Modeling of light absorption and scattering by metal nanoparticles coated with organic dye J-aggregate

The results of the theoretical study of optical properties of composite nanoparticles consisting of a metal core (Ag, Au, Cu, Al, Ni, Cr) and a J-aggregate shell of organic dye are presented. Light extinction, absorption, and scattering coefficients in colloidal solutions were calculated within the model based on the Mie theory modified taking into account dimensional phenomena and complemented by calculations of complex dielectric functions of the metal core and J-aggregate shell. The model adequately explains the features observed in light absorption and scattering spectra by hybrid nanoparticles, associated with the plasmon resonance in the metal core and with electronic excitation of the J-aggregate. The strong dependence of the results on geometrical parameters of nanoparticles and dielectric constants of core and shell materials was demonstrated. Methods for controlling the effects of the plasmon-exciton interaction in the system and optical properties of composite materials developed based on nanoparticles under study are discussed.     

All optical switch based on Fano resonance in metal nanocomposite photonic crystals

We investigate the potential of plasmonic resonance in metal nanocomposite materials for the design of photonic crystal all optical switches by numerical methods. We study the absorption effect of the plasmonic resonance on the Fano resonances of one dimensional photonic crystal slabs covered by a metal nanocomposite layer. It is shown that the absorption reduces the contrast of the Fano resonances. However, for adequate metal nanoparticle concentrations it is possible to achieve both sufficiently sharp Fano resonance and strong Kerr nonlinearity, which provides a suitable condition for the design of high contrast and low threshold switches.     

Investigation of resonant properties of metal core–shell nanoparticles using T-matrix calculations

Using T-matrix method, plasmon resonance properties of metal core–shell nanoparticles are systematically investigated. It is shown that dielectric/metal core–shell structure may be excited stronger at resonance than metal/dielectric and hetero-metal ones, but the resonance states are extremely sensible to the layers thickness. For three-layer nanospheres, resonance properties will be dominated by a sub-10 nm silver outermost shell, while only weakened by a silica one. Finally, tiny eccentric distance between the centers of core and shell in eccentric two-layer nanoparticles may fundamentally change the resonance mode of nanoparticles, and results in higher local electrical field enhancement than concentric nanospheres.     

Ag/Si核壳结构纳米颗粒粒子系的吸收特性研究

当电子振动频率与入射光的频率相同时,部分金属纳米颗粒可以在其表面激发局部表面等离子共振效应(LSPR),该波长下颗粒的吸收增强。这种效应也被应用于增强拉曼光谱信号的强度。本文研究了以Ag为外壳材料、Si为内核的核壳结构纳米颗粒粒子系的吸收特性。采用时域有限差分方法求解了颗粒随机分布粒子系的吸收率,分析了颗粒体积分数、内核外壳尺寸、椭球化等因素对粒子系吸收特性的影响以及对吸收峰的调控作用。     

Generation of electromagnetic waves by a rotating plasma

Generation of electromagnetic waves by an annular shell of plasma rotating in crossed radial electrostatic and axial magnetic fields in a cylindrical resonator is investigated theoretically. Dispersion relations are obtained describing the interaction of the waves with the plasma. It is shown that generation of waves by a narrow plasma shell is possible due to a cyclotron resonance, Čerenkov resonance, or plasma resonance. Here we consider a Čerenkov resonance, where the velocities of the plasma components and the phase velocities of the waves are perpendicular to the constant magnetic field. The frequencies and growth rates of the waves are found under conditions of the above-mentioned resonances in a uniform and in a nonuniform plasma shell. Advantages and disadvantages of wave generation under various conditions are noted. Zh. Tekh. Fiz. 69, 16–21 (February 1999)     

不同Ag壳厚度Au@Ag纳米粒子的调控制备表征及表面增强拉曼光谱的效应

采用化学还原法制备了以Au为核、包覆Ag的双金属核壳Au@Ag纳米粒子,并成功地用于表面增强拉曼光谱(SERS)分析测试。通过改变制备液中Ag/Au的量比来调控Ag壳包覆厚度。采用透射电子显微镜(TEM)和紫外-可见光谱仪(UV-Vis)对Au@Ag纳米粒子的构貌进行表征。TEM显示明显存在核壳结构,且Ag壳层随Ag/Au的量比的增加而逐渐变厚;UV-Vis表明随着Ag/Au的量比的增加,Au@Ag纳米粒子出现了Au核与Ag壳吸收峰的2个等离子体共振峰,同时伴随着Au峰的蓝移和Ag峰的红移。以双甲脒为分析物,考察了不同Ag/Au的量比时的Au@Ag纳米粒子的SERS活性。结果表明,SERS活性随Ag/Au的量比的增加先增大后减小,在6∶5时其SERS增强效应最佳,此时Ag壳厚度约为6 nm。以对巯基苯胺(4-ATP)、结晶紫(CV)和双甲脒为分析测试对象,对比了Au@Ag、Ag、Au 3种基底的SERS活性。结果表明,所制备的Au@Ag纳米粒子的SERS活性要明显优于单纯的Au、Ag纳米粒子。     

Surface plasmon resonance of Ag nanoparticles in the vicinity of a high impedance surface

Surface Plasmon resonance of Ag nanoparticles in the vicinity of a high impedance surface is investigated. Mushroom-like nanostructures were vertically grown on silicon substrate to form a high impedance surface operating in the range of optical frequencies. Formation of Ag nanoparticles on the fabricated high impedance surface was realized using plasma bombardment process. Optical measurements show an enhancement in the surface plasmon resonances of Ag nanoparticles. Also it was shown that the plasmon resonance peak of the Ag nanoparticles shifts to blue when Ag nanoparticles approach to the high impedance surface.     

Interaction of gold nanoparticles with bovine serum albumin

The interaction between gold nanoparticles and bovine serum albumin (BSA) in aqueous solutions was studied. The formation of nanoparticle—BSA associates was demonstrated, which is expressed in a bathochromic shift of the surface plasmon resonance band by 5–6 nm in the absorption spectrum. The results were approximated using the Drude model for metal spheres. The thickness of the dielectric (protein) shell of the nanoparticle and its permittivity (refractive index) were calculated.     

Collective plasmon resonances in monolayers of metal nanoparticles and nanoshells

The collective plasmon resonances in a monolayer formed by metal or metal-dielectric nanoparticles with dipole or quadrupole single-particle resonances are theoretically and experimentally studied. The extinction, scattering, and absorption spectra are calculated using an exact many-particle solution for the system of interacting particles. With increasing surface density of particles in the monolayer, the dipole resonance is suppressed, and the spectrum of the collective system is determined by the quadrupole plasmon only. It is shown that the selective suppression of the long-wavelength extinction band is caused by the collective suppression of the dipole scattering mode, whereas the short-wavelength absorption spectrum of the monolayer differs little from the single-particle spectrum. Using dark-field light and atomic force microscopy, the kinetics of self-assembling of nanoshells is studied. It is shown that the universal linear relation between the relative shift of the wavelength of the collective quadrupole resonance and the relative increment of the refractive index of the surrounding medium is implemented.     

Optical Properties of Metal-Dielectric Structures Based on Photon-Crystal Opal Matrices

Optical properties of novel metal–dielectric nanocomposite materials based on opal matrices have been investigated. The position of optical resonances of nanocomposites, obtained by embedding of silver into the opal matrix by the electrothermodiffusion method, is explained by the Bragg diffraction, and an asymmetric form of resonance curves is attributed to the Fano resonance. An anomalous transmission and absorption of light by hybrid plasmon-photonic layered heterostructures, which is apparently associated with excitation of surface plasmon-polaritons, propagating along “metal–dielectric” interfaces, was revealed.

     

Plasmonics properties of trimetallic Al@Al2O3@Ag@Au and Al@Al2O3@AuAg nanostructures

Bimetallic and trimetallic nanoparticles have attracted significant attention in recent times due to their enhanced electrochemical and catalytic properties compared to monometallic nanoparticles. The numerical calculations using Mie theory has been carried out for three-layered metal nanoshell dielectric–metal–metal (DMM) system consisting of a particle with a dielectric core (Al@Al₂O₃), a middle metal Ag (Au) layer and an outer metal Au (Ag) shell. The results have been interpreted using plasmon hybridization theory. We have also prepared Al@Al₂O₃@Ag@Au and Al@Al₂O₃@AgAu triple-layered core–shell or alloy nanostructure by two-step laser ablation method and compared with calculated results. The synthesis involves temporal separations of Al, Ag, and Au deposition for step-by-step formation of triple-layered core–shell structure. To form Al@Ag nanoparticles, we ablated silver for 40 min in aluminium nanoparticle colloidal solution. As aluminium oxidizes easily in water to form alumina, the resulting structure is core–shell Al@Al₂O₃. The Al@Al₂O₃ particle acts as a seed for the incoming energetic silver particles for multilayered Al@Al₂O₃@Ag nanoparticles is formed. The silver target was then replaced by gold target and ablation was carried out for different ablation time using different laser energy for generation of Al@Al₂O₃@Ag@Au core–shell or Al@Al₂O₃@AgAu alloy. The formation of core–shell and alloy nanostructure was confirmed by UV–visible spectroscopy. The absorption spectra show shift in plasmon resonance peak of silver to gold in the range 400–520 nm with increasing ablation time suggesting formation of Ag–Au alloy in the presence of alumina particles in the solution.     

Enhancement of photoluminescence of the CdSe/CdS quantum dots on quartz substrates in the presence of silver nanoparticles

Multilayer systems consisting of layers of hybrid quantum dots are fabricated. The quantum dots with the CdSe/CdS core/shell structure are chemically synthesized and deposited on the surface of quartz glass that contains ion-synthesized silver nanoparticles in the near-surface region. Silver nanoparticles exhibit optical absorption owing to the localized surface plasmon resonance. Variations in the photoluminescence intensity of the layer related to an increase in the distance from the quartz surface with metal nanoparticles are studied. An increase in the photoluminescence intensity is observed under excitation in the spectral region of the plasmon absorption of silver nanoparticles. An optimal distance between the layers is determined to maximize the enhancement of the photoluminescence of quantum dots in the presence of the near field of metal nanoparticles.     

Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

Pure metal iron nanoparticles are unstable in the air. By a coating iron on nanoparticle surface with a stable noble metal, these air-stable nanoparticles are protected from the oxidation and retain most of the favorable magnetic properties, which possess the potential application in high density memory device by forming self-assembling nanoarrays. Gold-coated iron core-shell structure nanoparticles (Fe/Au) synthesized using reverse micelles were characterized by transmission electron microscopy (TEM). The average nanoparticle size of the core-shell structure is about 8 nm, with about 6 nm diameter core and 1∼2 nm shell. Since the gold shell is not epitaxial growth related to the iron core, the morié pattern can be seen from the overlapping of iron core and gold shell. However, the gold shell lattice can be seen by changing the defocus of TEM. An energy dispersive X-ray spectrum (EDS) also shows the nanoparticles are air-stable. The magnetic measurement of the nanoparticles also proved successful synthesis of gold coated iron core-shell structure. The nanoparticles were then assembled under 0.5 T magnetic field and formed parallel nanobands with about 10 μm long. Assembling two dimensional ordered nanoarrays are still under going. Received 29 November 2000     

表面分子功能化银纳米粒子的光谱特征

通过玻片表面构筑银纳米粒子二维组装结构研究吸附分子对银粒子表面等离子体共振的影响.吸收光谱结果表明银纳米粒子表面吸附二硫代乙二酰胺分子可导致金属粒子的表面等离子体共振吸收红移,主要与金属粒子的微环境改变以及吸附分子与金属间电荷转移而导致的金属粒子内部电子密度改变有关.二硫代乙二酰胺分子通过其氨基和巯基共同吸附于金属表面.     

The effect of the size,shape, and structure of metal nanoparticles on the dependence of their optical properties on the refractive index of a disperse medium

The effect of the size, shape, and structure of gold and silver nanoparticles on the dependence of their extinction and integral scattering spectra on the dielectric environment has been investigated. Calculations were performed using the Mie theory for spheres and nanoshells and the T-matrix method for chaotically oriented bispheres, spheroids, and s cylinders with hemispherical ends. The sensitivity of plasmon resonances to variations in the refractive index of the environment in the range 1.3–1.7 for particles of different equivolume size, as well as to variations in the thickness of the metal layer of nanoshells, was studied. For nanoparticles with an equivolume diameter of 15 nm, the maximal shifts of plasmon resonances due to variation in the refractive index of the environment are observed for bispheres and the shifts decrease in the series nanoshells, s cylinders or spheroids, and spheres. For particles 60 nm in diameter, the largest shifts of plasmon resonances occur for nanoshells and the shifts decrease in the series bispheres, s cylinders or spheroids, and spheres. All other conditions being the same, silver nanoparticles are more sensitive to the resonance tuning due to a change in the dielectric environment.     

Theoretical studies on the near field properties of non-concentric core-shell nanoparticle dimers

The concentric core-shell nanoparticle dimers have “hot spots” with enhanced electric fields in their junctions, which can be used in the surface enhanced Raman spectra analysis. Here the non-concentric core-shell nanoparticle dimers are proposed by introducing a shift between the dielectric core and the metal shell. By using the three dimensional finite difference time domain method, the plasmon resonances and the near field properties of the core-shell nanoparticle dimers affected by the non-concentric shift, dimer separation, excitation wavelength and polarization are analyzed in detail. The results show that the local near fields of the non-concentric core-shell nanoparticle dimers can be much more enhanced than those of the concentric ones. Also the plasmon resonance wavelengths of the dimers can be effectively tuned by the non-concentric shifts between the core and shell. The proposed nanostructures can have great potential in various near field applications.     

银粒子的表面修饰及荧光表面增强效应

采用表面化学修饰制备了Ag-SiO2核-壳纳米粒子,发现SiO2包裹壳层形状随其厚度而改变,包裹初期SiO2壳层依托银核的形状生长,随着壳层厚度增加则趋于热力学稳定的球状。银纳米粒子的表面等离子体共振可由SiO2包裹壳层厚度调变,银核吸收谱峰随壳层厚度增大而红移。Ag-SiO2核-壳纳米粒子可极大增强罗丹明6G的荧光强度,且表面增强效应与壳层的厚度密切相关。     

Resonance scattering of canonical elastic shells in absorbing fluid medium

Resonance scattering of elastic spherical shell and cylindrical shell while the surrounding fluid medium has absorption is studied. The normal mode solution derived using exact elastic theory and the separation of variables is still applicable. However, the scattering form function has to be modified for the absorbing medium, otherwise the unreasonable result would be obtained. The backscattering form function in the absorbing medium is redefined, and the form function of elastic spherical and cylindrical shell with vacuum or solid matter filled is calculated in various absorption conditions. The results show that the absorption of surrounding fluid leads to notable attenuation of the coincidence resonances in the mid-frequency, but it has a little influence on the low-frequency resonance scattering induced by the filler inside the shell.     

Super scattering phenomenon in active spherical nanoparticles

Localized surface electromagnetic resonances in spherical nanoparticles with gain are investigated by using the Mie theory. Due to the coupling between the gain and resonances, super scattering phenomenon is raised and the total scattering efficiency is increased by over six orders of magnitude. The dual frequency resonance induced by the electric dipole term of the particle is observed. The distributions of electromagnetic field and the Poynting vector around nanoparticles are provided for better understanding different multipole resonances. Finally, the scattering properties of active spherical nanoparticles are investigated when the sizes of nanoparticles are beyond the quasi-static limit. It is noticed that more highorder multipole resonances can be excited with the increase of the radius. Besides, all resonances dominated by multipole magnetic terms can only appear in dielectric materials.     

Enhanced photoluminescence of conjugated polymer thin films on nanostructured silver

Photoluminescence of a conjugated polymer in the presence of surface plasmons on metallic nanoparticles is studied. A layered device structure was constructed that enabled control over nanoparticle diameter and separation between the polymer and nanoparticles layers. The dependence of the surface plasmon evanescent field and energy transfer has been investigated with the largest enhancement in photoluminescence observed at a 40 nm distance separation between the fluorophore and the surface plasmon. A spectrum of surface plasmon resonances ranging from the emission to the absorption energies of the conjugated polymer revealed largest enhancements when the resonance was tuned to the conjugated polymer emission energy. At peak photoluminescence the maximum photoluminescent enhancement was found to be 5.6 times of the photoluminescence of the control structure and the total integrated enhancement was 5.9 times.