The Nonlinear Optical Response of Hashin-Shtrikman Geometric Composite Materials

The nonlinear optical response of composite materials consisting of metal grains with insulator shells at finite frequency is investigated. It is found that the surface plasmon peak is stronger and the position of surface plasmon peak is "red-shifted" with the shell being thinner. We also found that the nonlinear optical response is related to the shape of the particles and the dielectric property of the shells.     

Lithography-free fabrication of large-area plasmonic nanostructures using colloidal gold nanoparticles

We report simple and efficient fabrication of large-area gold nanostructures using solution-processible gold nanoparticles, where lithography and vacuum evaporation techniques are not involved in the fabrication processes. These gold nanoisland structures exhibit strong particle plasmon resonance that is characterized by optical extinction spectroscopy in the visible spectral range. The tunability of the optical response is realized by controlling the annealing temperature and by changing the concentration of the colloidal solutions of gold nanoparticles. This enables a low-cost route for exploiting new photonic devices, biosensors, and optoelectronic devices with localized field-enhancement.     

Near-field spectroscopy of surface plasmons in flat gold nanoparticles

We use near-field interference spectroscopy with a broadband femtosecond, white-light probe to study local surface plasmon resonances in flat gold nanoparticles (FGNPs). Depending on nanoparticle dimensions, local near-field extinction spectra exhibit none, one, or two resonances in the range of visible wavelengths (1.6-2.6 eV). The measured spectra can be accurately described in terms of interference between the field emitted by the probe aperture and the field reradiated by driven FGNP surface plasmon oscillations. The measured resonances are in good agreement with those predicted by calculations using discrete dipole approximation. We observe that the amplitudes of these resonances are dependent upon the spatial position of the near-field probe, which indicates the possibility of spatially selective excitation of specific plasmon modes.     

Size-dependent denaturing kinetics of bovine serum albumin adsorbed onto gold nanospheres

We have used localized surface plasmon resonance (LSPR) to monitor the kinetics of thermal denaturing of bovine serum albumin (BSA) adsorbed onto gold nanospheres of size 5 nm-100 nm. The effect of the protein on the LSPR was monitored by visible extinction spectroscopy. The wavelength of the peak extinction (resonance) is affected by the conformation of the adsorbed protein layer, and as such can be used as a very sensitive probe of thermal denaturing that is specific to the adsorbed (as opposed to free) protein. The time dependence of the denaturing is measured in the temperature range 60 °C–70 °C, and the lifetimes are used to calculate an activation barrier for thermal denaturing. The results show that thermally activated denaturing of proteins adsorbed onto nanoparticles has a nanoparticle-size-dependent activation barrier, and this barrier increases for decreasing particle size. This may have important implications for other protein-nanoparticle interactions.     

Anomalous thermal denaturing of proteins adsorbed to nanoparticles

We have used localized surface plasmon resonance (LSPR) to monitor the structural changes that accompany thermal denaturing of bovine serum albumin (BSA) adsorbed onto gold nanospheres of size 5nm-60nm. The effect of the protein on the LSPR was monitored by visible extinction spectroscopy. The position of the resonance is affected by the conformation of the adsorbed protein layer, and as such can be used as a very sensitive probe of thermal denaturing that is specific to the adsorbed protein. The results are compared to detailed calculations and show that full calculations can lead to significant increases in knowledge where gold nanospheres are used as biosensors. Thermal denaturing on spheres with diameter > 20 nm show strong similarity to bulk calorimetric studies of BSA in solution. BSA adsorbed on nanospheres with d ⩽ 15nm shows a qualitative difference in behavior, suggesting a sensitivity of denaturing characteristics on local surface curvature. This may have important implications for other protein-nanoparticle interactions.     

Controlling the optical spectra of gold nano-islands by changing the aspect ratio and the inter-island distance: theory and experiment

The extinction spectrum of a dielectric film with periodic array of metallic islands of different shapes and different mutual distances was studied both theoretically and experimentally. It is shown, analytically, numerically and experimentally, that the positions of the surface plasmon resonances depend on the nano-structural details. We propose two ways of controlling plasmon resonance frequency: changing the aspect ratio of the elliptical (or rectangular) islands and changing their mutual distances. A new analytical asymptotic approach for calculating the optical properties of such plasmonic systems is developed. The results of our analytical and numerical studies are in good qualitative agreement with experiment.     

Controlling the interaction between light and gold nanoparticles: selective suppression of extinction

The interaction of visible light with the particle-plasmon resonance of metallic nanoparticles can be controlled by geometrical arrangement of nanoparticle arrays. These arrays are placed on a substrate that supports guided modes in the wavelength range of the particle plasmon. Coupling of this particle-plasmon resonance to the directly incident light and to the waveguide modes results in almost complete suppression of light extinction within narrow spectral bands due to destructive interference. Variation of the structure parameters allows continuous tuning of these high-transmission bands across the particle-plasmon resonance.     

Optical properties of Au–Ag core–shell nanorods on glass and ITO substrates

Gold-silver core–shell nanorods were deposited on glass and ITO plates. SEM observations indicated that some of these nanorods were standing on the ITO plate. The extinction spectra of the plates were measured by varying the angles of incidence of p-polarized monitor light. Deconvolution of these spectra gave six bands in the visible region. The dependence of the peak intensities on the incident angles indicated that the bands at 390 and 420 nm originated from surface plasmon bands in the transverse direction of the nanorods.     

The color of finely dispersed nanoparticles

We discuss the dependence of the color of low-concentrated nanoparticle systems on particle size and mass concentration for Ag, Au and TiN nanoparticles, which exhibit a surface plasmon polariton resonance in extinction spectra. Comparison is made with color data obtained for Ag and Au colloidal suspensions. When particles lump into aggregates, the splitting of the surface plasmon resonance into new resonances affects the extinction of light and, hence, the color of the particle assembly. This is demonstrated for aggregated colloidal suspensions of Ag and Au nanoparticles. Finally, for highly concentrated assemblies such as pigment films, we discuss the dependence of the color in diffuse reflectance and transmittance according to Kubelka and Munk (P. Kubelka, F. Munk: Z. Techn. Phys. 12, 593 (1931)), and extend this model by using optical properties of aggregates of spheres. Received: 2 July 2001 / Published online: 10 October 2001     

Retardation-effect-induced plasmon modes in a silica-core gold-shell nanocylinder pair

The retardation-effect-induced plasmon modes in a silica-core gold-shell nanocylinder pair is investigated by the two-dimension finite difference time domain method. We show that for light polarized perpendicular to the axis connecting the pair, the spectrum depends sensitively on the size of nanocylinder pair. As the size increases, several retardation-induced non-dipolar plasmon modes including multipolar modes appear in the spectrum and the resonance wavelength and strength of its plasmon modes can be tuned by changing separation width between the nanocylinder pair. Both extinction spectra as a function of size of the core-shell nanocylinder and near-field intensity associated with the coupling resonance modes are reported.     

Optimization of ultrathin carbon film coated silver nanoshell for biomedical applications in vivo

The extinction spectroscopy and near-field enhancement of dielectric-silver nanoshell coated by tetrahedral amorphous carbon [ta-C] layer (DSC) have been calculated by using Mie theory. With decreasing the Ag layer thickness, the localized surface plasmon resonance (LSPR) of DSC nanoshell moves from the visible region into the near-infrared region and the corresponding local field factor (LFF) increases first and then decreases. In addition, the increase of ta-C shell thickness leads to red-shift of LSPR and the decrease of LFF in DSC nanoshell. We further find that the increase of the dielectric constant for the outer shell can induce a significant enhancement of near-field. Based on the simulation analysis, we show that the DSC nanoshell can provide strong near-field in near-infrared region and may be suitable for the biomedical applications in vivo.     

Optical properties of planar structures containing oxidized copper nanoparticles

Planar structures consisting of oxidized copper granules obtained by laser electrodispersion are studied. The samples have different packing densities of granules and different amounts of their chains and aggregates. Each granule 5.5 ± 0.5 nm in size consists of a copper core with an amorphous structure and an oxide shell of about 0.7 nm thick. Some granules are randomly charged. The spectra of coherent transmission, diffusion transmission, and reflection of the samples are measured. Using the experimental data, the absorption spectra and the effective absorption, extinction, and scattering coefficients of monolayers are calculated and the luminescence spectra are estimated. A long-wavelength shift of the plasmon resonance of the copper granules with oxide shells as compared to that of the unoxidized granules is observed. The shift depends on the thickness of the oxide layer. A similar shift of the plasmon resonance is observed for the chains of copper granules. The spectra are compared with the spectra calculated theoretically taking into account some parameters of the planar structures and the size dependence of the optical constants of copper. The luminescence observed in some cases is associated with specifics of oxidation of copper granules.     

Design and synthesis of plasmonic magnetic nanoparticles

Core–shell nanoparticles containing both iron oxide and gold are proposed for bioseparation applications. The surface plasmon resonance of gold makes it possible to track the positions of individual particles, even when they are smaller than the optical diffraction limit. The synthesis of water-dispersible iron oxide-gold nanoparticles is described. Absorption spectra show the plasmon peaks for Au shells on silica particles, suggesting that thin shells may be sufficient to impart a strong surface plasmon resonance to iron oxide-gold nanoparticles. Dark field optical microscopy illustrates the feasibility of single-particle detection. Calculations of magnetophoretic and drag forces for particles of different sizes reveal design requirements for effective separation of these small particles.     

偏振方向及结构间耦合作用对空心方形银纳米结构表面等离子体共振的影响

空心方形纳米结构能够激发更大面积的增强电场,故其可以作为衬底用于表面增强拉曼散射.应用离散偶极子近似算法研究了空心方形银纳米结构的消光光谱及其近场电场分布与入射光偏振方向之间的关系.研究表明,空心方形银纳米结构的表面等离子体共振峰不随入射光偏振方向的改变而移动,但是其表面增强电场分布却强烈地依赖于入射光的偏振方向.另外,还讨论了空心方形银纳米结构间的耦合作用对其表面等离子体共振模式的影响.结果发现,可以通过调节结构间的距离来改变结构间的耦合作用,同时改变了表面等离子体共振峰的位置.这些结果将为理解闭合纳米 关键词： 空心方形银纳米结构 表面等离子体 偏振 电场耦合     

Simultaneous low extinction and high local field enhancement in Ag nanocubes

We theoretically investigate surface plasmon resonance properties in Au and Ag cubic nanoparticles and find a novel plasmonic mode that exhibits simultaneous low extinction and high local field enhancement properties. We analyse this mode from different aspects by looking at the distribution patterns of local field intensity, energy flux, absorption and charge density. We find that in the mode the polarized charge is highly densified in a very limited volume around the corner of the nanocube and results in very strong local field enhancement. Perturbations of the incident energy flux and light absorption are also strongly localized in this small volume of the corner region, leading to both low absorption and low scattering cross section. As a result, the extinction is low for the mode. Metal nanoparticles involving such peculiar modes may be useful for constructing nonlinear compound materials with low linear absorption and high nonlinearity.     

Electromagnetic coupling between a metal nanoparticle grating and a metallic surface

The electromagnetic coupling between a two-dimensional grating of resonant gold nanoparticles and a gold metallic film is investigated. We report on the observation of multipeaks in the extinction spectra attributed to resonant modes of the hybrid system, resulting from the coupling between the localized plasmon of the nanoparticles with the underlying surface plasmon mode. Simulations based on the Fourier modal method give good agreement with the experimental measurements and allow for the identification of the respective contributions.     

周期地嵌入电介质球壳的金属表层的表面等离子激元及其与电介质腔体模式的耦合

通过观察金属底板中周期地嵌入电介质球壳的体系的光学吸收性质，研究了表面等离子激元 以及与其他电磁模式的耦合特性.在这种周期结构的金属表面，发现存在两种响应频率，分 别对应于表面等离子激元模式和金属中的电介质腔体模式.在这些响应频率上，可观察到与 它们相对应的吸收峰.由于金属的表面模式不能与平面入射光直接耦合，而腔体模式与平面 入射光和表面等离子激元模式的耦合一般较弱，因而通常情况下这些吸收峰的峰值有限.然 而，通过调整体系中的某些参数，可以使腔体模式和表面模式的频率非常接近，这时二者之 间的耦合强度将大大提高.此时，在相应的频率附近可观察到极强的吸收峰.详细地研究了介 质球壳的物理和几何参数对此共振吸收的影响. 关键词： 腔体模式 表面等离子体模式 共振吸收     

Extinction properties of thin metallic nanowires

The classical electromagnetic scattering theory for a circular cylinder is extended so as to allow for the non-local response properties of metals. Using hydrodynamic dielectric functions and applying appropriate additional boundary conditions, the generalized scattering coefficients are derived. For very thin nanowires, the main extinction peak, due to the surface plasmon, is shifted from its classical position towards the high frequency side and subsidiary peaks, due to bulk plasmon excitation, appear above the plasma frequency.     

Fano resonances in dipole-quadrupole plasmon coupling nanorod dimers

We theoretically investigate the plasmon coupling in metallic nanorod dimers. A pronounced dip is found in the extinction spectrum due to plasmonic Fano resonance, which is induced by destructive interference between the bright dipole plasmon of a short nanorod and the dark quadrupole plasmon of a long nanorod. This Fano interference can also be explained as the coupling between the bright and dark modes both supported by the whole dimer. The Fano resonance can be tuned by adjusting the spatial or spectral separation between two nanorods in the dimer.     

Evolution of extinction spectra of plasmon resonance nanocolloids in the process of their crystallization

Changes in extinction spectra of nanostructured colloids of plasmon resonance particles are studied at different stages of their crystallization. The spontaneous crystallization is calculated by the method of Brownian dynamics, and the extinction spectra are calculated by the method of coupled dipoles. Based on the example of silver sols, we analyzed how separate parameters of the crystallizing disperse system affect the shape of the extinction contour in the plasmon absorption band.