Absorption and Scattering of Light by Hybrid Metal/J-Aggregate Nanoparticles: Plasmon–Exciton Coupling and Size Effects

We report the results of our theoretical studies of the optical properties of hybrid nanoparticles consisting of the metal core covered with molecular J-aggregates. We evaluate the cross sections of absorption and scattering of light by such particles on the basis of the extended Mie theory for two concentric spheres with material dielectric functions that take into account the size effect associated with scattering of free electrons from the core/shell interface. We carry out our calculations in a wide range of light wavelengths and geometrical parameters of the composite system for silver and gold core and for a J-aggregate shell composed of different cyanine dyes. The results obtained demonstrate the quite different behavior of the extinction spectra of such particles caused by the different strengths of interaction between the Frenkel exciton and the dipolar or multipolar plasmons. We pay particular attention to the investigation of spectral peak positions associated with the eigenfrequencies of hybrid modes in the system and peak intensities as functions of reduced oscillator strength in the molecular J-band for various relationships between the core radius and shell thickness. This provides an efficient means for the explanation of the main features in the optical properties of metal/J-aggregate nanoparticles and can be used for an effective control of the plasmon–exciton coupling strength in such hybrid complexes.     

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.     

Localized Surface Plasmon Resonance of Cu@Cu2O core-shell nanoparticles: Absorption, Scattering and Luminescence

By co-deposition via RF-Sputtering and RF-PECVD methods and using Cu target and acetylene gas, we prepared Cu@Cu₂O core-shell nanoparticles on the a-C:H thin film at room temperature. Mie absorption of Cu cores, scattering from Cu₂O shell and luminescence that rises from carrier transfer in Cu@Cu₂O interface were employed to fit the whole range of visible extinction spectrum of these core-shells. From simulation it was found that scattering and luminescence have an important effect on the energy, width and shape of LSPR absorption peak. Shift of LSPR peak is more affected by the dielectric coefficient of shell than Cu core size particularly for Cu core diameter above 4 nm. Also, the LSPR absorption peak is damped by decreasing Cu core size and dielectric coefficient of shell. The energy of LSPR absorption peak is independent of shell thickness and host dielectric coefficient. The LSPR peak is damped by increasing shell thickness and host dielectric coefficient too. The scattering contribution in extinction spectra was affected more by shell size than dielectric coefficient. These points are important for detection techniques based on LSPR peak.     

Optical properties of composite thin films containing silver nanoparticles

Absorption and reflection of electromagnetic radiation by a composite thin film consisting of a transparent dielectric matrix with inclusions of metal nanoparticles of radius much less than the wavelength were theoretically investigated based on the Maxwell–Garnett model. The absorption, reflection, and transmission of optical radiation in such a dielectric composite film were analyzed using effective optical parameters for the refractive index and absorption coefficient that depended on the nanoparticle size.     

CdSe/CdS核/壳型纳米晶的光谱特性

以巯基乙酸为稳定剂制备了CdSe/CdS核／壳型纳米晶。用光吸收谱（Abs)、光致发光谱（PL）及光致发光激发谱（PLE）研究了CdS壳层对CdSe纳米晶电子结构，从而对其吸收和发光性能的影响。根据PL和PLE的结果以及带边激子精细结构的计算结果，我们用尺寸很小的纳米晶中所形成的基激缔合物解释了PL光谱与吸收边之间较大的Stokes位移。     

Linear and nonlinear properties for a dilute suspension of coated ellipsoids

The effects of geometric structures of coated particles on the dielectric properties of composites are derived. For a dilute suspension of coated ellipsoids with dielectric core and metallic shell embedded in a linear dielectric host, we find that the optical absorption peak of maximum wavelength shifts due to the core-shell structure, and has a significant red shift from that of pure metallic particles, especially for thin metallic coating. Meanwhile, the shape of coated ellipsoid can tune the absorption peak in a wide frequency range by properly choosing the depolarization factor. When the composite is made of linear materials, we obtain the condition of partial resonance for coated ellipsoids, which is relative to the particle shape. Under such a condition, the property of the inner core can be extended to the outer shell. When the inner core is a weakly nonlinear material, the nonlinearity of the composite can be greatly enhanced at the linear partial resonance. To achieve the condition of partial resonance, a metallic shell may be suitable to reach the case if the frequency is far away from the plasmon frequency. It indicates that the nonlinearity can also be enhanced in terms of the geometric structure of materials as well as the properties of themselves.     

Composite‐Assisted Phase‐Matching: Efficient Wavelength Conversion in Nonlinear Optical Composite Materials Containing Metal Nanoparticles

A novel phase‐matching scheme which is based on the dispersion compensation in the nonlinear optical composite materials containing metal nanoparticles is proposed. Anomalous dispersion originating from the plasmon resonance in metal nanoparticles compensates the dispersion of the host nonlinear material, leading to the perfect phase‐matching and high efficiency of nonlinear optical wavelength conversion. The effectiveness of this approach is theoretically demonstrated, taking third‐order nonlinear processes such as the direct third‐harmonic generation and four‐wave mixing in ZnO composites containing silica‐core–silver‐shell nanoparticles as examples. The results show that with the proposed phase‐matching scheme, unprecedentedly high conversion efficiency can be obtained compared with preceding results in third‐order nonlinear optical solid‐state materials.     

Nonlocal effects in the optical response of composite materials with metallic nanoparticles

A phenomenological model for the optical response of composite materials with metallic nanoparticles is presented. This model applies the conventional effective medium theories (EMT) but takes into account the spatial dispersion effects in the dielectric response of the metallic nanoparticles. This leads to an EMT that depends on the size of the particles. Numerical results from a model computation shows that this effect due to the nonlocal optical response of the nanoparticles can increase the resonant absorption frequency of the composite significantly for particles of very small sizes; and can lead to resonant absorption even in the Bruggeman symmetric EMT—a feature which is believed to be absent in the conventional treatment where local response for the metal particles has been assumed.     

Optimal design of gold nanoshells for optical imaging and photothermal therapy

Gold nanoshells are of great interest in optical imaging based on their light scattering properties and photothermal therapy due to their light absorption properties. Strong light scattering is essential for optical imaging, while effective photothermal therapy requires high light absorption. In this article, the optimal core radii and shell thicknesses of silica–gold and hollow gold nanoshells, possessing maximal light scattering and absorption at wavelengths between 700 and 1100 nm, are obtained using the Mie theory of a coated sphere. The results show that large-sized gold nanoshells of high aspect ratios (the aspect ratio is defined as the ratio of core radius to shell thickness) are the efficient contrast agents for optical imaging, while smaller gold nanoshells of high aspect ratios are the ideal therapeutic agents for photothermal therapy. From the comparison of the numerical results for silica–gold and hollow gold nanoshells, the latter are seen to offer a little superior light scattering and absorption at smaller particle size. Fitting expressions for the optimal core radii and shell thicknesses are also obtained, which can provide design guidelines for experimentalists to optimize the synthetic process of gold nanoshells.     

Theoretical investigation on near-infrared and visible absorption spectra of nanometallic aluminium with oxide coating in nanoenergetic materials: size and shape effects

The effects of metal core dimension, oxide shell thickness and ellipsoid aspect ratio of Al-Al2O3 core-shell nanoparticles on the near-infrared and visible absorption spectra of nanocomposite Al-Al2O3/nitrocellulose（NC） film are investigated by numerical calculations. Both the size-dependent interband transitions and frequency-dependent free electron damping of the nanometallic aluminium are taken into account in the calculations. Oxidation effect of nanoaluminium is also analysed. It is shown that oxidation may enhance but may also reduce the optical absorption, depending on the excited light energy and initial dimension of nanoparticle. Metal core size and excited light energy dominate the absorption characteristic. The absorption ability of ellipsoidal nanoparticles is larger than that of spheroidal nanoparticles and increases by the square index as the aspect ratio increases. These calculations will provide some significant theoretical guidance for the preparation and laser ignition of nanoenergetic materials.     

非局域颗粒复合介质的相干完美吸收效应

研究了两束相干光以相同的入射角从左、右两侧分别入射到Au-SiO_2复合介质板时,在不同的体系参数下该复合材料体系发生相干完美吸收的情形.运用有效媒质理论推导出了复合介质的有效介电常数以及有效磁导率;在得到有效电磁参数的基础上进一步推导得到平面波入射复合介质板时的反/透射系数.通过比较分析非局域和局域情况下颗粒复合介质的相干完美吸收现象,发现当颗粒尺寸很小时非局域效应的影响会导致复合介质产生相干完美吸收的入射光的频率范围显著变宽.在进一步的解析计算中,通过调节复合介质板的厚度、入射光波长、金属颗粒体积分数等参数得到了不同情况下产生的相干完美吸收现象,并由此分析非局域情形下对于相干完美吸收现象的调控.     

Optical and spectral tunability of multilayer spherical and cylindrical nanoshells

This theoretical work presents a comparative study of the optical properties and spectral tunability of hybrid multilayer spherical and cylindrical nanoshells based on the quasi-static approximation of classical electrodynamics. The interband transitions have been considered using the Drude–Lorentz model for the complex dielectric function of metallic layers because the optical properties of metals arise from both the optical excitation of interband transitions and the free-electron response. A general formula for N-ayer concentric nanoshells is arranged, and numerical calculations are performed for the four-layer nanoshells as an example. We have analyzed in detail different configurations of nanoshells such as dielectric-metal-dielectric-metal with dielectric core, metal-dielectric-metal-dielectric with metal core and semiconductor-metal-dielectric-metal with semiconductor core because composition of nanoshells have dramatic influence on their optical properties. The absorbance spectrum behavior of the shell thicknesses, surrounding medium, shape and composition of each layer of the nanoshell is numerically investigated.     

芯-壳结构复合纳米颗粒

芯－壳结构复合纳米颗粒因其独特结构而具有许多奇异的性质，尤其体现在可人工设计和可控的光学性质上：根据不同的性质要求，通过改变组分和壳层与芯部的相对尺寸来实现光学性质在很宽波段范围内的可调特性，这一特性在光敏器件（如光开关，光过滤器）以及下一代的纳米光子光等很多领域有着广阔的应用前景，并在目前红外材料的改性上也会大显身手，文章介绍了几种芯－壳复合纳米颗粒的合成及其性质研究现状，并作相应的展望。     

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.     

Nanophotonics of isolated spherical particles

The problem of extreme focusing of an optical beam into the spatial region with wavelength dimensions is considered with the use of the special features of radiation interaction with isolated spherical particles. Results of numerical computations of the optical field intensity at the surface of silver particles of different radii upon exposure to laser radiation with different wavelengths are presented. It is demonstrated that the relative intensity of the plasmon optical field on the nanoparticle surface increases and the field focusing region decreases with increasing particle radius. Results of numerical computations illustrating the influence of the shell of composite nanoparticles comprising a dielectric core and a metal shell on the optical field intensity in the vicinity of the particle are presented. The problem of local optical foci of a transparent microparticle (photonic nanojets) is investigated. It is established that variation of the micron particle size, its optical properties, and laser radiation parameters allows the amplitude and spatial characteristics of the photonic nanojet region to be controlled efficiently.     

Light scattering calculations from Au and Au/SiO2 core/shell nanoparticles

Given the importance of the optical properties of Au and Au/SiO₂ core/shell nanoparticles, in this article we focus our attention on the light scattering properties of such systems and on a relative comparison. In particular, we report theoretical results of angle-dependent light scattering intensity and scattering efficiency for Au and Au/SiO₂ core/shell nanoparticles increasing the Au particle radius from 30 to 130 nm, and for Au/SiO₂ core/shell particles changing the core-to-shell sizes ratio. Finally, a comparison between the scattering efficiency of the Au and Au/SiO₂ core/shell nanoparticles is drawn. The results of this work can be used in the design of tunable efficiency light scattering devices (biological and molecular sensors, solar cells).     

Infrared and Raman spectroscopies of InP/II–VI core-shell nanoparticles

We use infrared (IR) and Raman spectroscopies to investigate the optically active phonon modes in InP nanoparticles and InP/II–VI core-shell nanoparticles fabricated by similar colloidal chemistry methods. The IR transmission spectra of several InP nanoparticle samples exhibit a common absorption feature, which we assign to the Fröhlich mode. The Raman results for the same samples show transverse and longitudinal optical phonon peaks, and scattering strength in between due to surface optical (SO) modes. Infrared spectra of the InP/ZnSe core-shell nanoparticles () exhibit three absorption features, one due to the InP core, and the others associated with the ZnSe shell layer. Raman measurements (12–292 K) also show three phonon-related peaks, whose intensities vary sharply with temperature. The frequencies of the IR and Raman lines are in approximate accord with dielectric continuum theory.     

Interaction dynamics of bright solitons in linearly coupled asymmetric systems

In this research work, composite media based on metamaterials including random distribution of spherical nanoparticles in a polymeric foam host are suggested to achieve negative effective refractive index in the visible spectrum. For this purpose structures including single, two and three layer spherical particles are investigated. Based on simulation results, media including single layer spheres (metallic and dielectric particles) and two layer nanospheres (core–shell particles consist of metallic core and dielectric shell) based on superposition of nanoparticles with different sizes and fill fractions are proposed for desired result. In this work, to obtain optimized band with negative RI media, superposition of three layer nanoparticles and doped semiconductor are designed.

     

Optical and magneto-optical properties of Co–SiO<Subscript>x</Subscript> thin films

The optical and magneto-optical properties of hybrid Co–SiO_x systems are studied as a function of Co concentration. The structures were prepared by alternate depositions of SiO_x thin films and layers of 10-nm-diameter Co nanoparticles produced by an Ion Cluster Source. Both optical and magneto-optical constants of the system gradually increase with the amount of Co, though maintaining low optical absorption values in the visible range. The experimental results are well reproduced assuming that the nanoparticles have a cobalt core (7–8 nm in diameter) surrounded by a cobalt oxide shell (1–2 nm thick). The magneto-optical activity versus optical absorption figure of merit of this system is compared with other magneto-optical dielectric systems.     

An opto-mechanical nanoshell–polymer composite

Metal nanoshells, which are nanoparticles consisting of a dielectric core surrounded by a metal shell, have an optical response dictated by the plasmon resonance. This optical resonance leads to large extinction cross-sections, which are typically several times the physical cross-section of the particles. The wavelength at which the resonance occurs depends on the core and shell sizes, allowing nanoshells to be tailored for applications. In this paper, we demonstrate how incorporating nanoshells transforms a thermoresponsivepolymer into a photothermally responsive nanoshell–polymer composite. When the thermoresponsive polymer, co-N-isopropylacrylamide-acrylamide (NIPAAm-co-AAm), is heated, the polymer undergoes a reversible decrease in volume. Pristine NIPAAm-co-AAm does not inherently absorb visible or near infrared light. However, by incorporating metal nanoshell particles with a resonance that has been placed at 832 nm into the NIPAAm-co-Aam, nanoshell–polymer composite hydrogels are fabricated. When the composite is illuminated with a diode laser at 832 nm, the nanoshells absorb light and convert it to heat. This induces a reversible and repeatable light-driven collapse of the composite with a weight change of 90% after illumination at 1.8 Wcm^-2. Received: 18 July 2001 / Published online: 10 October 2001