的表面等离子体不仅可以使电磁场在时间和空间上重新分布,还可以使被激发的载流子重新分布.采用机械剥离法制备了石墨烯材料,借助拉曼光谱扫描技术(M apping)研究了石墨的层数在二维区域内的分布情况.研究了2-萘硫醇(2-N T)作为探针分子在石墨烯衬底上的SERS增强特性.结果表明...     

A reflective surface-relief two-layer grating for splitting beams with the polarization-selective property

A polarization-selective beam splitter is presented based on a reflective surface-relief two-layer grating with a metal slab. The grating is composed of two dielectric layers and a metal slab on the substrate. For TE polarization, efficiencies of 97.58% can be diffracted into the reflective −1st order. For TM polarization, two-port output of 47.55% and 47.11% can be split into the 0th order and the −1st order, respectively. Such a polarization-selective beam splitter can be fulfilled by one grating in reflection. The grating depths of two layers are optimized by using rigorous coupled-wave analysis with the given duty cycle of 0.6 and period of 1100 nm. The performance for different incident conditions is investigated when the incident wavelength and angle deviate from the central wavelength and the Bragg angle, respectively. For TM polarization, good uniformity can still be achieved within the given incident wavelength and angle regions. For TE polarization, the reflective polarization-selective beam splitter can have merits of wideband for different incident wavelengths.     

基于金属表面等离子激元控制光束的新进展

表面等离子激元(Surface plasmon polaritons,SPPs)是一种在金属-介质界面上激发并耦合电荷密度起伏的电磁振荡,具有近场增强、表面受限、短波长等特性,在纳米光子学的研究中扮演着重要角色。近年来表面等离子光学和基于SPPs的纳米光子器件的研究引起了国际上科学家们的广泛关注。讨论了SPPs的基本原理和在亚波长结构下的光学特性,介绍了基于亚波长金属结构的表面等离子激元在空间光束准直与聚焦、平面内光束聚焦与传导和在近场纳米光束的控制等方面的研究情况,以及在纳米光子学器件中的潜在应用。     

Surface‐enhanced Raman scattering of molecules adsorbed on Co‐doped ZnO nanoparticles

Transition‐metal‐doped semiconductor nanoparticles (NPs) have been well studied for their optical and catalytic properties but seldom studied by surface‐enhanced Raman scattering (SERS). In this paper, transition‐metal‐doped semiconductor NPs are investigated for their SERS property. Four groups of Co‐doped (0.5, 1, 3, and 5%) ZnO (Co ZnO) NPs and pure ZnO NPs were synthesized and studied. When 4‐mercaptobenzoic acid was used as probing molecule, significant SERS signals were obtained on all the five samples. Moreover, it is very interesting to observe a relationship between the Co‐doping concentration and enhancement of the SERS signals. SERS intensities first increase with doping concentration (up to 1%), and then decrease with further increase in doping concentration (up to 5%). Charge transfer (CT) is considered to be the main contribution to this phenomenon. Different CT ratios from substrates to molecules seem to induce different intensities of the SERS signals. In our experiments, the crystalline defects of Co ZnO NPs caused by the Co dopant affect the CT ratios. A possible mechanism of CT from the valance band of Co ZnO NPs to the lower unoccupied molecular orbital of the molecules via energy of the surface states is suggested. X‐ray photoelectron spectra, UV vis spectra, and Raman spectra were used to characterize the structure and defects in Co ZnO NPs. Copyright © 2011 John Wiley & Sons, Ltd.     

Engineering gold alloys for plasmonics

We demonstrate the formation of metal alloys in Au–Ag, Au–Cu and Au–Pd systems and the experimental determination of their optical properties using optical transmission and reflection spectroscopy. The optical constants define the plasmon resonance wavelength and electromagnetic field local intensity. However, the optical constants behavior cannot be precisely modeled based on the data of pure metals due to unknown morphology and composition of the alloy. It has to be determined experimentally. We demonstrate the surface-enhanced Raman scattering using alloy metals. Depending on the metal to which molecules are adsorbed, we observe enhancement of different Raman modes. It is mainly due to the chemical enhancement effect between metal and molecules.     

Goldstone mode of a magnon Bose−Einstein condensate in MnCO<Subscript>3</Subscript>

The dependence of the enhancement of the Raman scattering on the size of a dielectric column is measured in structures with the spatial modulation of the height and lateral sizes of the dielectric coated with a thick metal layer (10–80 nm). It is established that, in the case of a thick metal coating (silver, gold, and copper coatings are used) at dimensions of the dielectric column close to the laser pump wavelength, considerable enhancement of the Raman signal oscillating upon the variation of the geometrical dimensions of the structure is observed. It is shown that the observed resonance enhancement of the Raman signal is associated with the transformation of the electromagnetic radiation into localized plasmon–polariton modes, and the efficiency of such transformation is determined by the commensurability of the wavelength of the plasmon–polariton mode and the planar size of the metal film. For different metal coatings, the dependence of the enhancement of the Raman scattering on the laser wavelength is measured.     

Identification of two Ag‐2,2′:6′,2″‐terpyridine surface species on Ag nanoparticle surfaces by excitation wavelength dependence of SERS spectra and factor analysis: evidence for chemical mechanism contribution to SERS of Ag(0)–tpy

Measurement and interpretation of the excitation wavelength dependence of surface‐enhanced Raman scattering (SERS) spectra of molecules chemisorbed on plasmonic, e.g. Ag nanoparticle (NP) surfaces, are of principal importance for revealing the charge transfer (CT) mechanism contribution to the overall SERS enhancement. SERS spectra, their excitation wavelength dependence in the 445–780‐nm range and factor analysis (FA) were used for the identification of two Ag‐2,2′:6′,2″‐terpyridine (tpy) surface species, denoted Ag⁺–tpy and Ag(0)–tpy, on Ag NPs in systems with unmodified and/or purposefully modified Ag NPs originating from hydroxylamine hydrochloride‐reduced hydrosols. Ag⁺–tpy is a spectral analogue of [Ag(tpy)]⁺ complex cation, and its SERS shows virtually no excitation wavelength dependence. By contrast, SERS of Ag(0)–tpy surface complex generated upon chloride‐induced compact aggregate formation and/or in strongly reducing ambient shows a pronounced excitation wavelength dependence attributed to a CT resonance (the chemical mechanism) contribution to the overall SERS enhancement. Both the resonance (λ_exc = 532 nm) and off‐resonance (λ_exc = 780 nm) pure‐component spectra of Ag(0)–tpy obtained by FA are largely similar to surface‐enhanced resonance Raman scattering (λ_exc = 532 nm in resonance with singlet metal to ligand CT (¹ MLCT) transition) and SERS (λ_exc = 780 nm) spectra of [Fe(tpy)₂]²⁺ complex dication. Copyright © 2014 John Wiley & Sons, Ltd.