Comparing the interparticle coupling effect on sensitivities of silver and gold nanoparticles

The wavelength shift of surface plasmon resonance peak resulting from the electromagnetic coupling noble metal nanoparticle increases with the increase in the dielectric constant of the medium and the decrease in the interparticle separation distance. In this work, the discrete dipole approximation method was used to calculate the extinction efficiency spectra of the silver–silver and gold–gold nanoparticle pairs. This work shows that the silver coupled-particle system has higher plasmon resonance sensitivity as compared to the gold coupled-particle system. However, the silver coupled-particle system has lower and a faster near-exponential decay of sensitivity enhancement factor than the gold coupled-particle system. Thus, the silver coupled-particle may be more suited for sensing applications as compared to the gold coupled-particle, but the interparticle coupling effect displays more pronounced effect on the gold coupled-particle system as compared to the silver coupled-particle system.     

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].     

Optical Properties of Ag and Au Nanoparticles Dispersed within the Pores of Monolithic Mesoporous Silica

The optical absorption of silver and gold nanoparticles dispersed within the pores of monolithic mesoporous silica upon annealing at elevated temperatures has been investigated. With decreasing particle size, the surface plasmon resonance position of the particles blue-shifts first and then red-shifts for silver/silica samples, but only red-shifts for gold/silica samples. This size evolution of the resonance position is completely different from that previously reported for fully embedded particles. We assume a local porosity at the particle/matrix interface, such that free surface of particles within the pores may be in contact with ambient air, and present a two-layer core/shell model to calculate the optical properties. These calculations also consider deviations from the optical constants of bulk matter to account for corresponding effects below about 10 nm particle size. From the good agreement between experimental results and model calculations, we conclude a peculiar particle/ambience interaction dominating the size evolution of the resonance. Because of the difference of core electron structure, the relative importance of the effects of local porosity and free surface, respectively, are different for silver and gold. For silver, the effect of the local porosity is stronger, but for gold the opposite is found.     

Optical properties and biomedical applications of plasmonic nanoparticles

Nanoparticle plasmonics is a rapidly emerging research field that deals with the fabrication and optical characterization of noble metal nanoparticles of various size, shape, structure, and tunable plasmon resonances over VIS-NIR spectral band. The recent simultaneous advances in synthesis, characterization, electromagnetic simulation, and surface functionalization of plasmonic nanoparticles by biospecific molecular probes have led to a perfect publication storm in discoveries and potential biomedical applications of plasmon-resonant nanoparticle bioconjugates. Here, we present an overview of these topics. First, we discus basic wet-chemical routes to fabricate conjugates of gold, silver, or composite particles with controllable size, shape, structure and with surface functionalization by biospecific molecules. Second, we consider the single-particle dipole and multipole optics and coupled plasmonic nanoparticle arrays. Finally, we discus application of plasmonic bioconjugates to such fields as homogeneous and solid-phase assays, biomedical sensing and imaging, biodistribution and toxicity aspects, drug delivery and plasmonic photothermal therapy.     

Broadening of resonances in yttrium nanoparticle optical spectra

The dielectric function of yttrium in the range between 0.2 μm and 2 μm is composed of a harmonic oscillator contribution due to a discrete interband transition and the contribution of free electrons. Hence, it is possible to discuss surface plasmon polaritons as well as other electronic resonances in the optical extinction spectra of yttrium nanoparticles. For the latter, we discuss the broadening of the resonance caused by the aggregation of particles. When particles are lumped into aggregates, the color of the particle system also changes. Aggregation also affects the surface plasmon resonance in yttrium nanoparticles in a way comparable to silver or gold nanoparticle aggregates. Comparison is made with the first experimental results on yttriumnanoparticles, showing that aggregation is the dominant effect for the broad resonance in the measured extinction spectra. Received: 2 July 2001 / Revised version: 10 September 2001 / Published online: 15 October 2001     

Surface effect on the size evolution of surface plasmon resonances of Ag and Au nanoparticles dispersed within mesoporous silica

The optical absorption has been investigated for silver and gold nanoparticles dispersed within the pores of monolithic mesoporous silica after annealing at different temperatures. It has been shown that with reduction of the particle size, the surface plasmon resonance position blue-shifts first and then red-shifts for silver/silica samples, but only red-shifts for gold/silica samples. This size evolution of the resonance is completely different from that previously reported for fully embedded particles. Based on the interaction of the particle surface with ambient air and the porosity at the particle/matrix interface, we present a multi-layer core/shell model and assume that the chemical adsorption of gas molecules from the air on the free surface of nanoparticles within the pores is mainly responsible for the observed size evolution of the resonance.     

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.     

Optical properties of gold nanorings

The optical response of ring-shaped gold nanoparticles prepared by colloidal lithography is investigated. Compared to solid gold particles of similar size, nanorings exhibit a redshifted localized surface plasmon that can be tuned over an extended wavelength range by varying the ratio of the ring thickness to its radius. The measured wavelength variation is well reproduced by numerical calculations and interpreted as originating from coupling of dipolar modes at the inner and outer surfaces of the nanorings. The electric field associated with these plasmons exhibits uniform enhancement and polarization in the ring cavity, suggesting applications in near-infrared surface-enhanced spectroscopy and sensing.     

Spectral characterization and intracellular detection of Surface‐Enhanced Raman Scattering (SERS)‐encoded plasmonic gold nanostars

Plasmonic gold nanostars offer a new platform for surface‐enhanced Raman scattering (SERS). However, due to the presence of organic surfactant on the nanoparticles, SERS characterization and application of nanostar ensembles in solution have been challenging. Here, we applied our newly developed surfactant‐free nanostars for SERS characterization and application. The SERS enhancement factors (EF) of silver spheres, gold spheres and nanostars of similar sizes and concentration were compared. Under 785 nm excitation, nanostars and silver spheres have similar EF, and both are much stronger than gold spheres. Having plasmon matching the incident energy and multiple ‘hot spots’ on the branches bring forth strong SERS response without the need to aggregate. Intracellular detection of silica‐coated SERS‐encoded nanostars was also demonstrated in breast cancer cells. The non‐aggregated field enhancement makes the gold nanostar ensemble a promising agent for SERS bioapplications. Copyright © 2012 John Wiley & Sons, Ltd.     

Plasmonic abilities of gold and silver spherical nanoantennas in terms of size dependent multipolar resonance frequencies and plasmon damping rates

Absorbing and emitting optical properties of a spherical plasmonic nanoantenna are described in terms of the size dependent resonance frequencies and damping rates of the multipolar surface plasmons (SP). We provide the plasmon size characteristics for gold and silver spherical particles up to the large size retardation regime where the plasmon radiative damping is significant. We underline the role of the radiation damping in comparison with the energy dissipation damping in formation of receiving and transmitting properties of a plasmonic particle. The size dependence of both: the multipolar SP resonance frequencies and corresponding damping rates can be a convenient tool in tailoring the characteristics of plasmonic nanoantennas for given application. Such characteristics enable to control an operation frequency of a plasmonic nanoantenna and to change the operation range from the spectrally broad to spectrally narrow and vice versa. It is also possible to switch between particle receiving (enhanced absorption) and emitting (enhanced scattering) abilities. Changing the polarization geometry of observation it is possible to effectively separate the dipole and the quadrupole plasmon radiation from all the non-plasmonic contributions to the scattered light.     

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.     

A novel method of nanocrystal fabrication based on laser ablation in liquid environment

Metal nanoparticles can be prepared by a novel technique that consists of the laser ablation of a solid target immersed in a water solution of a metal salt. Silicon was chosen as the most adequate target to synthesize silver and gold nanoparticles from a water solution of either AgNO₃ or HAuCl₄. The influence of both the silver nitrate concentrations and the irradiation time of the Si target on the optical properties of the Au and Ag nanoparticles have been investigated. The crystalline nature of the metal nanoparticles has been determined by X-ray diffraction (XRD). Average size and particle size distribution have been measured by means of TEM. The absorbance spectra show the characteristic band of the surface resonant plasmon of silver and gold nanoparticles.     

Surface enhanced Raman scattering of molecules related to highly ordered gold cavities

We presented a controlled particles‐in‐cavity (PIC) pattern for surface‐enhanced Raman scattering (SERS) detection. The periodic gold cavity array was fabricated by electrodeposition using highly ordered polystyrene spheres as a template. The as‐prepared gold cavities can be used as a SERS active substrate with significant spectral enhancement and reproducibility, which was evaluated by SERS signals using 4‐mercaptobenzoic acid (4‐MBA) as probe molecules. The surface of these gold cavities was further functionalized with cetyltrimethylammonium bromide molecules, which may immobilize the 4‐MBA‐modified silver nanoparticles in the gold cavity to form a PIC structure via the electrostatic interaction. We have demonstrated that there exists a pH window for the immobilization of the nanoparticles inside cavities. Therefore, the silver nanoparticles can be selectively immobilized into the functionalized gold cavities under the optimized pH value of the media. Further enhancement of the Raman scattering of the labeled molecules can be achieved due to the interconnection between the silver nanoparticles and gold cavity. Copyright © 2013 John Wiley & Sons, Ltd.     

Tunability and linewidth sharpening of plasmon resonances on a periodic gold nanowire array coupled to a thin textured silver film

We theoretically study the plasmon mode spectrum of a multilayer structure consisting of a periodic gold nanowire array and a spatially separated thin silver film with periodic slits. Results show that the plasmon mode spectrum of the multilayer structure depends sensitively on the relative lateral displacement of the Au nanowire array with respect to the textured silver film. This is due to the interaction between the localized surface plasmon (LSP) of the nanowire array and the plasmon modes, including the horizontal LSP and the antisymmetric short-range surface plasmon polariton (SPP), of the textured thin silver film. The strong coupling between the LSP and the antisymmetric short-range SPP results in a redshifted plasmon resonance with a significantly narrow linewidth and a large electromagnetic field enhancement. Moreover, the lateral displacement also has a great influence on the spacer layer controlled dipole-surface interaction. Therefore, this relative lateral displacement provides an efficient way to tune the optical properties of the multilayer structure, and this kind of highly tunable nanostructure can be used as a tunable plasmonic filter or a substrate for LSPs sensor.     

Surface plasmon polariton scattering by small ellipsoid particles

Scattering of surface plasmon polaritons (SPP’s) by small ellipsoid particles placed near a dielectric–metal interface is theoretically considered. Using the Green’s function formalism and the dipole approximation, we consider the differential and total scattering cross-sections associated with the SPP-to-SPP scattering as well as with the SPP scattering into waves propagating away from the interface, analyzing the influence of system parameters. As an example, scattering cross-sections of differently shaped gold spheroid particles placed near an air–gold interface are evaluated at the light wavelength of 800 nm. It is shown that the differential and total cross-sections depend strongly upon the particle-to-surface distance, the ratio between the major and minor axes and their orientation with respect to both the interface and the direction of SPP incidence. Implications of the obtained results to the design of SPP micro-optical components are also discussed.     

基于芯片实验室技术的表面增强光谱学在分析科学中的应用

集成具有一序列微流控操作单元的芯片实验室技术,在微流控通道内铺陈金属纳米粒子(尤其是金、银以及铜纳米粒子)作为衬底,泵入多通道微纳升分析物,用于联用表面增强光谱在痕量、实时、原位、过程反应等检测中具有重要的意义。这种联用检测技术集成了芯片实验室和表面光谱两种技术的优点：芯片实验室技术集成流程式分步操作,实现筛选取样,分段、实时反应检测,减小样品量,稳定测试环境等优势以及表面增强光谱的光谱响应快,灵敏性和选择性强、原位检测等优点。借助于Drude模型以及适当的边界条件,外电场引发金属颗粒价电子的局域等离子振荡,并推导了产生共振的局域表面等离子增强以及受激感应偶极子振荡产生表面拉曼增强的物理电磁增强机制。综述了芯片实验室表面局域等离子检测在生物、医药、食品安全等方面的应用,检测通道的增加促使检测效率有较大的提高,同时检测限能力获得较大的突破。综述了芯片实验室技术结合表面增强拉曼光谱公共安全、生物医学、电化学和生物传感器等领域的应用, 表面增强拉曼光谱的高度灵敏性以及指纹性应用于痕量检测。根据芯片实验室技术在研究开发和应用已经获得不断的进展,结合3D打印技术,精准控制多通道结构尺寸,更好地满足设计的需求。表面等离子增强光谱以及表面增强拉曼光谱等表面光谱检测技术在应用上日趋成熟,获得突破传统显微镜的光学极限的分辨能力。这种联用技术在实际定性或者半定量痕量分析检测应用中具有光明的前景。     

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.     

Advanced Nanotools for Imaging of Solid Tumors and Circulating and Disseminated Cancer Cells

We propose methods for creating spherical gold particles of submicron size and silver rod-like particles with transverse dimensions of ~10 nm and an aspect ratio of 1: 10. Factors determining the frequency of plasmon resonances are considered, reagents are selected, and their ratios for obtaining prolate silver particles are determined. An optimal concentration of the surfactant is determined for creating most elongated silver particles. A shift of the plasmon absorption toward the near-IR range of the spectrum is obtained.     

Improving power conversion efficiency of perovskite solar cells by cooperative LSPR of gold-silver dual nanoparticles

Enhancing optical and electrical performances is effective in improving power conversion efficiency of photovoltaic devices. Here, gold and silver dual nanoparticles were imported and embedded in the hole transport layer of perovskite solar cells. Due to the cooperative localized surface plasmon resonance of these two kinds of metal nanostructures, light harvest of perovskite material layer and the electrical performance of device were improved, which finally upgraded short circuit current density by 10.0%, and helped to increase power conversion efficiency from 10.4% to 11.6% under AM 1.5G illumination with intensity of 100 m W/cm~2. In addition, we explored the influence of silver and gold nanoparticles on charge carrier generation, dissociation, recombination, and transportation inside perovskite solar cells.     

Measuring the quantum efficiency of the optical emission of single radiating dipoles using a scanning mirror

Using scanning probe techniques, we show the controlled manipulation of the radiation from single dipoles. In one experiment we study the modification of the fluorescence lifetime of a single molecular dipole in front of a movable silver mirror. A second experiment demonstrates the changing plasmon spectrum of a gold nanoparticle in front of a dielectric mirror. Comparison of our data with theoretical models allows determination of the quantum efficiency of each radiating dipole.