Nonlinear susceptibility of a metal-dielectric nanocomposite caused by induced dipole-dipole forces between particles

The optical coefficients of a nonlinearity for a macroscopic ensemble of aggregates of metal nanoparticles that is caused by deformation of the spatial structure of clusters in a strong light field are calculated for the first time. For a continuous medium that consists of a nonabsorbing dielectric containing aggregated silver nanoparticles that do not possess an intrinsic optical nonlinearity, coefficients of nonlinear absorption are obtained in relation to the intensity and frequency of incident light. It is shown that, at intensities of up to a few megawatts per square centimeter, the addition to the absorption of a nanocomposite to be modeled is adequately described by a third-order nonlinearity. The magnitude and sign of the nonlinear absorption coefficient agree well with the previously obtained experimental data for aggregated silver and gold colloids under nanosecond excitation.     

Molecules with a permanent dipole moment in a periodic medium with quadratic nonlinearity

Nonlinear optical effects in a one-dimensional periodic medium containing spatially oriented molecules of J aggregates of a dye and silver nanoparticles are studied. It is shown that, in such composite medium, the presence of a permanent dipole moment of an exciton transition of molecules of J aggregates results in the appearance of new nonlinear optical properties.     

Processes in resonant domains of metal nanoparticle aggregates and optical nonlinearity of aggregates in pulsed laser fields

Optical nonlinearities in aggregates of nanoparticles formed in silver hydrosols (SHs) are studied under pico- and nanosecond pulsed laser excitation. The dependence of the nonlinear refractive index n ₂ on the degree of hydrosol aggregation is studied experimentally at the wavelength λ=1.064 μm. It is found that n ₂ changes sign when the degree of hydrosol aggregation is increased. Various physical effects occurring in resonant domains of the aggregates are analyzed using a simple physical model of two bound silver nanoparticles. The theory takes into account thermal, elastic, electrostatic, and light-induced effects. Experimental results are discussed in the context of this theory.     

聚集效应对银纳米粒子的二阶非线性光学特性的影响研究

运用超瑞利散射(HRS)技术,对由KNO3诱导聚集的银纳米粒子的二阶光学非线性特性进行了实验研究.通过粒子尺寸测量和透射电镜观察，表明银纳米粒子的聚集方式为链状聚集.当聚集体平均尺寸为120nm时，银纳米粒子聚集体的HRS信号强度比聚集前增大了约15倍.分析表明，聚集导致银纳米粒子表面电场极化强度的增强和极化分布的改变，并通过表面和体贡献机理对二阶非线性极化过程产生影响. 关键词： 银纳米粒子 超瑞利散射 二阶光学非线性 聚集     

Anisotropy in the nonlinear absorption of elongated silver nanoparticles in silica, probed by femtosecond pulses

We present measurements of the anisotropy of the nonlinear absorption of a silica matrix doped with aligned spheroidal silver nanoparticles, produced by a double ion-implantation process of silver nanoparticles followed by an irradiation with Si ions. The nonlinear response was studied using the z-scan technique with fs pulses at 530 nm, which lies very close to the surface-plasmon absorption peak of the sample. The observed saturable absorption is studied for different angles of the input linear polarization of the pulses, showing a strong anisotropy, which is consistent with the fact that the nanorods are aligned.     

Size-dependent nonlinear optical properties and thermal lens in silver nanoparticles

We have investigated the nonlinear response of the silver nanoparticle samples in a low-power regime of electromagnetic field based on nonlocal thermo-optic models. In this work, the experimental investigation of the thermo-optic nonlinear response of Ag colloids containing different size of silver nanoparticles is reported. The colloidal nanoparticle samples were synthesized by nanosecond pulsed laser ablation of Ag bulk in acetone. The sample containing Ag was characterized by linear absorption spectroscopy and transmission electron microscopy. Using the z-scan technique, the behavior of thermal nonlinear refractive index of colloid was studied at different concentrations of silver nanoparticles. Observation of asymmetrical configurations of the z-scan data indicates that nonlinear refraction occurring in the Ag samples is related to the thermo-optical process. The optical limiting here is due to nonlinear refraction of the samples arising from thermal lens formation under low-power CW excitation. When the laser power is low, the self-defocusing effect is mainly dominated by surface plasmon resonance effect. Results show that with increasing concentration of nanoparticles in acetone, the nonlinear refractive index increases while the threshold power of optical limiting decreases.     

Thiol‐immobilized silver nanoparticle aggregate films for surface enhanced Raman scattering

We report a novel method for the fabrication of films of silver nanoparticle aggregates that are strongly attached to Si substrates (Thiol‐immobilized silver nanoparticle aggregates or TISNA). The attachment is achieved by chemically modifying the surface of a Si(100) surface in order to provide SH groups covalently linked to the substrate and then aggregating silver nanoparticles on these thiol covered surfaces. The transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) characterization show a high coverage with single nanoparticles or small clusters and a partial coverage with fractal aggregates that provide potential hot spots for surface enhanced Raman scattering (SERS). We have confirmed the SERS activity of these films by adsorbing rhodamine 6G and recording the Raman spectra at several concentrations. By using the silver‐chloride stretching band as an internal standard, the adsorbate bands can be normalized in order to correct for the effects of focusing and aggregate size, which determine the number of SERS active sites in the focal area. This allows a quantitative use of SERS to be done. The adsorption–desorption of rhodamine 6G on TISNA films is reversible. These features make our TISNA films potential candidates for their use in chemical sensors based on the SERS effect. Copyright © 2008 John Wiley & Sons, Ltd.     

飞秒光脉冲Z扫描技术测量纳米银颗粒非线性折射率

本文首次报道了用飞秒脉冲光Z扫描技术测量纳米银悬浮粒子的非线性折射率。从物理机制及理论上对Z扫描进行了分析,并对纳米悬浮粒子的有效长度进行了估算。利用标准样品对系统进行了标定。最后得到了纳米银粒子的非线性折射率为6.75×10^-10esu.     

A simple method for the preparation of ultrahigh sensitivity surface enhanced Raman scattering (SERS) active substrate

By immersing mica modified with cetyltrimethylammonium bromide (CTAB) into the silver colloid, a high efficient surface enhanced Raman scattering (SERS) active substrate was formed within 2 h at room temperature. The limit of detection of the substrate for Rhodamine 6G is up to 1×10⁻¹⁴ M. Changing the concentration of silver colloid and the treating time, various silver aggregates such as nanocrystals, clusters and films were found, and the SERS spectra of these aggregates were also obtained. The results of SERS revealed that CTAB could accelerate aggregation of the silver colloid and cause great Raman enhancement. Bilayer of CTAB is very important for aggregation of silver colloid and the aggregation extent is the main factor for the enormous enhancement on this substrate.     

A mechanism of the anti-Stokes luminescence of a dye-sensitized silver halide emulsion

A two-photon stepwise mechanism of the low-temperature anti-Stokes luminescence of a sensitized AgBrI emulsion, caused by photoexcitation of dye aggregates, is proved experimentally. According to this mechanism, the photoexcitation energy is transferred from the dye to the AgHal microcrystal through silver cluster centers. It is found that the luminescence with the maximum at λ ≈ 750 nm is caused by the recombination of an electron localized at the silver cluster with a free hole in the valence band of the AgHal microcrystal. The migration of an electron from a silver cluster to a iodine pair center with a captured hole creates a nonradiative recombination channel, which is responsible for the flare buildup of the green anti-Stokes luminescence upon excitation of dye aggregates.     

Processes involved in the formation of silver clusters on silicon surface

We analyze scanning electron microscopy measurements for structures formed in the deposition of solid silver clusters onto a silicon(100) substrate and consider theoretical models of cluster evolution onto a surface as a result of diffusion and formation of aggregates of merged clusters. Scanning electron microscopy (SEM) data are presented in addition to energy dispersive X-ray spectrometry (EDX) measurements of the these films. Solid silver clusters are produced by a DC magnetron sputtering source with a quadrupole filter for selection of cluster sizes (4.1 and 5.6 nm or 1900 and 5000 atoms per cluster in this experiment); the energy of cluster deposition is 0.7 eV/atom. Rapid thermal annealing of the grown films allows analysis of their behavior at high temperatures. The results exhibit formation of cluster aggregates via the diffusion of deposited solid clusters along the surface; an aggregate consists of up to hundreds of individual clusters. This process is essentially described by the diffusion-limited aggregation (DLA) model, and thus a grown porous film consists of cluster aggregates joined by bridges. Subsequent annealing of this film leads to its melting at temperatures lower than to the melting point of bulk silver. Analysis of evaporation of this film at higher temperatures gives a binding energy in bulk silver of ɛ₀= (2.74 ± 0.03) eV/atom. The text was submitted by the authors in English.     

Polarization effects in nanoaggregates of silver caused by local and nonlocal nonlinear-optical responses

A theoretical and experimental study is made into the combined manifestation of local and nonlocal optical responses in a cubic nonlinear isotropic medium such as an aggregated colloidal silver solution. The phenomenological treatment of polarization effects is performed for the general case with due regard for the frequency dispersion of both local and nonlocal nonlinearities and for the noncollinear propagation of pump and probe light waves. The inverse Faraday effect, the optical Kerr effect, and the self-rotation of the polarization ellipse in a fractal-disordered nonlinear medium are observed for the first time. The tensor components of the local and nonlocal cubic nonlinearities of colloidal silver solutions are measured for different degrees of aggregation. It is demonstrated that, as the size of silver aggregate increases, the nonlocal nonlinear response increases much more strongly than the local one. An inference is made that the mechanical motion of metal nanoparticles because of their dynamic interaction with the light wave field can contribute to the nonlinear polarization effects.     

SERS study of pyridine vapor exposed to silver substrates electrochemically prepared.

Silver electrodes, previously prepared in KCl, KBr and KNO₃ electrolyte solutions, are exposed to a saturated vapor of pyridine, at room temperature. Surface complexes involving a silver halide and pyridine are detected during the gas - solid interaction. A low frequency band was observed, without exposure to pyridine, when a large amount of silver halide deposited on the electrode, is irradiated with a laser blue line. Photoreduction of the silver halide into metal aggregates occurs during the exposure to the laser.

Some hypothesis about the adsorption of pyridine at room temperature are advanced from results obtained with a silver electrode prepared in a KNO₃ solution.     

Rapid and simple detection of sodium thiocyanate in milk using surface‐enhanced Raman spectroscopy based on silver aggregates

Surface‐enhanced Raman spectroscopy (SERS) was used for rapid detection of sodium thiocyanate in milk employing silver aggregates as active substrate. Silver nanoparticles were induced to silver aggregates by trichloroacetic acid (TCA). The limit of detection (LOD) for sodium thiocyanate was 10⁻² µg ml⁻¹ in water with an analytical enhancement factor of 5.4 × 10⁶. The silver aggregates represent good reproducibility and stability. Good linear relationship was obtained for sodium thiocyanate in milk at concentration ranges from 0.1 to 10 µg ml⁻¹ (R² = 0.995). Using TCA as protein precipitator, silver colloid would aggregate spontaneously when mixing with samples during SERS measurement without the need of additional aggregating agent. The simple pretreatment procedures and analytical methods are less time consuming (<10 min) and environmentally friendly, making the proposed method much practical for in situ detection of sodium thiocyanate in market milk. Copyright © 2014 John Wiley & Sons, Ltd.     

Saturable absorption and reverse saturable absorption on silver particles with different shapes

Micro/nanostructured silver particles with different shapes (flower, wire, and rod) have been prepared and characterized. All the open aperture z-scan curves of silver microrods and silver nanoflowers present a typical reverse saturable absorption. With the increase of incident intensity, the nonlinear absorption coefficients and the third-order optical susceptibilities ImX⁽³⁾ of nanoflowers increase, but those of silver microrods decrease. Moreover, the silver nanowires show the conversion from saturable absorption to reverse saturable absorption. There was no definite correlation between incident intensity and nonlinear absorption coefficient (β) under the conditions studied herein. And nonlinear optical properties of micro/nanostructured silver particles are dependent on the particle shape in suspensions at 800 nm.     

The effect of concentration on the thermo-optical properties of colloidal silver nanoparticles

The thermo-optical properties of colloidal silver nanoparticles (AgNPs) are investigated under a low power laser irradiation at 532 nm. Colloidal AgNPs are synthesized by nanosecond pulsed laser ablation of a pure silver plate in distilled water. The morphology and size of the AgNPs are determined by transmission electron microscopy. Closed Z-scan measurements reveal that nonlocal thermo-optic process is responsible for the nonlinear refractive index of colloid containing different concentrations of silver nanoparticles. The Z-scan behavior of the nanoparticle samples has been investigated based on a nonlocal thermo-optic process and it is shown that the aberrant thermal lens model is in excellent agreement with the experimental results. Z-scan measurement fits have allowed the values of nonlinear refractive index (n₂) and thermo-optic coefficients (dn/dt) to be determined at different concentrations of silver nanoparticles. Large enhancement factors were measured for values of n₂ and dn/dt of the colloids at higher silver nanoparticle volume fraction. Our results suggest that nonlocal thermal nonlinear processes will play an important role in the development of photonic applications involving metal nanoparticle colloids.     

Coarsening and pearling instabilities in silver nanofractal aggregates

We investigate the morphological changes of 3D supported fractal aggregates generated through the deposition of silver clusters on graphite. The fractal relaxation, activated after their formation by perturbing them either by thermal annealing or by using a surfactant, as oxide molecules, carried by silver clusters in a subsequent deposition, shows evidence of two distinct fragmentation patterns. The post coarsening, driven by thermal heating, gives a broad asymmetrical distribution of fragments in agreement with a random process, whereas the entire silver fractal pearling fragmentation is driven by chemical adjunction of the surfactant.     

Investigation of the nonlinear optical characteristics of composite materials based on sapphire with silver, copper, and gold nanoparticles by the reflection Z-scan method

The nonlinear optical characteristics of silver, copper, and gold nanoparticles synthesized in a sapphire matrix by ion implantation are studied. The measurements are performed by the RZ-scan method with optical reflection at the radiation wavelength of a picosecond Nd:YAG laser (λ = 1064 nm). The nonlinear refractive indices and the real parts of the third-order nonlinear susceptibility of the composites are determined. It is shown that the nonlinear refraction in the samples is caused by the Kerr effect.     

Nonlinear refraction of silver nanowires from nanosecond to femtosecond laser excitation

In order to investigate the effect of pulse width and solvent on the nonlinear properties of metal nanostructures, silver nanowires were fabricated in a direct current electric field (DCEF) using a solid-state ionic method and characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The nonlinear refractive index (γ) of silver nanowires suspended in ethanol was measured using the Z-scan technique and laser radiation of various (femto-, pico-, and nanosecond) pulse durations. Experimental results indicated that silver nanowires have obvious positive refractive nonlinearities and γ (the Kerr-induced self-focusing) increases as the pulse duration increases from 7.4×10⁻⁸ cm²/GW at 110 fs to 1.6×10⁻⁴ cm²/GW at 8 ns, due to the additional influence of the atomic reorientational Kerr effect in the case of longer pulses. Due to the solvent dependence of the nonlinear behavior of the silver nanowires, the nonlinear absorption and refraction of silver nanowires suspended in de-ionized water are smaller than those of silver samples suspended in ethanol. The thermal nonlinearities are insignificant in our experimental conditions.     

Understanding the Interaction of Glutamate Salts with Serum Albumin Protected Prism‐Shaped Silver Nanoparticles toward Glutamate Sensing

Surface plasmon spectroscopy of serum albumin protected prism‐shaped silver nanoparticles is used as simple and effective sensing tool to detect glutamate salts. The approach does not require any electrochemical setup to detect glutamates, in contrast to common techniques to detect glutamates in general. Experiments reveal that upon presence of high concentrations of glutamate salts, the prism‐shaped nanoparticles are transformed to smaller‐sized nanoclusters, while the remaining nanoparticles are assembled to form aggregates. Control experiments confirm that the interaction is specific to the serum albumin coating, the prism shape of the nanoparticles, and to silver.