Synthesis of indium–silver bimetallic nanocomposites for surface-enhanced Raman scattering

We report on the synthesis of indium–silver bimetallic nanocomposites by chemical reduction method under atmospheric condition and their activity for surface-enhanced Raman scattering (SERS). It is found that the indium–silver bimetallic nanocomposites have better SERS activity with larger enhancement factors (EF) than pure silver nanoparticles with similar size. The SERS EF can reach 10⁷ for 4-mercaptobenzoic acid and 10⁹ for crystal violet and rhodamine 6G adsorbed on the nanocomposites and the detection limits can be at least down to 10^?7 and 10^?10 M, respectively. The results demonstrate that the indium–silver bimetallic nanocomposites are promising as SERS substrate for a myriad of chemical and biological sensing applications.     

Electrical characteristics of etched ion-tracks in polyimide filled with silver nanoparticles

Silicon ions, of energy 150?MeV and fluence ～10¹²?ions/cm², were used to register latent tracks in 40?µm thick polyimide samples. Different sizes of tracks were obtained by etching the ion irradiated polyimide samples, in chemical solutions, by varying the temperature and etching period. Silver nanoparticles were diffused into the etched tracks by immersing the polyimide samples in silver solution and then irradiating with 6.5?MeV electrons at different fluences varying from 1?×?10¹⁵ to 5?×?10¹⁵?cm^?2. Results of morphological and elemental analysis, carried out by Scanning Electron Microscopy and Energy Dispersive X-ray. Analysis revealed that the conical tracks could be fully filled with silver nanoparticles at electron fluence of 5?×?10¹⁵?cm^?2. The minimum d. c. resistance of an array of tracks, filled with silver nanoparticles and measured across the polyimide film, was orders of magnitude higher as compared to that of silver wires of equivalent sizes connected in parallel. In addition, these silver nanoparticles filled tracks exhibited rectifying I–V behavior and frequency dependent a. c. resistance, characteristic of metal–polymer nano-composites. Possible mechanisms have been discussed, which can justify the asymmetric current–voltage characteristics in such nano-composites.     

Optical properties of metal nanoparticles synthesized in a polymer by ion implantation: A review

Polymer composite layers irradiated by 30-keV Ag⁺ ions with doses from 3.1×10¹⁵ to 7.5×10¹⁶ cm^?2 and an ion current of 4 µA/cm² are investigated. The composites were examined using Rutherford backscattering (RBS), transmission electron microscopy (TEM), and optical spectroscopy. As follows from electron microscopy and electron microdiffraction data, ion implantation is a promising tool for synthesizing silver nanoparticles in the surface region. The optical density spectra taken of these composites demonstrate that the silver nanoparticles exhibit unusually weak plasma resonance. The formation of silver nanoparticles in layers carbonized by ion implantation is considered. Based on the Mie theory, optical extinction spectra for silver particles in the polymer and carbon matrices are simulated and optical spectra for complex silver core-carbon sheath nanoparticles are calculated. The physics behind the experimental optical spectra of the composite is discussed.     

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.     

SERS observation of the effects of pressure and water on the absorbed state of nitrogen dioxide on a silver powder surface

The effects of pressure and water on the adsorbed state of nitrogen dioxide on silver powder produced from an aqueous solution of AgNO₃ were studied by SERS. NO₂ of 10² Pa was added to the silver powder in the sample chamber and then pressure was raised up to ∼10⁵ Pa with dry Ar, N₂ or O₂. The observed surface species are NO₃⁻ and NO₂⁻ ions under atmospheric pressure. When the total pressure decreases, NO₂⁻ is transformed into NO₃⁻ and NO⁺. This reaction is reversible with the total pressure variation of dry gases regardless of kind. Once the silver powder adsorbing nitrogen oxides is exposed to moistened gas or air of ∼10⁵ Pa, the reversible variation was interrupted, and NO₃⁻ and NO₂⁻ ions are observed on the silver surface.     

Dislocation diffusion mechanism in Pd/Ag crystals

In epitaxial Pd/Ag crystals, dislocations in the palladium film have a large influence on the effective diffusion coefficient. In silver the diffusion coefficient hardly depends on the dislocation density. With a dislocation density of 10¹⁰m⁻² the diffusion coefficient in silver is larger than in the palladium, and at 773 K it is 10⁻¹⁸ m²/s. At a dislocation density of 3·10¹² m⁻², the diffusion coefficient in the palladium becomes larger than in silver, and at 773 K it is 3·10⁻¹⁸ m²/s. It is most likely that diffusion in silver takes place via the lattice, while in palladium it occurs at mobile dislocation sites. State Technical University, Samarsk. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 116–118, August, 1996.     

Ion synthesis of silver nanoparticles in viscous-fluid epoxy resin

A method is described for the ion synthesis of silver nanoparticles in epoxy resin that is in a viscousfluid state (viscosity 30 Pa s) during irradiation. The viscous-fluid or glassy polymer is implanted by 30-keV silver ions at a current density of 4 μA/cm² in the ion beam in the dose range 2.2 × 10¹⁶–7.5 × 10¹⁶ ions/cm². The epoxy layers thus synthesized contain silver nanoparticles, which are studied by transmission electron microscopy and optical absorption spectroscopy. The use of the viscous-fluid state increases the diffusion coefficient of the implanted impurity, which stimulates the nucleation and growth of nanoparticles at low implantation doses and allows a high factor of filling of the polymer with the metal to be achieved.     

The Effect of L-Cysteine on Surface-Enhanced Raman Scattering of Malachite Green in Silver Colloids

ABSTRACT

Colloidal silver nanoparticles were prepared by a simple chemical reduction method. The effect of L-cysteine on the surface-enhanced Raman scattering activity of colloidal silver nanoparticles was investigated by using malachite green as a probe molecule. It was found that the surface-enhanced Raman scattering activity of colloidal silver nanoparticles was improved tremendously with the help of L-cysteine. The possible reasons for this enhancement effect were given. Specifically, in silver colloidal solution, no surface-enhanced Raman scattering spectrum of malachite green was observed at a relatively low concentration (≤2.5 × 10^?5 mol/L). However, well-resolved and high-quality surface-enhanced Raman scattering spectra of malachite green were successfully obtained after the addition of L-cysteine to silver colloids, and the minimum detection limit for malachite green was down to 10^?8 mol/L.     

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.     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.     

A field emission study of silver on rhenium

Field emission measurements of the change in average work function ?f of rhenium with adsorbed silver indicate that a rhenium-silver dipole forms with silver positive, of moment μ₀=5.2±1.5 ×10^?30 C m and polarizability $\text{α=29±12}\text{A}\text{?}{}^3$. Measurement of the rate of thermal desorption yields a mean binding energy of 2.31 ± 0.04 eV for sub-monolayer silver and 2.69±0.04 eV for a 2.5 monolayer deposit. Changes in work function induced by adsorption of silver on low-index rhenium plane surfaces are characterised by the formation of well-defined states and in this, silver resembles gold. These states are thought to result from a relatively large difference between the binding energy of adatoms on the low-index planes and on the surrounding surfaces, and this differnce is maintained when the surfaces are covered with silver. At the lowest coverage, silver is believed to be absent from all four observed planes and the measured rise in work function is thought to be apparent and to result from a decrease in field strength on the plane due to extension of the plane area by surrounding adsorbed silver. The structures adopted by silver overlayers are not known, but it is argued that on (101?0) and (101?1?) the final state at high coverage has the Ag(111) surface structure. On (112?0) and (112?2?) the silver layer at high coverage is thought to have either Ag(110) or Ag(100) surface structure. The structures of intermediate states found on all four low-index planes remain unkown. Field emission spectroscopy shows that emission from clean (101?0) is free-electron like and confirms earlier observations that emission from (202?1) is not. Spectroscopy also reveals a feature in the spectrum from silver on (101?0) which may be identified with a known surface state on Ag(111), thus providing some support for the assignment of Ag(111) to the surface structure of thick silver layers (> 3 monolayers) on (101?0).     

Fabrication of silver stabilization layer of coated conductor using organic silver complexes

Silver stabilizing layer of coated conductor has been prepared by dip coating method using organic silver complexes containing 10 wt.% silver as a starting material. Coated silver complex layer was dried in situ with hot air and converted to crystalline silver by post heat treatment in flowing oxygen atmosphere. A dense continuous silver layer with good surface coverage and proper thickness of 230 nm is obtained by multiple dip coatings and heat treatments. The film heat treated at 500 °C showed good mechanical adhesion and crystallographic property. The interface resistivity between superconducting YBCO layer and silver layer prepared by dip coating was measured as 0.67 × 10⁻¹³ Ω m².     

Structure and conformation of Arg8 vasopressin modified analogs

Fourier‐transform Raman and infrared spectra were acquired for four arginine vasopressin (AVP) analogs containing L ‐diphenylalanine (Dpa): [Dpa²]AVP, [Cpa¹,Dpa²]AVP, [Dpa³]AVP, and [Cpa¹,Dpa³]AVP (where Cpa denotes 1‐mercaptocyclohexaneacetic acid). We compared and analyzed these spectra. In addition, the Raman spectra were compared to the corresponding surface‐enhanced Raman scattering spectra recorded in an aqueous silver colloidal dispersion. Silver colloidal dispersions prepared by the simple borohydride reduction of silver nitrate were used as substrates. The geometry of these molecules etched on the silver surface was deduced from the observed changes in the intensity enhancement, breadth, and shift in wavenumber of the Raman bands in the spectra of the bound versus free species. Based on the obtained data, adsorption mechanisms were proposed for each case, and the suggested adsorbate structures were compared. All the molecules were thought to adsorb onto a silver surface via a phenyl ring, free electron pairs on the sulfur atom, and CO and  CONH‐bonds. However, the orientation of these fragments on the colloidal silver surface and the strength of the interactions with this surface are different. For [Dpa³]AVP and [Cpa¹,Dpa³]AVP, a strong interaction among the—CCN‐peptide fragment and the colloidal silver surface occurs. Copyright © 2011 John Wiley & Sons, Ltd.     

Enhancement of Raman scattering of light by ultramarine microcrystals in presence of silver nanoparticles

Approximately 10²‐fold enhancement of Raman scattering by ultramarine microcrystals is reported by means of interaction with silver nanoparticles in films and powders. Theoretical modeling predicts the maximal 10¹⁰‐fold enhancement in close vicinity of a silver spherical nanoparticle (0.24 nm) with rapid decay of enhancement factor to 1 in the range of approximately 50 nm. Experimental enhancement factor is treated as overall effect within the small portion of every microcrystal in the close vicinity of silver nanoparticle(s). The results are considered as an important extension of traditional surface enhanced molecular Raman spectroscopy towards bigger inorganic probes. Copyright © 2012 John Wiley & Sons, Ltd.     

pH‐dependent surface‐enhanced Raman scattering observation of sulfanilamide on the silver surface

Monolayers of sulfanilamide on metallic surface can serve as an ideal model for understanding the interaction mechanism between the metal and the sulfanilamide molecule. In the present paper, the surface‐enhanced Raman scattering (SERS) technique was employed to obtain the SERS spectra of sulfanilamide monolayers formed on the silver surface under different pH values. Assignments of the spectra were carried out with the aid of density functional theory (DFT) calculations (BLYP/6‐311G). It can be found that the adsorption function of sulfanilamide on the silver surface was influenced by the pH value. The fully protonated sulfanilamide molecule adsorbed on the silver surface through N¹³H₂ group and the benzene ring anchored in a relatively perpendicular manner leading to N⁷H₂ and S¹⁰O₂ groups near the surface, while the completely deprotonated sulfanilamide molecule attached on the silver surface via N⁷H₂ and the benzene ring was perpendicular to, and the N¹³H₂ and S¹⁰O₂ groups were far from the silver surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Slow surface plasmons in amplifying media and ultrahigh-resolution nonlinear optical microscopy

The technique of ultrahigh-resolution nonlinear fluorescent microscopy based on standing surface plasmons is proposed. On the wavelength of a surface plasmon of 20 nm the expected lateral resolution should be 1–2 nm. Slow surface plasmons with the required mean free path of ～1 m are possible in the planar amplifying medium-metal-dielectric structures due to the compensation of loss in the metal by the amplification in the active medium. In the optical and near infrared range the undamped surface plasmons with the wavelength of 20–50 nm in thin silver films can be obtained at the material gain of active medium of (1–2) × 10⁴ cm ^?1. Possibilities of obtaining this gain in the plasmon structures remain to be seen.     

Adsorbed states of substituted α‐aminophosphinic acids on a silver electrode surface: comparison with a colloidal silver substrate

We investigated the interfacial structures of various aromatic (each compound contains one or two phenyls) di‐α‐amino ( L¹ – L³ ) and α‐amino‐α‐hydroxyphosphinic ( L⁴ – L⁶ ) acids immobilized onto an electrochemically roughened silver electrode surface in an aqueous solution using surface‐enhanced Raman scattering (SERS). These structures were compared to those on a colloidal silver surface to determine the relationship between adsorption strength and geometry. The presence of an enhanced ν_19a ring band in the SERS spectra of L⁶ , L² , and L³ on the electrode indicated that the benzene rings of those molecules interact with the electrode surface through localized CC bond(s). We observed significant band broadening of the benzene ring modes for all α‐hydroxyphosphinic acids on both substrates, except for L¹ deposited onto the electrode surface. This suggests the possibility of direct interaction between the ring and Ag, although the benzene ring–surface π overlap is weaker for the colloidal silver than for the Ag electrode. The downward shift in wavenumber and alternations in the enhancement of a ν₁₂ ring band indicate a general increase of tilt angle on both silver substrates in the order L³ < L⁴ < L⁵ < L⁶ . The altered enhancement of the bands due to the vibrations of the  NH₂ and O PO fragments, a finding observed on both silver substrates, strongly suggests that the groups interact with different strength and geometry with these substrates. Copyright © 2009 John Wiley & Sons, Ltd.     

Fabrication of a range of SERS substrates on nanostructured multicore optical fibres

An effective method for producing arrays of nanoscale triangles, rods and wells on the distal end of a silica optical fibre is presented. The structures are produced by applying a wet‐etch procedure to drawn‐down imaging fibres. Structural variation is achieved by altering the final diameter of the drawn fibre. Feature sizes of less than 100 nm can be readily achieved in this way. When coated with silver, surface‐enhanced Raman scattering enhancement factors of over 10⁶ can be achieved, depending on the size and shape of the structures present. Copyright © 2006 John Wiley & Sons, Ltd.     

Nanostructured substrate with nanoparticles fabricated by femtosecond laser for surface-enhanced Raman scattering

A simple and fast method to fabricate nanostructured substrates with silver nanoparticles over a large area for surface-enhanced Raman scattering (SERS) is reported. The method involves two steps: (1) dip the substrate into a silver nitrate solution for a few minutes, remove the substrate from the solution, and then air dry and (2) process the silver nitrate coated substrate by femtosecond (fs) laser pulses in air. The second step can create silver nanoparticles distributed on the nanostructured surface of the substrate by the photoreduction of fs multiphoton effects. This study demonstrates that an enhancement factor (EF) greater than 5×10⁵, measured by 10⁻⁶ M Rhodamine 6G solution, can be achieved. The proposed technique can be used to integrate the SERS capability into a microchip for biomedical and chemical analysis.     

EELS plasmon studies of silver/carbon core/shell nanocables prepared by simple arc discharge

A method for the fabrication of large quantities of high quality silver nanocables encapsulated in carbon nanotubes (Ag@C) using a hydrogen arc is presented. A growth mechanism based on the generation of poly-aromatic hydrocarbons by the hydrogen arc is proposed. The size-dependent electronic structures of the resultant materials are investigated using electron energy loss spectroscopy (EELS). The surface plasmon and bulk-excitation character observed by EELS are discussed. As the diameter of Ag@C nanocable decreases, the surface and bulk plasmons of the silver core shift to lower energy and the peaks broaden. Measurements of electrical conductivity exhibits a liner current–voltage character with a conductivity of 0.5×10⁴ S/cm for the nanocable structure. PACS 81.05.Tp; 81.07.-b