Simultaneous excitation of cavity resonance and surface plasmon resonance in Ag/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Ag layer structure

Simultaneous excitation of cavity resonance (CR) and surface plasmon resonance (SPR) was observed in the angular spectrum by substituting Ag/Al₂O₃/Ag layers for the metal film in a Kretschmann structure. Two reflective valleys, elicited respectively by CR and SPR, appeared at different positions in the angular spectrum. The former is the sum of enhanced transmission of CR and absorption of the metal, expressed in the reflection spectrum and extremely insensitive to the changes of the surface environment (refractive index). The latter behavior is like that when two metal films are stuck together: it has almost the same resonance depth and width, and is extremely sensitive to the changes of the surface environment. Moreover, two SPR peaks could be excited simultaneously at one angle but with different wavelengths in the frequency spectrum, which is not seen in traditional Kretschmann structures.     

Photoinduced nanocomposites—creation, modification, linear and nonlinear optical properties

UV irradiation of materials consisting of a polymer matrix that possesses precursors of noble metals followed by annealing results in creation of metal nanoparticles within the irradiated domains. Such photoinduced nanocomposites are promising for photonics applications due to the strong alteration of their optical properties compared to initial nonirradiated materials. We report our results on the synthesis and investigation of two kinds of these materials:

1. Photoinduced Au nanocomposites based on PMMA matrices, including bulk materials prepared by means of the polymerization technique;
2. photoinduced Ag nanocomposites with an organic–inorganic hybrid matrix based on TiO₂ gels.

The experimental data on evolution of absorption spectra of these materials due to laser irradiation at different wavelengths are presented. The linear and nonlinear refractive index changes in these materials owing to light-induced nanonstructuring are investigated.     

Nonlinear optical characteristics of nanoparticles in suspensions and solid matrices

The study of the nonlinear optical parameters of suspensions and glass matrices doped with various nanoparticles (Ag, Cu, Co, Au, Pt, GaAs, CdS, As₂S₃) are presented. Various techniques for the preparation of nanoparticles in suspensions and solid matrices, in particular laser ablation, chemical methods, and ion implantation are discussed. We present our measurements of the nonlinear refractive indices, nonlinear absorption coefficients, saturation intensities, and nonlinear susceptibilities of nanoparticles-containing media using laser pulses generating in various spectral and temporal ranges. PACS 42.65.An; 42.65.Hw; 42.65.Jx; 61.46.Df; 78.67.Bf     

Efficient fabrication of transparent antimicrobial poly(vinyl alcohol) thin films

We have explored in situ synthesis of Ag nanoparticles in transparent PVA films in view of increasing areas of application of those films. The two-step procedure consists of ion incorporation in the matrix and subsequent thermal reduction. Smooth and transparent PVA films containing Ag nanoparticles of 5–20 nm were fabricated by this approach. The optical property of the films and the size of metal nanoparticles could be controlled by changing the reaction conditions. By increasing heating temperature, the absorbance and wavelength of surface plasmon resonance (SPR) of the composite film increased, and nanoparticles with larger particle sizes and broader size distributions were obtained. In the temperature range of 130–170 °C, the wavelength of SPR increased with increasing the AgNO₃ concentration. At 190 °C, however, the wavelenght of SPR blue-shifted initially when the AgNO₃ concentration increased from 10 to 80 mmol/L, and red-shifted thereafter. The composite films showed excellent antimicrobial performance toward bacteria such as Escherchia coli. Such hybrids afford very effective and environment-friendly antimicrobial surface coatings.     

First-principles study of electrical structures and optical properties of Ag or Au doped MgF2 crystal

The geometric structure, electronic and optical properties of MgF₂ crystal mixed with Ag, Au are obtained by adopting the first-principles calculation of plane wave ultra-soft pseudo-potential technology based upon the density function theory (DFT). The calculation results show that the doping of Ag and Au diminishes of the MgF₂ system and the occurrence of half-metallic properties with a greater influence of Au than Ag. In addition, the refractive index and absorption coefficient of the MgF₂ system are enhanced because of the doping. The modulation action on the refractive index of MgF₂ indicates potential application of the forbidden bandwidth doping in optical devices.     

Concentration-related enhancement of the sensitivity of surface plasmon resonance of metallic nanoparticles to the characteristics of a dielectric environment

We present the results of theoretical and experimental studies of the optical attenuation spectra of planar nanocomposites consisting of close-packed monolayers of metallic nanoparticles placed in different dielectric matrices. We have analyzed the dependence of the spectral position of the collective surface plasmon resonance (collective SPR) on the refractive index of the dielectric environment. The experimental samples were created by successive thermal vaporization under vacuum of a metal and a dielectric. The theoretical calculations were performed using the quasicrystal approximation of multiple wave scattering theory. We have shown that an increase in the concentration of nanoparticles of noble metals shifts the maximum of the collective SPR band toward longer wavelengths, and significantly increases the sensitivity of its spectral position to the refractive index of the dielectric environment. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 568–572, July–August, 2008.     

Adjustable surface plasmon resonance with Au,Ag, and Ag@Au core-shell nanoparticles

We report an experimental study on the synthesis of metal nanoparticles （NPs） with adjustable optical density based on surface plasmon resonance （SPR）. Metal NPs prepared by laser ablation in liquid method and the effect of laser parameters on the size, distribution, wavelength of SPR of Ag, Au, and mixture of Ag-Au, and Ag core/Au shell NPs are investigated. Our results show that the adjustable SPR band can be achieved in each class of NPs which is suitable for adjustable optical window applications.     

Plasmonics properties of trimetallic Al@Al2O3@Ag@Au and Al@Al2O3@AuAg nanostructures

Bimetallic and trimetallic nanoparticles have attracted significant attention in recent times due to their enhanced electrochemical and catalytic properties compared to monometallic nanoparticles. The numerical calculations using Mie theory has been carried out for three-layered metal nanoshell dielectric–metal–metal (DMM) system consisting of a particle with a dielectric core (Al@Al₂O₃), a middle metal Ag (Au) layer and an outer metal Au (Ag) shell. The results have been interpreted using plasmon hybridization theory. We have also prepared Al@Al₂O₃@Ag@Au and Al@Al₂O₃@AgAu triple-layered core–shell or alloy nanostructure by two-step laser ablation method and compared with calculated results. The synthesis involves temporal separations of Al, Ag, and Au deposition for step-by-step formation of triple-layered core–shell structure. To form Al@Ag nanoparticles, we ablated silver for 40 min in aluminium nanoparticle colloidal solution. As aluminium oxidizes easily in water to form alumina, the resulting structure is core–shell Al@Al₂O₃. The Al@Al₂O₃ particle acts as a seed for the incoming energetic silver particles for multilayered Al@Al₂O₃@Ag nanoparticles is formed. The silver target was then replaced by gold target and ablation was carried out for different ablation time using different laser energy for generation of Al@Al₂O₃@Ag@Au core–shell or Al@Al₂O₃@AgAu alloy. The formation of core–shell and alloy nanostructure was confirmed by UV–visible spectroscopy. The absorption spectra show shift in plasmon resonance peak of silver to gold in the range 400–520 nm with increasing ablation time suggesting formation of Ag–Au alloy in the presence of alumina particles in the solution.     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.     

Surface Plasmon Resonance and Field Enhancement of Au/Ag Alloyed Hollow Nanoshells

We investigate the nanostructure, surface plasmon resonance （SPR） absorption and nonlinear enhancement of Au/Ag alloyed hollow nanoshells prepared by the replacement reaction of Ag nanoparticles in a HAuCI4 aqueous solution. As the volume of HAuCl4 increases from OmL to 0.S mL, the SPR band of the Au/Ag alloyed nanoshells is tuned from 430nm to 780nm, and the third-order nonlinear optical susceptibility is enhanced nearly by an order of magnitude, which indicates a large enhancement of local field in the Au/Ag alloyed hollow nanoshells with hole defects.     

利用激光烧蚀法制备表面等离子体可调谐的金核银壳层纳米颗粒胶体

利用激光烧蚀方法在水中制备了金核银壳层纳米颗粒胶体,发现这种复合胶体的等离子体振动吸收峰频率会随着激光烧蚀时间的不同而发生改变。利用等离子杂化理论定性解释了共振吸收峰可调谐的物理机制.     

High-Sensitivity Sensor Based on Surface Plasmon Resonance Enhanced Lateral Optical Beam Displacements

We present a new optical sensor based on surface plasmon resonance （SPIt） enhanced lateral optical beam displacements. Compared with the traditional SPIt methods, the new method provides higher sensitivity to the sensor system. Theoretical simulations show that the refractive index （RI） detection sensitivity of the SPR sensor based on the displacement measurement has a strong dependence on the thickness of the metal film. When the optimal thickness of the metal film is selected, the RI resolutlon of the SPIt sensor is predicted to be 2.2 × 10^-7 refractive index units （RIU）. Furthermore, it is found that the incidence angle can be used as a parameter to adjust the operating range of the sensor to different refractive index ranges.     

A facile strategy to synthesize bimetallic Au/Ag nanocomposite film by layer-by-layer assembly technique

A facile strategy has been developed for the preparation of bimetallic gold–silver (Au–Ag) nanocomposite films by alternating absorption of poly-(ethyleneimine)–silver ions and Au onto substrates and subsequent reduction of the silver ions. The composition, micro-structure and properties of the {PEI–Ag/Au}_n nanocomposite films were characterized by ultraviolet visible spectroscopy (UV–vis), transmisson electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), surface enhanced Raman scattering (SERS) and cyclic voltammetry (CV). The UV–vis characteristic absorbances of {PEI–Ag/Au}_n nanocomposite thin film increase almost linear with the number of bilayers, which indicates a process of uniform assembling. Appearance of a double plasmon bands in the visible region and the lack of apparent core–shell structures in the TEM images confirm the formation of bimetallic Au–Ag nanoparticles. The result of XPS also demonstrates the existence of Ag and Au nanoparticles in the nanocomposite films. TEM and FESEM images show that these Ag and Au nanoparticles in the films possess sphere structure with the size of 20–25 nm. The resulting {PEI–Ag/Au}_n films inherit the properties from both the metal Ag and Au, which exhibits a unique performance in SERS and electrocatalytic activities to the oxidation of dopamine. As a result, the {PEI–Ag/Au}_n films are more attractive compared to {PEI–Ag/PSS}_n and {PEI/Au}_n films.     

Optical properties of sol-gel fabricated Ni/SiO2 glass nanocomposites

Nickel nanoparticles were grown in silica glass by annealing of the sol-gel prepared silicate matrices doped with nickel nitrate. TEM characterization of Ni/SiO₂ glass proves the formation of isolated spherical nickel nanoparticles with mean sizes 6.7 and 20 nm depending on annealing conditions. The absorption and photoluminescence spectra of Ni/SiO₂ glasses were measured. In the absorption spectra, we observed the band related to the surface plasmon resonance (SPR) in Ni nanoparticles. The broadening of SPR was observed with decrease of Ni nanoparticle size. The width of the surface plasmon band decreases 1.5 times at the lowering of temperature from 293 to 2 K because of strong electron-phonon interaction. The spectra proved the creation of nickel oxide NiO clusters and Ni²⁺ ions in silica glass as well.     

Performances of different metals in optical fibre-based surface plasmon resonance sensor

The capability of various metals used in optical fibre-based surface plasmon resonance (SPR) sensing is studied theoretically. Four metals, gold (Au), silver (Ag), copper (Cu) and aluminium (Al) are considered for the present study. The performance of the optical fibre-based SPR sensor with four different metals is obtained numerically and compared in detail. The performance of optical fibre-based SPR sensor has been analysed in terms of sensitivity, signal-to-noise (SNR) ratio and quality parameter. It is found that the performance of optical fibre-based SPR sensor with Au metal is better than that of the other three metals. The sensitivity of the optical fibre-based SPR sensor with 50 nm thick and 10 mm long Au metal film of exposed sensing region is 2.373 μm/RIU with good linearity, SNR is 0.724 and quality parameter is 48.281 RIU^− 1. The thickness of the metal film and the length of the exposed sensing region of the optical fibre-based SPR sensor for each metal are also optimized.     

Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

Non-linear optical properties of silver nanoparticles prepared by hydrogen reduction method

Silver nanoparticles have been prepared using hydrogen gas as the reducing agent for silver nitrate and poly(vinyl pyrrolidone) as the capping agent; the reaction was carried out at 70 °C for 3 h. The size of the nanoparticles was found to be about 20 nm as analyzed using transmission electron micrographs. The X-ray diffraction pattern revealed the face-centered cubic (fcc) structure of silver nanoparticles. The linear absorption of Ag nanoparticles, α, is obtained about 3.71 cm⁻¹. The non-linear refractive indices of silver nanoparticles were defined by the z-scan technique using CW He-Ne laser (λ = 632.8 nm) at different incident intensities. The magnitude of non-linear refractive index (n₂) was measured to be in the order of 10⁻⁷ (cm²/W) with a negative sign. Therefore self-defocusing phenomena is taking placed for Ag nanoparticles.     

Measurement of nonlinear refractive index of Ag and Au nano-particles using moiré technique

In this paper we have measured second order nonlinear refractive index of Ag and Au nano-particles using the moiré deflectometry with a CW He-Ne laser at wavelength of 632.8 nm. The main advantages of this technique are its extreme experimental simplicity and low sensitivity to external distribution in comparison with other interfrometric methods that need very stable experimental set-up. Because of self-focusing (or self-defocusing) that is due to intensity dependent refractive index, presence of sample in the moiré deflectometry set-up lead to rotation of moiré fringes. By moving the sample in set-up we have measured these rotation angles in different displacements from focus point of lens used in this set-up and then we have calculated the nonlinear refractive index of Ag and Au nano-particles using their values. Also we have obtained the sign of n₂ regard to the direction of rotations. Consequently by using the Mathematica software we have exhibited the suitable fitness of theoretical curve with experimental results.     

Nanoparticles-chemistry, new synthetic approaches, gas phase clustering and novel applications

In this paper, an overview of the synthesis, chemistry and applications of nanosystems carried out in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and applications. In ‘chemistry of nanoparticles’ we describe a novel reaction between nanoparticles of Ag and Au with halocarbons. The reactions lead to the formation of various carbonaceous materials and metal halides. In ‘development of new synthetic approaches’ our one-pot methodologies for the synthesis of core-shell nanosystems of Au, Ag and Cu protected with TiO₂ and ZrO₂ as well as various polymers are discussed. Some results on the interaction of nanoparticles with biomolecules are also detailed in this section. The third section covers the formation of gas phase aggregates/clusters of thiol-protected sub-nanoparticles. Laser desorption of H₂MoO₄, H2WO₄, MoS₂, and WS₂ giving novel clusters is discussed. The fourth section deals with the development of simple devices and technologies using nanomaterials described above.     

Surface plasmon optical sensor with enhanced sensitivity using top ZnO thin film

Surface plasmon resonance (SPR) is one of the most sensitive label-free detection methods and has been used in a wide range of chemical and biochemical sensing. Upon using a 200 nm top layer of dielectric film with a high value of the real part ε′ of the dielectric function, on top of an SPR sensor in the Kretschmann configuration, the sensitivity is improved. The refractive index effect of dielectric film on sensitivity is usually ignored. Dielectric films with different refractive indices were prepared by radio frequency magnetron (RF) sputtering and measured with spectroscopic ellipsometry (SE). The imaginary part ε′′ of the top nanolayer permittivity needs to be small enough in order to reduce the losses and get sharper dips. The stability of the sensor is also improved because the nanolayer is protecting the Ag film from interacting with the environment. The response curves of the Ag/ZnO chips were obtained by using SPR sensor. Theoretical analysis of the sensitivity of the SPR sensors with different ZnO film refractive indices is presented and studied. Both experimental and simulation results show that the Ag/ZnO films exhibit an enhanced SPR over the pure Ag film with a narrower full width at half maximum (FWHM). It shows that the top ZnO layer is effective in enhancing the surface plasmon resonance and thus its sensitivity.