Drastic reduction of plasmon damping in gold nanorods

The dephasing of particle plasmons is investigated using light-scattering spectroscopy on individual gold nanoparticles. We find a drastic reduction of the plasmon dephasing rate in nanorods as compared to small nanospheres due to a suppression of interband damping. The rods studied here also show very little radiation damping, due to their small volumes. These findings imply large local-field enhancement factors and relatively high light-scattering efficiencies, making metal nanorods extremely interesting for optical applications. Comparison with theory shows that pure dephasing and interface damping give negligible contributions to the total plasmon dephasing rate.     

Chemical interface damping of surface plasmon excitation in metal nanoparticles: a study by persistent spectral hole burning

As demonstrated recently, persistent spectral hole burning in the optical spectra of metal nanoparticles makes possible the determination of the ultrafast dephasing time T₂ of surface plasmon excitation. Here, the influence of the chemical environment on the dephasing process is investigated under ultrahigh vacuum conditions by depositing an adsorbate on the nanoparticles. By comparing the optical spectra and the widths of the generated holes of the nanoparticles with and without adsorbate coverage, the influence of chemical interface damping on the dephasing process is examined. The potential of the novel procedure is demonstrated for silver nanoparticles on sapphire and quartz substrates using SO₂ as the adsorbate. A drastic decrease of T₂ for the adsorbate-covered nanoparticles is observed and explained by dynamic charge transfer of electrons from the particles into and out of adsorbate states of the SO₂ molecules. PACS 78.67.Bf; 61.46.+w; 71.45.Gm; 73.22.Lp; 68.43.-h     

Damping of the localized surface plasmon polariton resonance of gold nanoparticles

We report on a strong damping of the localized surface plasmon polariton resonance of gold nanoparticles. The ultra-fast dephasing time of localized surface plasmon polariton resonances in gold nanoparticles was systematically studied as a function of the particle size at a fixed photon energy of h ν=1.85 eV. Dephasing times ranging from T₂^expT_{2}^{\mathrm{exp}} = 5.5 fs to 15.0 fs were extracted and an influence of the reduced dimensions was detected. We have identified two dominant damping mechanisms: the well-known surface scattering and, for the first time, band structure changes. We have quantified the influence of these band structure changes on the optical properties by determining the essential damping parameter A to be A ^exp=0.32 nm/fs.     

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].     

二维自组装结构中银纳米粒子的吸收光谱特征

通过静电相互作用在聚乙烯吡啶修饰的玻璃表面组装了银纳米粒子的二维结构。吸收光谱结果表明,组装银粒子间的相互作用导致银粒子的偶极子表面等离子体共振发生较大的位移,但基本不改变四极子表面等离子体共振。银粒子表面吸附分子及周围介质直接影响其表面等离子体共振。     

Ultrafast dephasing of localized surface plasmons in colloidal silver nanoparticles: the influence of stabilizing agents

Localized surface plasmon dephasing times for aqueous colloidal silver nanoparticles (NPs) stabilized with three different capping agents (trisodium citrate??TSC, poly(vinylpyrrolidone)??PVP, and poly(vinylalcohol)?? PVA) were measured using the persistent spectral hole burning technique. The results obtained by fitting a theoretical curve to the experimental data show that the dephasing times are dependent on the chosen stabilizer (3.0, 2.3, and 1.8?fs for TSC, PVP, and PVA, respectively), and the differences are attributed to changes in the electronic density of states due to the interaction between the NPs and the capping agents. The results are supported by ab initio calculations for the chemisorbate and metallic cluster interaction.     

Double plasmonic profile of tryptophan–silver nano-crystals—Temperature sensing and laser induced antimicrobial activity

Surface plasmon resonance (SPR) for spherical shaped silver nanoparticles showing double maxima at ～390 nm and ～520 nm respectively is reported. Self assembly of silver nanoparticles grown on tryptophan template leads to emergence of equal intensity double plasmon resonance (EIDPR). While for rod shaped nano-forms such double plasmon is explainable but for spherical shaped forms, such double plasmon can be explained on the basis of bidirectional formation of silver cluster in which attachment of silver at two nitrogen atom locations of tryptophan molecule seems to be obligatory. The absence of double resonance in case of silver nanoclusters formed with other amino acids or N-acetyl l-tryptophanamide (NATA), where bidirectional NH₂ attachment is not possible, validates the proposed EIDPR mechanism. Electron micrograph of EIDPR particle indicates a bi-periodic fringe pattern indicating unusual crystalline property. Apart from sensing tryptophan, the double plasmon peaks are sensitive to temperature. Furthermore, the particle can be used as a smart killing agent showing bactericidal activity only upon exposure to low power laser.     

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.     

Diagnostics of aqueous colloids of noble metals by extinction modeling based on mie theory

Two-factor dependences of the maximum and half-width of a surface plasmon resonance band on both the average diameter of nanoparticles and the scatter in their particle-size distributions were defined for colloidal silver and gold aqueous solutions based on modeling the extinction effectiveness factor by Mie theory. The obtained three-dimensional surfaces determined the shape of calibration curves used to define the average particle diameters and the scatter in their particle-size distributions from measurements of the maximum and half-width of the surface plasmon resonance band in spectra of the silver and gold colloidal solutions. The calibration curves were correlated with experimental samples of aqueous ultradispersed media containing silver and gold nanoparticles.     

纳米银组装结构的表面增强荧光效应

采用表面自组装技术,在玻片表面构筑银纳米粒子二维组装结构.银纳米粒子组装结构的吸收光谱表明银粒子表面等离子体共振与粒子间电磁偶合密切相关,偶极子表面等离子体共振更为敏感而发生较大位移.在银纳米粒子组装结构上,荧光素分子的荧光得到极大增强,其表面增强效应强烈依赖于组装金属粒子的表面等离子体共振.     

纳米银组装结构上罗丹明B的表面增强荧光效应

采用表面自组装技术,在玻璃表面构筑银纳米粒子的二维组装结构。银纳米粒子组装结构的表面等离子共振光谱中偶极子表面等离子体共振对组装结构更为敏感而表现出较大位移。组装银纳米粒子可极大增强罗丹明B的荧光。荧光的表面增强效应主要来自银纳米粒子对荧光分子所处区域的局部电磁场增强,银纳米粒子的表面分子修饰对其表面增强效应有较大的影响。     

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.     

微乳液法制备纳米银粒子的结构及其荧光现象研究

采用微乳液法合成了不同粒径的纳米银粒子,考察了环己烷和甲苯作为油相对制备纳米银的影响.对纳米银粒子的尺寸与结构进行了表征,观察到近球形多晶粒子,并有孪晶结构存在,对晶体结构的分析表明银粒子存在不同程度的点阵畸变,晶面间距增大.不同粒径的纳米银粒子氯仿体系可呈现荧光光谱,而纳米银甲苯体系则无荧光发射.结合紫外—可见吸收光谱和电子自旋共振谱对该体系的荧光发射机理进行了分析 关键词： 微乳液 纳米银粒子 纳米晶结构 荧光     

Influence of processing time on nanoparticle generation during picosecond-pulsed fundamental and second harmonic laser ablation of metals in tetrahydrofuran

The influence of fundamental and second harmonic wavelength on ablation efficiency and nanoparticle properties is studied during picosecond laser ablation of silver, zinc, and magnesium in polymer-doped tetrahydrofuran. Laser ablation in stationary liquid involves simultaneously the fabrication of nanoparticles by ablation of the target material and fragmentation of dispersed nanoparticles by post irradiation. The ratio in which the laser pulse energy contributes to these processes depends on laser wavelength and colloidal properties. For plasmon absorbers (silver), using the second harmonic wavelength leads to a decrease of the nanoparticle productivity over process time along with exponential decrease in particle diameter, while using the fundamental wavelength results in a constant ablation rate and linear decrease in particle diameter. For colloids made of materials without plasmon absorption (zinc, magnesium), laser scattering is the colloidal property that limits nanoparticle productivity by Mie-scattering of dispersed nanoparticle clusters.     

Analysis of dynamics of excitation and dephasing of plasmon resonance modes in nanoparticles

A novel theoretical approach to the dynamics analysis of excitation and dephasing of plasmon modes in nanoparticles is presented. This approach is based on the biorthogonal plasmon mode expansion, and it leads to the predictions of time dynamics of excitation of specific plasmon modes as well as their steady state amplitude and their decay. Temporal characteristics of plasmon modes in nanoparticles are expressed in terms of their shapes, permittivity dispersion relations, and excitation conditions. In the case of the Drude model, analytical expressions for time-dynamics of plasmon modes are obtained.     

Dipole and quadrupole surface plasmon resonance contributions in formation of near-field images of a gold nanosphere

Multipolar plasmon optical excitations at spherical gold nanoparticles and their manifestations in the particle images formatted in the particle surface proximity are studied. The multipolar plasmon size characteristic: plasmon resonance frequencies and plasmon damping rates were obtained within rigorous size dependent modelling. The realistic, frequency dependent dielectric function of a metal was used. The distribution of light intensity and of electric field radial component at the flat square scanning plane scattered by a gold sphere of radius 95 nm was acquired. The images resulted from the spatial distribution of the full mean Poynting vector including near-field radial components of the scattered electromagnetic field. Monochromatic images at frequencies close to and equal to the plasmon dipole and quadrupole resonance frequencies are discussed. The changes in images and radial components of the scattered electromagnetic field distribution at the scanning plane moved away from the particle surface from near-field to far-field region are discussed.     

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.     

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.     

Fluorescent silver nanoparticles via exploding wire technique

Aqueous solution containing spherical silver nanoparticles of 20–80 nm size have been generated using a newly developed novel electro-exploding wire (EEW) technique where thin silver wires have been exploded in double distilled water. Structural properties of the resulted nanoparticles have been studied by means of X-ray diffractometer (XRD) and transmission electron microscopy (TEM). The absorption spectrum of the aqueous solution of silver nanoparticles showed the appearance of a broad surface plasmon resonance (SPR) peak centered at a wavelength of 390 nm. The theoretically generated SPR peak seems to be in good agreement with the experimental one. Strong green fluorescence emission was observed from the water-suspended silver nanoparticles excited with light of wavelengths 340, 360 and 390 nm. The fluorescence of silver nanoparticles could be due to the excitation of the surface plasmon coherent electronic motion with the small size effect and the surface effect considerations