Surface plasmon spectroscopy of metal/dielectric structures

Surface electromagnetic waves (i.e. plasmons) were excited in metal—oxide—metal (MOM) multi-layer thin film structures by the tunnel current from an external dc source. Surface plasmons decayed to photons in the visible region with typically 10⁻¹⁰−10⁻¹²W cm⁻² light intensity.A very sensitive single channel optical spectrometer was constructed to study both spectral and angular distributions of light emitted from aluminum—oxide—noble-metal (Ag, Au, Cu) thin film diodes mounted into a cold-finger type liquid nitrogen optical cryostat. When MOM structures were prepared on substrates with regular surface modulation of 300–900 nm periods, spectral and angular measurements of the emitted light allowed one to construct the energy—wave-vector dispersion diagram of surface plasmons. This was of help in identifying the top meta/vacuum fast mode plasmons as the source of photon emission.     

Plasmon hybridization in spherical nanoparticles

We show that the plasmon resonances in single metallic nanoshells and multiple concentric metallic shell particles can be understood in terms of interaction between the bare plasmon modes of the individual surfaces of the metallic shells. The interaction of these elementary plasmons results in hybridized plasmons whose energy can be tuned over a wide range of optical and infrared wavelengths. The approach can easily be generalized to more complex systems, such as dimers and small nanoparticle aggregates.     

Interplay between collective and single electron excitations in large metal clusters

Collective and single electron excitations of large metal clusters supported on transparent substrates are investigated. The applied experimental techniques include extinction spectroscopy and laser induced dissociation accompanied by the ejection of individual atoms. The optical spectra depend on the electromagnetic far field and reflectcollective electron excitations of the conduction electrons, i.e. surface plasmons. Dissociation, however, is correlated to repulsivesingle electron energy levels. The characteristics of these localized excitations indicate a strong influence of collective excitations. In particular, it is found that nonlocal optical effects are important. In this picture surface plasmons catalytically enhance the number of single electron excitations and therefore of the metal atoms ejected as a result of the absorption of visible light. Results will be presented, which illustrate this interplay between collective and single electron excitations.     

Plasmon modes of curvilinear metallic core/shell particles

The plasmon hybridization method is generalized to calculate the plasmon modes and optical properties of solid and dielectric-core/metallic-shell particles of geometrical structures that can be described using separable curvilinear coordinates. The authors present a detailed discussion of the plasmonic properties of hollow metallic nanowires with dielectric cores and core/shell structures of oblate and prolate spheroidal shapes. They show that the plasmon frequencies of these particles can be expressed in a common form and that the plasmon modes of the core/shell structures can be viewed as resulting from the hybridization of the solid particle plasmons associated with the outer surface of the shell and of the cavity plasmons associated with the inner surface.     

Plasmon microscopy and imaging ellipsometry of Artrobacter oxydans attached on polymer films

The attachment of Artrobacter oxydans 1,388 on a newly synthesized biodegradable copolymer of poly-(hexanlactam)-co-block-poly-(delta-valerolactone) is investigated by optical, microscopic and biochemical methods. The potentials of surface plasmon microscopy and imaging ellipsometry for detecting microorganisms when Al films are used to excite plasmons is assessed by comparing images obtained by these methods with dark field microscopy pictures. The experimental results demonstrate that in this case imaging ellipsometry and plasmon microscopy in transmission are promising methods and can be used in optical sensors for monitoring cell adhesion.     

贵金属纳米材料的液相合成及其表面等离子体共振性质应用

金属中的表面等离子体共振是描述其导带电子在电磁场作用下集体振荡的一个物理概念。金属纳米颗粒由于其表面等离子体共振性质表现出独特的光学应用。本文在相关研究的基础上,综述了具备表面等离子体共振性质的不同形貌及多种复合结构的贵金属纳米材料的制备和应用,并对其发展及应用前景进行了展望。     

贵金属纳米材料的液相合成及其表面等离子体共振性质应用

金属中的表面等离子体共振是描述其导带电子在电磁场作用下集体振荡的一个物理概念。金属纳米颗粒由于其表面等离子体共振性质表现出独特的光学应用。本文在相关研究的基础上,综述了具备表面等离子体共振性质的不同形貌及多种复合结构的贵金属纳米材料的制备和应用,并对其发展及应用前景进行了展望。     

Plasmon resonances on metal tips: understanding tip-enhanced Raman scattering

Calculations of the electric-field enhancements in the vicinity of an illuminated silver tip, modeled using a Drude dielectric response, have been performed using the finite difference time domain method. Tip-induced field enhancements, of application in "apertureless" Raman scanning near-field optical microscopy (SNOM), result from the resonant excitation of plasmons on the metal tip. The sharpness of the plasmon resonance spectrum and the highly localized nature of these modes impose conditions to better exploit tip plasmons in tip-enhanced apertureless SNOM. The effect of tip-to-substrate separation and polarization on the resolution and enhancement are analyzed, with emphasis on the different field components parallel and perpendicular to the substrate.     

Integration of gold nanoparticles in optical resonators

The optical absorption of one-dimensional photonic crystal based resonators containing different types of gold nanoparticles is controllably modified by means of the interplay between planar optical cavity modes and localized surface plasmons. Spin-casting of metal oxide nanoparticle suspensions was used to build multilayered photonic structures that host (silica-coated) gold nanorods and spheres. Strong reinforcement and depletion of the absorptance was observed at designed wavelength ranges, thus proving that our method provides a reliable means to modify the optical absorption originated at plasmonic resonances of particles of arbitrary shape and within a wide range of sizes. These observations are discussed on the basis of calculations of the spatial and spectral dependence of the optical field intensity within the multilayers.     

Exciton-plasmon interaction in a composite metal-insulator-semiconductor nanowire system

We report about the synthesis and optical properties of a composite metal-insulator-semiconductor nanowire system which consists of a wet-chemically grown silver wire core surrounded by a SiO2 shell of controlled thickness, followed by an outer shell of highly luminescent CdSe nanocrystals. With microphotoluminescence (micro-PL) experiments, we studied the exciton-plasmon interaction in individual nanowires and analyzed the spatially resolved nanocrystal emission for different nanowire length, SiO2-shell thickness, nanocrystal shape, pump power, and emission polarization. For an SiO2 spacer thickness of approximately 15 nm, we observed an efficient excitation of surface plasmons by excitonic emission of CdSe nanocrystals. For nanowire lengths up to approximately 10 microm, the composite metal-insulator-semiconductor nanowires ((Ag)SiO2)CdSe act as a waveguide for 1D-surface plasmons at optical frequencies with efficient photon outcoupling at the nanowire tips, which is promising for efficient exciton-plasmon-photon conversion and surface plasmon guiding on a submicron scale in the visible spectral range.     

Size dependent index of refraction and absorption of a spherical metal cluster

Size-dependent optical properties of large metal clusters are studied on the example of spherical sodium clusters. The model is based on the fact, that a sphere filled with free-electron gas forms a cavity with size dependent eigenfrequencies of the optically excitable TM plasmons. Therefore the dielectric function of the system gains the resonant character. The dielectric function defines the size-dependent indices of absorption and of refraction.     

Electric field amplification of plasmon-molecule hybrids revealed by first-principles time dependent density functional theory calculations

Using first-principles quantum mechanical calculations, we investigate the electric field amplification in hybrid nanostructures composed of few-atom Ni linear chains attached to an organic molecule. We found that the pristine Ni linear chains exhibit localized plasmons and produce nanoscale hotspot regions, acting as a plasmon-like nanoantenna. We demonstrate that localized plasmons provide massive electric field amplification in the vicinity of the molecule. Besides, we also investigated the active modulation of the optical absorption spectra due to the inclusion of a positive and/or negative electric field in the Hamiltonian. We believe that the results presented in this work are important for the emerging field of cavity induced photo-catalysis and will aid in the realization of new quantum nano-optic devices.     

Modeling molecular effects on plasmon transport: silver nanoparticles with tartrazine

Modulation of plasmon transport between silver nanoparticles by a yellow fluorophore, tartrazine, is studied theoretically. The system is studied by combining a finite-difference time-domain Maxwell treatment of the electric field and the plasmons with a time-dependent parameterized method number 3 simulation of the tartrazine, resulting in an effective Maxwell∕Schro?dinger (i.e., classical∕quantum) method. The modeled system has three linearly arranged small silver nanoparticles with a radius of 2 nm and a center-to-center separation of 4 nm; the molecule is centered between the second and third nanoparticles. We initiate an x-polarized current on the first nanoparticle and monitor the transmission through the system. The molecule rotates much of the x-polarized current into the y-direction and greatly reduces the overall transmission of x-polarized current.     

Designing the plasmonic response of shell nanoparticles: spectral representation

A spectral representation formalism in the quasistatic limit is developed to study the optical response of nanoparticles, such as nanospheres, nanospheroids, and concentric nanoshells. A transfer matrix theory is formulated for systems with an arbitrary number of shells. The spectral representation formalism allows us to analyze the optical response in terms of the interacting surface plasmons excited at the interfaces by separating the contributions of the geometry from those of the dielectric properties of each shell and surroundings. Neither numerical nor analytical methods can do this separation. These insights into the physical origin of the optical response of multishelled nanoparticles are very useful for engineering systems with desired properties for applications in different fields ranging from materials science and electronics to medicine and biochemistry.     

NIR-plasmon-enhanced Systems for Energy Conversion and Environmental Remediation

The introduction of plasmons is an important method to solve the insufficient utilization of the full spectrum of solar energy by semiconductor catalysts. However, semiconductor catalysts combined with traditional noble metal plasmons(Au, Ag) can only extend the absorption spectrum to partially visible light. In order to further improve the photoenergy absorption efficiency of catalysts, they need to be able to effectively utilize near-infrared light, which has become a new research direction. Recent studies have shown that traditional noble metal plasmons can absorb a part of NIR through special morphology, size control and material composite. At the same time, gratifying achievements have been made in the application of plasmonic semiconductors with broad spectrum absorption in catalysis. This article reviews the principles of generating and regulating plasmonic effects in different catalytic systems. The applications of plasmon absorption of near-infrared light in energy conversion and environmental remediation have also been presented.     

Recent advancements in optical DNA biosensors: exploiting the plasmonic effects of metal nanoparticles

The emerging field of plasmonics, the study of electromagnetic responses of metal nanostructures, has revealed many novel signal enhancing phenomena. As applied to the development of label-free optical DNA biosensors, it is now well established that plasmon-based surface enhanced spectroscopies on nanostructured metal surfaces or metal nanoparticles can markedly improve the sensitivity of optical biosensors, with some showing great promise for single molecule detection. In this review, we first summarize the basic concepts of plasmonics in metal nanostructures, as well as the characteristic optical phenomena to which plasmons give rise. We will then describe recent advances in optical DNA biosensing systems enabled by metal nanoparticle-derived plasmonic effects, including the use of surface enhanced Raman scattering (SERS), colorimetric methods, "scanometric" processes, and metal-enhanced fluorescence (MEF).     

Micro-chemical sensors based on fiber-optic excitation of surface plasmons

In this paper the theoretical base and experimental results of a new class of fiber optical supported surface plasmon resonance spectroscopy (SPRS) transducer is given. Surface plasmons were excited by polychromatic light, and the resonant excitation is detected as an intensity minimum in the measured spectra at certain wavelengths. The excitation takes place at the end zone of a multimode fiber coated with a thin surface plasmon resonance supporting metal layer. As examples for the large application field of this transducer a fiber optical immunosensor for the detection of antibodies against bovine serum albumin and a gas sensor for remote detection of tetrachloroethene was constructed and tested successfully. The sensors were constructed following the theoretical predictions for an optimal performance.     

Optical switching of coupled plasmons of Ag-nanoparticles by photoisomerisation of an azobenzene ligand

The optical switching of coupled plasmons of silver nanoparticles derivatised with a photoisomerisable azobenzene ligand is presented. It is shown that nanoparticle clusters, linked with an azobenzene dithiol molecule, display switchable optical properties. The photoisomerisation of the linker molecule was used to vary the separation between nanoparticles, which was monitored by changes in the UV-Vis-spectra of the plasmon band of adjacent nanoparticles. A red-shift due to the appearance of a coupled longitudinal plasmon band was observed resulting from the formation of nanoparticle clusters. The maximum absorbance wavelength of this secondary plasmon band was altered by isomerisation of the linker and the spectral changes observed were in good agreement with theory and earlier measurements for gold. Evidence of energy transfer between a nanoparticle and an azobenzene terminated monothiol attached to it was also observed in the UV-Vis spectra.     

Plasmon modes of nanosphere trimers and quadrumers

Using the plasmon hybridization method, we investigate the plasmon frequencies and optical absorption spectra of symmetric configurations of nanosphere trimers and quadrumers. Plasmon hybridization allows us to express the fundamental plasmon modes of these multinanosphere systems as linear combinations of the plasmons of individual nanospheres in a manner analogous to molecular orbital theory. We show how group theory may be used to interpret the plasmon modes of each multiparticle system as specific structure-dependent symmetric combinations of the plasmon modes of the individual nanoparticles. We compare the optical absorption spectra calculated using plasmon hybridization with the spectra obtained using finite difference time domain simulations.     

Liquid-supported membranes in chromium(VI) optical sensing: transport modelling

Flat sheet liquid-supported membranes (FSLSM) containing Aliquat 336 as a carrier have been evaluated as sample interface in an optical sensor for Cr(VI) monitoring. A model describing the transport mechanism of Cr(VI) through the membrane is reported. The model considers a diffusion process through a feed aqueous diffusion layer, a fast interfacial chemical reaction and a diffusion of ALQHCrO₄ and (ALQ)₂CrO₄ species through the membrane (Aliquat 336, ALQ). The mathematical equations describing the transport rate are derived and they correlate the membrane permeability coefficient to diffusional and equilibrium parameters as well as to the chemical composition of the system, i.e. extractant concentration in the membrane phase and acidity in the feed phase. The experimental data are explained by the derived equations and the diffusion resistances to mass transfer are evaluated. The influence of other experimental parameters, such as stirring speed in the feed phase and nature of the diluent and stripping agent on the transport is also discussed. Experiments with optical detection demonstrate the suitability of liquid-supported membranes (LSM) containing ALQ as interfaces for optical sensing.