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.     

金纳米球壳对的局域表面等离激元共振特性分析

应用有限元方法, 研究金纳米球壳对的几何结构参数及物理参量对其表面等离激元共振的散射及消光光谱的影响, 并根据等离激元杂化理论进行了理论分析. 结果表明, 随着金壳厚度的增加, 金纳米球壳对的散射及消光共振峰先发生蓝移而后红移, 而随着金纳米球壳间隙的减小, 或者随着金纳米球壳的内核尺寸或内核介质折射率的增大, 散射及消光共振峰均发生红移; 随着金壳厚度或内核尺寸减小, 或者随着内核介质折射率增大, 金纳米球壳对的散射与消光共振强度减弱, 而随着金壳间隙的减小, 金纳米球壳对的散射共振强度先增强后减弱, 而消光共振强度逐渐增强, 数值模拟与理论分析一致.     

Flow Synthesis of Plasmonic Gold Nanoshells via a Microreactor

Gold nanoshells with tunable surface plasmon resonances are a promising material for optical and biomedical applications. They are produced through seed‐mediated growth, in which gold nanoparticles (AuNPs) are seeded on the core particle surface followed by growth of the gold seeds into a shell. However, synthetic gold nanoshell production is typically a multistep, time‐consuming batch‐type process, and a simple and scalable process remains a challenge. In the present study, a continuous flow process for the seed‐mediated growth of silica–gold nanoshells is established by exploiting the excellent mixing performance of a microreactor. In the AuNP‐seeding step, the reduction of gold ions in the presence of core particles in the microreactor enables the one‐step flow synthesis of gold‐decorated silica particles through heterogeneous nucleation. Flow shell growth is also realized using the microreactor by selecting an appropriate reducing agent. Because self‐nucleation in the bulk solution phase is suppressed in the microreactor system, no washing is needed after each step, thus enabling the connection of the microreactors for the seeding and shell growth steps into a sequential flow process to synthesize gold nanoshells. The established system is simple and robust, thus making it a promising technology for producing gold nanoshells in an industrial setting.     

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.     

Reflectance spectroscopy of gold nanoshells: computational predictions and experimental measurements

Gold nanoshells are concentric spherical constructs that possess highly desirable optical responses in the near infrared. Gold nanoshells consist of a thin outer gold shell and a silica core and can be used for both diagnostic and therapeutic purposes by tuning the optical response through changing the core–shell ratio as well as the overall size. Although optical properties of gold nanoshells have already been well documented, the reflectance characteristics are not well understood and have not yet been elucidated by experimental measurements. Yet, in order to use gold nanoshells as an optical contrast agent for scattering-based optical methods such as reflectance spectroscopy, it is critical to characterize the reflectance behavior. With this in mind, we used a fiber-optic-based spectrometer to measure diffuse reflectance of gold nanoshell suspensions from 500 nm to 900 nm. Experimental results show that gold nanoshells cause a significant increase in the measured reflectance. Spectral features associated with scattering from large angles (~180°) were observed at low nanoshell concentrations. Monte Carlo modeling of gold nanoshells reflectance demonstrated the efficacy of using such methods to predict diffuse reflectance. Our studies suggest that gold nanoshells are an excellent candidate as optical contrast agents and that Monte Carlo methods are a useful tool for optimizing nanoshells best suited for scattering-based optical methods.     

Synthesis and characterization of silica-gold core-shell (SiO<Subscript>2</Subscript>@Au) nanoparticles

This paper reports a systematic investigation of the growth and attachment of small gold nanoparticles to the functionalized surface of larger silica nanoparticles by three different methods. Nearly monodispersed silica particles and gold nanoparticles were prepared by sol-gel method. The size of the particle could be altered by changing the concentration of reactants, temperature and the time for which they react. The nanocoreshell particles prepared by three different methods were studied using scanning electron microscopy (SEM), UV-vis spectroscopy and Fourier transform infrared spectroscopy. We have found that the third method (c), a combination of the first two methods (a) and (b), has given better results.      

The effect of pH value on the formation of gold nanoshells

The effect of the pH value of gold ion plating (PCG) solution on the growth of gold nanoshells with about 100-nm silica cores and 15-nm gold shells was systematically investigated by dynamic light scattering, UV–Vis spectroscopy, scanning electron microscopy, and transmission electron microscopy. The results showed that in PCG solutions, the rapid formation of monomers which intensively influenced by the reducibility of formaldehyde contributed to the growth of gold nanoshells. The reducibility of formaldehyde increased following the increasing pH value from 4.70 to 11.71. Thus at high pH value, it was easy to fabricate the complete gold nanoshells (except of the Cannizzaro reaction of formaldehyde at high pH value). Furthermore, we found that chloride ions also influenced the surface morphology of gold nanoshells by Ostwald ripening process through the Au–Cl complex.     

Linear and nonlinear optical properties of Au/SiO2 nanocomposite prepared by P123

Mesoporous silica thin films loaded with gold nanoparticles are synthesized in the presence of EO20PO70EO20（P123）.Transmission electron microscope images show that the matrix of the nanocomposite is an ordered porous structure with a two-dimensional hexagonal phase.The wide-angle X-ray diffraction pattern implies that the nanocomposite contains gold crystals.These metallic nanoparticleembedded solid thin films show some linear and nonlinear optical properties due to their special structure and composition.Gold nanoparticles bring about surface plasmon resonance,and an absorption peak stemming from this effect has been observed.The linear absorption property is analyzed by a quantum mechanism,and the results show that it is influenced by the size and volume fraction of gold nanoparticles. Furthermore,it shows an obviously clear nonlinear optical property measured by the z-scan technique.The magnitude of the nonlinear refractive index of the nanocomposite is estimated to be about 10？ 10 cm 2 /W.     

硫醇衍生化的纳米金与癌胚抗原相互作用的光学分析

纳米金已在在药物靶向传输体系、疾病检测、分子识别、生物标签等领域有着广泛的应用,但是,由于纳米金的表面效应,大量的表面原子具有巨大剩余成键能力,使得纳米金粒子较容易团聚、沉聚,影响了其稳定性。为了实现对肿瘤靶标之一-癌胚抗原的痕量检测,需要制备出对癌胚抗原检测具有良好的增色效应与荧光增敏效应的纳米材料。该工作采用纳米金的硫醇衍生法制备了一种新型的硫醇衍生化的纳米金材料,并对此新型硫醇衍生化的纳米金材料的特性用透射电子显微镜,紫外-可见吸收光谱,荧光发射光谱和红外光谱等方法进行了研究。紫外-可见吸收光谱,荧光发射光谱的实验结果表明,在新的配体乙二硫醇存在下,有更多的电子从配体的轨道跃迁到与中心离子相关的轨道上,导致荧光增强。这种新型硫醇衍生化的纳米金与癌胚抗原作用时表现出增色效应与荧光增敏效应,而纳米金与癌胚抗原作用时看不到这种增色效应与荧光增敏效应。红外方法的研究结果表明,这种材料的蛋白增色机理为当硫醇衍生化纳米金与癌胚抗原蛋白作用时,体系中蛋白的—OH表现出更多的面外弯曲振动,有利于电子从硫醇衍生化纳米金配合物向蛋白转移而导致其增色和荧光增敏效应。因而这种新的硫醇衍生化纳米金材料比纳米金将具有更好的生物检测应用价值。     

Scattering behavior of nonabsorbing metallic nanoparticles

The optical property of nanosized metallic particles is unique and size-dependent, which cause color variation. In this work, the relationship between diameter and refractive index of nonabsorbing metallic nanoparticles and their scattering properties is studied by using Mie theory. Obtained results indicate that the optical scattering of metallic nanoparticle depends on their refractive index and diameter. The effect of refractive index on optical scattering depends on the nanoparticle diameter. So that, for very fine nanoparticle (10 nm diameter) the effect of refractive index on scattering is not significant. But the effect of refractive index of large size nanoparticle (700–900 nm diameter) on their optical scattering is higher than fine and medium size nanoparticles. The wavelength with maximum scattering depends on refractive index and nanoparticles diameter. In addition, the colorimetric study indicates that the color of nanoparticle depends on their size and refractive index. So that, the lightness, hue, and colorfulness of nanoparticles is changed by changing size and refractive index.     

Enhanced nonlinearity for filamentation in gold-nanoparticle-doped water

We report a universal approach based on the surface plasmon resonances(SPRs) attained in filamentation in water doped with gold nanoparticles for enhancing the nonlinear refractive index. The filament-induced supercontinuum spectrum in water overlaps with SPRs of gold nanospheres, which further leads to a modification on the Kerr nonlinear refractive index. In our experiment, the measured nonlinear refractive index(n_2) in water doped with gold nanoparticles increases by six times, as compared with that in pure water. Such enhancement may be useful for filament-induced nonlinear applications with modest incident intensity.     

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.     

金纳米旋转椭球的折射率传感特性分析与优化

对于金纳米颗粒在化学和生物传感中的应用,找到具有高品质因子的金纳米颗粒形状是近年来的研究热点。基于T矩阵方法和介电函数的尺寸修正模型,本文从理论上定量研究了金纳米旋转椭球的尺寸对其折射率灵敏度、半峰宽以及品质因子的影响。为了获得最佳传感性能,对品质因子进行了优化,并得到了最优的颗粒尺寸参数。结果发现,短半轴为11 nm和长半轴为49 nm的金纳米旋转椭球具有最大品质因子6.76。优化后的金纳米旋转椭球可以作为理想的化学和生物传感器。本研究为金纳米旋转椭球在化学和生物传感的应用中提供重要的理论依据。     

提拉法SiO_2化学膜厚度与折射率的变化规律研究

采用提拉法在硅基底上制备了多孔溶胶凝胶SiO2膜,用椭偏法测量薄膜的厚度与折射率,考察了提拉速度和胶体浓度对膜层厚度与折射率的影响。对厚度与提拉速度的关系进行线性与幂函数拟合,并比较分析两种拟合的关系及其对工艺流程的作用。比较了不同浓度胶体所得到的同一厚度薄膜的折射率变化规律。结果表明:对于同一胶体浓度下薄膜厚度与提拉速度的正相关关系,线性拟合相比幂函数拟合可以更好地解释实验结果的规律性。同时,折射率在一定范围内也会随着提拉速度的增加而减小。镀同一厚度膜时,浓度大的胶体膜层折射率大。通过对提拉速度和胶体浓度的控制可以得到理想的薄膜厚度与折射率。     

Optical bistability in plasmonic nanoparticles: Effect of size,shape and embedding medium

We theoretically investigate the optical bistability, which one input signal allows two possible outputs, from single spherical/cylindrical nanoparticles and also nanoshells in the frame work of quasi-static formalism. It is shown that the bistability behavior greatly depends on several parameters such as the nanoparticle size, material and the surrounding dielectric environment. We demonstrated the width of the bistability region and also the bistable threshold depends on the geometrical parameters, and can be tuned by adjusting the size of nanoparticle, the shell thickness and the dielectric constant of the embedding medium. It is also shown that the optical bistable behavior depends strongly on the shape of plasmonic nanoparticles and nanoshells. However, these dependences of optical bistability of spherical/cylindrical nanoparticles and nanoshells on changing of their geometrical parameters can be used for realize optical switching and sensing purposes.     

Attenuation,scattering, and depolarization of light by gold nanorods with silver shells

Gold nanoparticles with silver nanoshells are obtained by synthesizing gold nanorods in a growing solution containing cetyltrimethylammonium bromide, subsequent separation in a concentration gradient of glycerol, and reduction of silver nitrate by ascorbic acid under alkaline conditions in the presence of polyvinylpyrrolidone. The formation of silver nanoshells was monitored by the shift of plasmon resonances of extinction and differential light scattering, by the appearance of characteristics peaks of silver in the energy dispersive X-ray (EDX) spectra of samples, by the data of transmission electron microscopy, and by visual changes in the color of colloids. The spectrum of the intensity ratio of the co- and cross-polarized compo- nents of light scattered by gold-silver nanorods is measured for the first time, and it is observed that the maximum is shifted by 80–100 nm compared to previously published spectra of gold nanorods (Khlebtsov et al., J. Phys. Chem. C 112, 12760 (2008)). The extinction and light scattering spectra are calculated by the method of separation of variables using the model of a confocal two-layer spheroid and these calculations are found to agree with spectral measurements. A method for determining the thickness of a silver nanolayer by the spectral shift of an extinction longitudinal resonance is described. The obtained data of optical spectroscopy and transmission electron microscopy and estimations of the mass of the deposited metal show that the aver-age thickness of the silver layer varies from 0.12 to 4 nm as the Ag/Au ratio changes from 2/80 to 90/80 μg/μg.     

Absorption spectrum of surface-bound cap-shaped gold particles

A surface-adsorbed monolayer of cap-shaped gold particles upon submicrometer-sized polystyrene spheres exhibits pronounced absorption in the visible region. When the surrounding refractive index was altered by immersion in a fluid, the direction of the shift in the absorption spectrum was dependent on the incidence angle of the irradiation. When a thiol molecule, known to adsorb selectively on gold upon polystyrene, was added, the resultant shift in the absorption spectrum's peak was consistently toward longer wavelengths. Consequently, at certain incidence angles, a change in the refractive index of the surrounding fluid produces no shift, whereas thiol adsorption results in a clear shift, apparently reflecting the different spatial regions in which the refractive index is altered by these two procedures.     

Investigation of surface plasmon biosensing using gold nanoparticles enhanced ellipsometry

We present a label-free, nondestructive and high sensitivity biosensor by using the phase information of a gold nanoparticles enhanced ellipsometry signal. The refractive index (RI) resolution from ellipsometric phase information is of the order of 1.6×10(-6) RI units. Furthermore, spectroscopic and dynamic measurements show substantial change in the phase signal when biomolecules are coated on gold nanoparticles. The detection limit of our proposed technique is up to ～18?pM concentration of the target biomolecules.     

A facile route to prepare hierarchical magnetic cobalt–silica hollow nanospheres with tunable shell thickness

Magnetic nanoshells composed of close-packed cobalt–silica nanoparticles have been successfully fabricated on silica spheres. The synthesis is facile and no high pressure, high temperature, or other severe reaction conditions were required. TEM images showed that two batches of the hollow-structured products have a good spherical morphology with an average diameter of 380 and 550 nm, respectively. The surface area and magnetic properties of cobalt–silica nanoshells are measured. By varying the times of the precipitation procedure, the shell thickness is successfully controlled within the 5–30 nm range and each time of procedure might increase the thickness about 5 nm. It is expected that the in situ reaction method can be extended to the synthesis of other hollow metal spheres. The prepared microcapsule with controllable shell thickness and interspaces has the potential to be used for controlled release applications.     

Enhanced light trapping for the silver nanoparticles embedded in the silica layer atop the silicon substrate

The optical properties of the structures with silver nanoparticles embedded in the silica layer atop the silicon substrate are simulated by the finite-difference time-domain method. The effects of nanoparticle size, period, silica layer thickness, and the angle of incidence of the illuminated light on optical transmissions are studied. It is found that there is the red-shift for the maximum of the total light transmitting into the silicon substrate as the silica layer thickness increases. The electric field intensity distributions and the average power densities for the structure with largest optical transmission is studied, and the strong electric field intensities are found in the silica regions surrounding to the silver nanoparticles, which can help the light energy going into the silicon substrate. By controlling the structure parameters, the optical transmissions of the structures with the silica layer can have higher optical transmissions than the cases without the silica layer. The silica layer plays the role as the graded refractive index layer between the air and the silicon substrate, and the light power from the incident wave can transmit into the silicon substrate with less optical reflections for choosing a suitable silica layer thickness. A guideline to design the structures with high optical transmissions for the solar spectra is given. This study cannot only be useful for the solar cells applications, but also other antireflection applications.