Size characteristics of surface plasmons and their manifestation in scattering properties of metal particles

The change of the scattering properties of sodium, gold and silver spherical particles with size is discussed in the context of surface multipolar plasmon resonances. The presented surface plasmon size characteristics are abstracted from the quantity which is observed and deliver multipolar plasmon resonance frequencies and plasmon damping rates in the form of a continuous function of particle radius. The performed analysis of the plasmon dispersion relation is analogous to the problem of surface plasmon localized at a semi-infinite, flat metal/dielectric interface.Correlation between the multipolar plasmon resonance parameters, and the spectroscopic optical properties of conductive nanoparticles appearing as peaks in the measurable light intensities is analyzed. We discuss the fact, that such peaks arise from interference of all the electromagnetic fields contributing to the measured intensity, and not solely to the fields due to surface plasmon multipolar modes.We describe the results of light scattering experiment in orthogonal polarization geometries with use of spontaneously growing sodium droplets. The polarization geometry of the experiment allows for distinct separation of resonant contribution of dipole and quadrupole plasmon TM mode contributions to the measured intensities as a function of size.Predictions concerning size characteristics for dipole and quadrupole plasmons are compared with the results of light scattering experiments using spherical sodium droplets (our results) and gold and silver particles in suspension [other authors: Sönnichsen C, Franzl T, Wilk T, von Plessen G, Feldmann J. Plasmon resonances in large noble-metal clusters. New J Phys 2002; 4:93.1–8; Haiss W, Thanh NTK, Aveyard J, Fernig DG. Determination of size and concentration of gold nanoparticles from UV–vis spectra. Anal Chem 2007; 79:4215–21; Njoki PN, Lim I-IS, Mott D, Park H-Y, Khan B, Mishra S, et al. Size correlation of optical and spectroscopic properties for gold nanoparticles. J Phys Chem C 2007; 111:14664–9; Mock JJ, Barbic M, Smith DR, Schultz DA, Schultz S. Shape effects in plasmon resonance of individual colloidal silver nanoparticles. J Chem Phys 2002; 116:6755–9].     

Large optical-frequency shift of molecular radiation via coherent coupling to an off-resonance plasmon

We demonstrate coherent optical coupling between molecular and plasmon resonances that are well separated in energy. In the presence of metallic nanoparticles, the second harmonic spectrum of organic dyes no longer peaks at the absorption wavelength but is instead blueshifted by 25 nm towards the localized plasmon resonance. The phase of the light generated by the dyes displays a large modulation across the plasmon resonance and no change across the molecular one. The second harmonic signal contributed by the nanoparticles, which is peaked at the plasmon frequency when no molecules are present, similarly displays a shift towards the molecular resonance in their presence. A model based on the interplay of the nonlinear optical near fields is able to account for these observations.     

Optical Resonances of the Systems of Nanoparticles with a Metallic Shell

Characteristic features of the formation of the plasma resonance absorption spectra of double-layer nanoparticles with a dielectric core and metal shell were investigated theoretically and experimentally. Two peaks of the surface plasma resonances were observed with the example of an AgI–Ag system. The model of the conductivity electron free path limitation suggested by Kreibig for describing the dimensional dependence of the optical constants of homogeneous spherical metal nanoparticles was extended to the case where metal is concentrated in the shell of the particle. It is established that allowance for the dimensional effect leads to a decrease in plasma resonance absorption and expansion, with the two-peak band structure being preserved. The influence of the metal shell granularity and the degree of the polydispersity of particles on the spectral position, halfwidth, and absolute value of absorption resonances was investigated.     

Optical absorption by small metallic particles

We study theoretically the dependence of absorption by small metallic particles on particle shape and wave polarization in the IR frequency range. We examine the electric and magnetic absorption by small particles. The particles may be either larger or smaller than the electron mean free path. We show that for asymmetric particles smaller than the mean free path the light-induced conductivity is a tensor. We also show that the total absorption and the electric-to-magnetic absorption ratio are strongly dependent on particle shape and wave polarization. Finally, we construct curves representing the dependence of the ratio of the electric and magnetic contributions to absorption on the degree of particle asymmetry for different wave polarizations. Similar curves are constructed for the ratio of the components of the light-induced conductivity tensor. Zh. éksp. Teor. Fiz. 112, 661–678 (August 1997)     

Shaping nanoparticles and their optical spectra with photons

An experimental method to tailor the shape and the optical absorption spectra of metallic nanoparticles is presented. It exploits the influence of laser irradiation on particle growth by self-assembly of atoms deposited on a substrate surface. By applying nanosecond light pulses of appropriate fluence and three different wavelengths, oblate silver particles with three fixed axial ratios have been fabricated. Their optical extinction spectra were measured with s- and p-polarized light and are dominated by plasmon resonances at fixed photon energies determined by the axial ratio. Possible applications of such tailormade nanoclusters include catalytic converters and optical components with narrow-band extinction, the magnitude and center frequency of which can be specified in advance. Received: 9 September 1999 / Published online: 20 October 1999     

Surface-enhanced Raman scattering using bismuth nanoparticles: a study with amino acids

Bismuth nanoparticles produced by laser ablation synthesis in solution (LASiS) show localized surface plasmon resonances (LSPRs). The nanoparticles show surface-enhanced Raman scattering (SERS) activity for several tested amino acids. Optical absorption, dynamic light scattering (DLS), and transmission electron microscopy (TEM) as well as Raman scattering were used to characterize the samples. The search for new biocompatible nanoparticles for diagnostic purposes is important, and the demonstration that a semimetal is capable to act as a SERS active system opens new possibilities for molecular detection.     

Absorption and Scattering of Light by Silver and Gold Nanodisks and Nanoprisms

We study the influence of the shape of silver and gold nanoparticles on the spectra of absorption and scattering of the optical-range electromagnetic radiation. We perform numerical calculations of the cross sections of absorption and scattering of light on the basis of the FDTD method for the particles having the shape of a disk and a triangular prism. We establish that the positions of plasmon resonance peaks and the spectral distributions of intensities differ significantly for nanoparticles of different shapes even when the characteristic sizes of the particles are equal. The calculations carried out thus demonstrate that, along with the size and material of the plasmonic particle, its shape is yet another factor that essentially determines its optical features. The results of the study can be utilized in the development of the spectroscopic method of determining the shape of the metal nanoparticles and the quantitative estimate of their characteristic sizes.     

染料掺杂聚合物薄膜中金纳米颗粒增强的随机激光

基于金属纳米结构而获得随机激光的增强,其独特的性质及其潜在的应用价值具有重要的研究意义,在表面增强荧光、光学开关器件、表面等离子激元激光等方面实现了较多应用。报道一种快捷有效的制备纳米颗粒的手段并基于该纳米颗粒结构分析了染料掺杂聚合物薄膜涂覆的随机激光现象和规律。利用离子溅射沉积和高温热处理在石英基底上制备了Au纳米颗粒,改变溅射时间Au纳米颗粒的尺寸发生可控变化,该方法便捷、工艺简单。研究采用40,80和120 s三种不同的时间进行Au膜溅射并在650 ℃下高温处理,得到粒径尺寸不同的Au纳米颗粒,随着溅射时间延长Au纳米颗粒的尺寸逐渐变大。通过涂覆有机荧光染料DCJTB掺杂的PMMA聚合物薄膜构建光致激射系统,利用纳秒脉冲激光对样品进行激发,得到随机激光并研究其出射光强度和阈值的变化规律特征。40,80和120 s三种溅射时间下所得Au纳米颗粒的平均粒径尺寸分别为230,250和390 nm,在532 nm激光激发下产生随机激光的阈值分别为20.5,17.5和12.5 μJ·pulse-1。Au纳米颗粒尺寸越大、粒子间距越小时,光子散射的平均自由程越短,光在金属颗粒之间可以多次有效散射,从而显著提高散射效率,产生较低阈值的激光发射;Au纳米颗粒的吸收峰与染料的荧光峰恰好匹配时,将会显著增强染料的荧光效应,激发更多染料分子发生能级跃迁,增加光子态密度,获得峰值更高、阈值更低的激射现象;泵浦光不破坏染料分子的情况下,可以多次循环泵浦获得激光,染料分子的发光效率随着多次激发略有降低,有助于随机激光器件的研究开发。实验研究结果与理论分析相一致,进一步明确了Au纳米颗粒对光子散射和等离子共振对光吸收增强的随机激光发射机理。该研究以Au纳米结构对光子的强散射效应为增益,通过理论分析和实验测量获得随机激光,为实现高效率、低阈值的随机激光研究提供了一种便捷的技术手段,有望促进随机激光器件的开发和应用。     

Extremely narrow plasmon resonances based on diffraction coupling of localized plasmons in arrays of metallic nanoparticles

We experimentally demonstrate extremely narrow plasmon resonances with half-width of just several nanometers in regular arrays of metallic nanoparticles. These resonances are observed at Rayleigh's cutoff wavelengths for Wood anomalies and based on diffraction coupling of localized plasmons. We show experimentally that reflection from an array of nanoparticles can be completely suppressed at certain wavelengths. As a result, our metal nanostructures exhibit pi-jump for the phase of the reflected light.     

Stable optical trapping based on optical binding forces

Various trapping configurations have been realized so far, either based on the scattering force or the gradient force. In this Letter, we propose a new trapping regime based on the equilibrium between a scattering force and optical binding forces only. The trap is realized from the interaction between a single plane wave and a series of fixed small particles, and is efficient at trapping multiple free particles. The effects are demonstrated analytically upon computing the exact scattering from a collection of cylindrical particles and calculating the Lorentz force on each free particle via the Maxwell stress tensor.     

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.     

Doppler-free resonances of the second-order raman scattering

The possibility of the observation of Raman scattering resonances completely free from the influence of the Doppler effect has been examined for the first time. The phenomenon is based on the excitation of a Raman oscillation standing wave in a gas by two standing light waves, whose frequency difference is equal to half the Raman frequency. The complete compensation of Doppler shifts results from the simultaneous interactions between atomic particles and two pairs of counter-propagating waves. Doppler-free resonances of the second-order Raman light scattering appear in the number of particles excited to the upper Raman level and in the radiation at the Stokes and anti-Stokes frequencies. The amplitude estimate for the resonance in the number of particles is given for the example of neon.     

Spectra of resonance light scattering of gold nanoshells: Effects of polydispersity and limited electron free path

The effects of the polydispersity of the structure of gold nanoshells and of the limited electron free path in a thin metal layer on the spectra of resonance light scattering of a suspension of two-layer nanoparticles are studied theoretically and experimentally for the first time. It is shown theoretically that both factors lead to a broadening of the plasmon resonance in light scattering and to a change in its magnitude. To experimentally test the calculations, two samples of nanoshells based on gold and silicon dioxide (silica) were synthesized. Nanoshells of sample 1 have a diameter of the core of 90 nm and a broad thickness distribution of shells (with an average value of 30 nm), whereas nanoshells of sample 2 have a diameter of the core of 70 nm and a narrow thickness distribution of shells (with an average value of 12 nm). The core diameter, the shell thickness, and the polydispersity of the structure of nanoparticles are estimated by dynamic light scattering. It is shown that the simulation of the optical properties of nanoparticles with their parameters estimated from the dynamic light scattering data makes it possible to obtain good agreement between experimental and theoretical spectra of light scattering. For nanoshells of sample 1, the inhomogeneous broadening of the scattering spectrum is completely determined by the polydispersity; therefore, the bulk constants of gold can be used in simulation of the spectra of such nanoshells. The main mechanism of the broadening for nanoshells of sample 2 is connected with the limitation of the free path length of electrons, whereas the contribution from the thickness distribution of shells can be neglected.     

Decay times of surface plasmon excitation in metal nanoparticles by persistent spectral hole burning

We describe a new technique to determine the homogeneous linewidths of surface plasmon resonances of metal nanoparticles and thus measure the decay time of this collective electron excitation. The method is based on spectral hole burning and has been applied to supported oblate Ag particles with radii of 7.5 nm. From the experimental results and a theoretical model of hole burning the linewidth of 260 meV corresponding to a decay time of 4.8 fs was extracted. This value is shorter than expected for damping by bulk electron scattering. We conclude that additional damping mechanisms have been observed and reflect confinement of the electrons in nanoparticles with sizes below 10 nm.     

Size-controlled aerosol synthesis of silver nanoparticles for plasmonic materials

Aerosol techniques were used to synthesize spherical and monodisperse silver nanoparticles for plasmonic materials. The particles were generated with an evaporation-condensation technique followed by size selection and sintering with a differential mobility analyzer and a tube furnace, respectively. Finally, the nanoparticles were collected on a glass substrate with an electrostatic precipitator. The particle size distributions were measured with a scanning mobility particle sizer and verified with a transmission electron microscope. A spectrophotometer was used to measure the optical extinction spectra of the prepared samples, which contained particles with diameters of approximately 50, 90 and 130?nm. By controlling the particle size, the dipolar peak of the localized surface plasmon resonance was tuned between wavelengths of 398 and 448?nm. In addition, quadrupolar resonances were observed at shorter wavelengths as predicted by the simplified theoretical model used to characterize the measured spectra.     

Resonant mechanisms of inelastic light scattering by low-dimensional electron gases

The contribution of elementary excitations in low-dimensional electron gases to resonant inelastic light scattering is found to be determined by interband transitions involving states at specific wave vectors. In modulation-doped GaAs/GaAlAs quantum wells, we detect only the single-particle excitations (SPE) at resonances with electron-hole transitions at the Fermi wave vector, and only plasmons at resonances with zone-center excitons. The plasmon cross section is comparable to the SPE when double electronic resonance is achieved by tuning the plasmon energy to a valence subband separation.     

Zn/ZnO纳米颗粒的表面声子Raman散射

Ｚｎ／ＺｎＯ纳米颗粒的表面声子Ｒａｍａｎ散射许建峰黄亚彬莫育俊（河南大学物理系开封４７５００１）ＲａｍａｎＳｃａｔｅｒｉｎｇｆｒｏｍＳｕｒｆａｃｅＰｈｏｎｏｎｓｉｎＺｎ／ＺｎＯＮａｎｏｐａｒｔｉｃｌｅｓＸｕＪｉａｎｆｅｎｇ，ＨｕａｎｇＹａｂｉｎ，Ｍｏ...     

Light absorption by island metal films in the infrared range

This study reports on theoretical investigations of the electric and magnetic absorption of small metallic particles as functions of their shape, with the wavelength of incident e/m radiation assumed to be much greater than the size of the particles. A general expression for the absorption cross-section is derived for the cases when both the bulk and surface electron scattering are dominant. In the IR-region the absorption cross-section is shown to be extremely sensitive to the shape of particles; for particles of a constant volume, yet different in shape, it can change by several orders of magnitude. It is also shown that under dominant surface scattering the optical conductivity of an asymmetric particle is described by a tensor whose principal values are calculated for the ellipsoidal shape. The expression obtained for the electric and magnetic absorption renders ground to infer that the ratio of the contributions due to these absorption mechanisms greatly depends on the shape of particles and polarization of light.     

Plasmon resonance modulated photoluminescence and Raman spectroscopy of diindenoperylene organic semiconductor thin film

In a comparison between a bare diindenoperylene (DIP) film and a DIP film spin-coated with a layer of gold nanoparticles, we have investigated the influence of plasmon resonances in the gold particles on spectroscopic properties of the molecular film. Under off-resonant excitation with a laser at 633 nm, the bare DIP film showed only weak photoluminescence (PL) and Raman signals, but after spin-coating gold nanoparticles on such a DIP film, we found an enhancement of both the PL and Raman signals by a factor of about 3, whereas no enhancement could be observed when the same sample was excited with laser light of 488 nm. This difference reveals that at 633 nm, plasmon resonances in the gold nanoparticles are excited, leading in turn to an enhancement of PL and Raman signals of the weakly absorbing DIP film via coupling between plasmons in the gold particles and exciton-polaritons in the molecular film. For the laser at 488 nm, due to a much larger absorption coefficient of DIP, excitons in the molecular film are directly excited, out-weighing the influence of an off-resonant coupling to the plasmon resonances in the gold particles occurring at much lower energy.     

Ensembles of plasmonic nanospheres at optical frequencies and a problem of negative index behavior

Arrays of metallic nanoparticles support individual and collective plasmonic excitations that contribute to unusual phenomena like surface-enhanced Raman scattering, anomalous transparency, negative index, and subwavelength resolution in various metamaterials. We examined the electromagnetic response of dual Kron’s lattice and films containing up to three monolayers of metallic nanospheres. It appears that open cubic Kron’s lattice exhibits ‘soft’ electromagnetic response but no negative index behavior. The close-packed arrays behave similarly: there are plasmon resonances and very high transmission at certain wavelengths that are much larger than the separation between the particles, and a ‘soft’ magnetic response, with small but positive effective index of refraction. It would be interesting to check these predictions experimentally. PACS 78.20.Ci; 42.30.Wb; 73.20.Mf; 42.25.Bs