Time-dependent micro-Raman scattering studies of polyvinyl alcohol and silver nitrate thin films

In-situ monitoring of silver nanoparticle formation was studied in thin films of polyvinyl alcohol and silver nitrate. We proposed the observation of surface-enhanced Raman spectroscopy (SERS) as a novel and simple technique to record the growth of silver nanoparticles in polyvinyl alcohol thin films. Observed enhancement in the Raman bands of polyvinyl alcohol is explained through the localized surface plasmon resonance of silver nanoparticles. Influence of temperature generated by silver nanoparticles on the formation of nanoparticles is also discussed.     

Deposition and wettability of silver nanostructures on Si(1 0 0) substrate based on galvanic displacement reactions

A new route for silver electroless deposition on Si(1 0 0) substrate is developed based on the galvanic displacement process. The basic electroless bath contains NaF and AgNO₃ with different concentrations. The morphologies of electrolessly deposited silver nanostructures, including silver nanowires and nanoparticles, are strongly dependent on the electrolyte composition. Adding an excess dosage of polyvinylpyrrolidone into the basic electrolyte yields final silver films of porous structures composed by multitudinous Ag nanoparticles. The porous silver films possess the surface hydrophobic property after the modification with n-dodecanethiol. Unidirectional wetting and spreading of a water droplet are also demonstrated on the patterned porous Ag films.     

Ageing of plasma-mediated coatings with embedded silver nanoparticles on stainless steel: An XPS and ToF-SIMS investigation

Nanocomposite thin films (∼170 nm), composed of silver nanoparticles enclosed in an organosilicon matrix, were deposited onto stainless steel, with the aim of preventing biofilm formation. The film deposition was carried out under cold plasma conditions, combining radiofrequency (RF) glow discharge fed with argon and hexamethyldisiloxane and simultaneous silver sputtering. XPS and ToF-SIMS were used to characterize Ag-organosilicon films in native form and after ageing in saline solution (NaCl 0.15 M), in order to further correlate their lifetime with their anti-fouling properties. Two coatings with significantly different silver contents (7.5% and 20.3%) were tested. Surface analysis confirmed the presence of metallic silver in the pristine coating and revealed significant modifications after immersion in the saline solution. Two different ageing mechanisms were observed, depending on the initial silver concentration in the film. For the sample exhibiting the low silver content (7.5%), the metal amount decreased at the surface in contact with the solution, due to the release of silver from the coating. As a result, after a 2-day exposure, silver nanoparticles located at the extreme surface were entirely released, whereas silver is still present in the inner part of the film. The coating thickness was not modified during ageing. In contrast, for the high silver content film (20.3%), the thickness decreased with immersion time, due to significant silver release and matrix erosion, assigned to a percolation-like effect. However, after 18 days of immersion, the delamination process stopped and a thin strongly bounded layer remained on the stainless steel surface.     

SERS characterization of metallic silver nanoparticle self‐assembly within thin films

Clusters of silver nanoparticles are generated by the thermally initiated reduction of silver carboxylates (long‐chain fatty acids) in the thin polymer films. The size, shape, and aggregation of these nanoparticles are affected by the reduction reaction in the presence of capping agents. In order to understand the mechanism(s) controlling the silver structure formation, it is essential to understand the surface coordination chemistry occurring during this process. We now report the first application of surface‐enhanced Raman spectroscopy (SERS) to directly characterize adsorbates on the surfaces of silver nanoparticles within a thin film imaging construction containing multiple components. In addition, SERS investigation of model silver substrates was used to confirm the identify of specific adsorbates of silver complexes. This is a powerful tool for revealing the chemistry involved with the control of silver nanoparticle aggregation during thermally induced metallic silver formation within thin films. Both the catechol‐reducing agent and the phthalazinone (PAZ) particle aggregation agent are observed on the metallic silver surface at the initial particle formation and during its crystal growth. However, careful attention to excitation wavelength is required in order to observe all the surface species. PAZ appears to be more effective at stabilizing individual silver particles than other aggregation agents investigated. An understanding of the roles of the aggregation/reducing agents in the growth and aggregation of silver nanoparticles is important for preparing different types of silver particles for specific applications including silver‐based thermal imaging systems. Copyright © 2008 John Wiley & Sons, Ltd.     

Magnetization reversal studies of continuous and patterned exchange biased NiFe/FeMn thin films

In this article we present a detailed investigation of the structural and magnetic properties of exchange biased NiFe (ferromagnet)/FeMn (antiferromagnet) thin films. The influence of the shape anisotropy on exchange bias and the magnetization reversal mechanism in a sample with patterned lines is compared with a continuous two-dimensional reference sample. Polarized neutron reflectivity (PNR) is employed to study the magnetization reversal by analyzing the spin-flip and non-spin-flip reflectivities. PNR measurements show that the magnetization reversal in the reference two-dimensional film and patterned lines is by domain wall motion rather than coherent rotation of magnetization.     

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     

银表面光学二次谐波参数的研究

本文测量了几种玻璃-银膜界面反射二次谐波随入射光偏振角的变化,测量了超高真空中多晶银基底上冷凝银膜表面退火前后的反射二次谐波,以及超高真空中纯度为99.99%多晶银表面的反射二次谐波,计算了垂直和平行表面谐波电流参数a、b,得到对棱镜-银界面b=-0.97;α=2.1,多晶银表面α=-9,冷凝银膜退火前后α分别为7和-5.结果表明.α对表面状况极为敏感.     

Formation of sub-surface silver nanoparticles in silver-doped sodium–lead–germanate glass

The formation of silver nanoparticles in 60GeO₂–20PbO–20Na₂O bulk glass doped with 0.15 wt% of Ag has been studied by optical methods in the near ultraviolet-to-near infrared and mid-infrared ranges. A clear optical absorption band, which grows when increasing the annealing temperature, is observed around 460 nm, as a consequence of the surface plasmon resonance in the Ag nanoparticles. From the simultaneous analysis of optical transmittance and spectroscopic ellipsometry spectra in the near ultraviolet-to-near infrared range, it is demonstrated that the nanoparticles are surprisingly formed only in a thin layer (some tens of nm thick) underneath the sample surfaces. The potential of such a simultaneous optical analysis for determining the localization of the nanoparticles in glasses of any nature is underlined. Based on the results of a complementary mid-infrared spectroscopy characterization, the processes involved in silver migration to the surfaces and further aggregation to form nanoparticles are discussed.     

Second-harmonic generation from ellipsoidal silver nanoparticles embedded in silica glass

Second-harmonic generation of uniformly oriented, ellipsoidal silver nanoparticles in a glass matrix was observed and investigated as a function of incidence angle, light polarization, and spatial arrangement of the particles. The results can be explained by the symmetry of the spatial nanoparticle arrangement and by resonance enhancement that is due to the localized surface plasmons of the particles. Second-harmonic enhancement is observed only in sufficiently thin layers (deltakl < pi); on a sample with two separate layers, strong modulation owing to quasi-phase matching is obtained.     

Significant modifications in the electrical properties of poly(methyl methacrylate) thin films upon dispersion of silver nanoparticles

Electrical conductivity of thin solid films of PMMA with dispersed silver nanoparticles, synthesized by a novel method, was studied in dark conditions by changing the applied voltage and temperature and also under photoexcitation (by a mercury lamp, 125 W) at room temperature. Anomalous hysteresis in current-temperature characteristics during heating and cooling cycles was observed. The hysteresis-like behaviour was explained on the basis of the movements of molecules associated with different parts of a PMMA matrix and diffusion of silver nanoparticles in the PMMA matrix. Dark current in the PMMA films with dispersed silver nanoparticles has been observed to be higher than the corresponding current in the PMMA films without silver nanoparticles due to the creation of conduction paths by the silver nanoparticles/nanoclusters. The photoresponse in the thin solid films of PMMA with dispersed silver nanoparticles was the reverse of that observed in thin solid films of PMMA without silver nanoparticles. A decrease in photocurrent under illumination of light was observed due to the destruction of conduction paths by the illumination of light.     

Cerium oxide nanoparticles protect primary mouse bone marrow stromal cells from apoptosis induced by oxidative stress

The sintering of a silver (Ag) nanoparticle film by laser beam irradiation was studied using a CW DPSS laser. The laser sintering of the Ag nanoparticle thin film gave a transparent conductive film with a thickness of ca. 10 nm, whereas a thin film sintered by conventional heat treatment using an electronic furnace was an insulator because of the formation of isolated silver grains during the slow heating process. The laser sintering of the Ag nanoparticle thin film gave a unique conductive network structure due to the rapid heating and quenching process caused by laser beam scanning. The influences of the laser sintering conditions such as laser scan speed on the conductivity and the transparency were studied. With the increase of scan speed from 0.50 to 5.00 mm/s, the surface resistivity remarkably decreased from 4.45 × 10⁸ to 6.30 Ω/sq. The addition of copper (Cu) nanoparticles to silver thin film was also studied to improve the homogeneity of the film and the conductivity due to the interaction between the oxidized surface of Cu nanoparticle and a glass substrate. By adding 5 wt% Cu nanoparticles to the Ag thin film, the surface resistivity improved to 2.40 Ω/sq.     

掺杂Ag纳米粒子对偶氮聚合物光致异构效应的影响

报道了通过宏观测量偶氮聚合物光致异构效应,及其引起的光学各向异性变化,讨论了一种影响偶氮聚合物顺反异构效应的有效途径。在偶氮高分子聚合物中,添加了不同浓度的Ag纳米粒子,采用了波长为442nm的He-Cd偏振激光为激发光源,当Ag纳米粒子掺杂质量浓度为0.12μg/ml的时候,激发了薄膜样品中Ag纳米粒子的等离子体共振效应,增强了粒子周围纳米尺度的电磁场强度,相当程度上提高了偶氮聚合物光致异构的转换效率;另外,研究了不同的取代基同纳米Ag粒子的相互作用对光致异构效应的影响,探讨了一种能够有效地控制光致异构效应的方法。     

Excimer laser-assisted annealing of silicate glass with ion-synthesized silver nanoparticles

The effect of KrF excimer laser radiation on a composite layer consisting of sodium-potassium silicate glass with silver nanoparticles is studied as a function of the number of laser nanosecond pulses. The silver nanoparticles are synthesized by ion implantation. The measured optical absorption of the composite layer demonstrates that the silver nanoparticle size decreases monotonically as the number of laser pulses increases. Rutherford backscattering shows that laser annealing is accompanied by silver diffusion into the bulk of the glass and partial metal evaporation from the sample surface. The detected decrease in the silver nanoparticle size is discussed in terms of simultaneous melting of silver nanoparticles and the glass matrix due to the absorption of laser radiation.     

银纳米粒子/碳纳米管阵列SERS基底增强因子分析和实验

为了直观、准确地定量分析表面拉曼增强散射基底结构的拉曼增强,利用磁控溅射和高温退火的方法制备了银纳米粒子修饰垂直排列的碳纳米管阵列三维复合结构样品;实验采用罗丹明6G(R6G)溶剂作为探针分子,结合共聚焦显微拉曼系统,开展了表面增强拉曼增强因子(EF)分析计算的相关实验。SEM结果表明：在有序碳纳米管阵列的表面和外壁均匀地负载了大量银纳米粒子。对退火温度为450 ℃,退火时间为30 min的样品进行了EF计算,得到其增强因子约为2.2×103,并分析了EF值低的原因主要是：在碳纳米管上溅射的银膜膜厚不均匀,导致退火后银颗粒分布不均,使得样品粗糙度值偏大,EF值较低;实验中所用的激励光源并非银纳米颗粒的优化光源。     

Mechano-chemical AFM nanolithography of metallic thin films: A statistical analysis

A mechano-chemical atomic force microscope (AFM) nanolithography on a metallic thin film (50 nm in thickness) covered by a spin-coated soft polymeric mask layer (50–60 nm in thickness) has been introduced. The surface stochastic properties of initial grooves mechanically patterned on the mask layer (grooves before chemical wet-etching) and the lithographed patterns on the metallic thin film (the grooves after chemical wet-etching) have been investigated and compared by using the structure factor, power spectral density, and AFM tip deconvolution analyses. The effective shape of cross section of the before and after etching grooves have been determined by using the tip deconvolution surface analysis. The wet-etching process improved the shape of the grooves and also smoothed the surface within them. We have indicated that relaxation of the surface tension of the deposited mask layer after the AFM scribing is independent from surface density of the grooves and also their length scale. Based on the statistical analysis, it was found that increase of the width of the grooves after the wet-etching and also relaxation of surface tension of the mask layer resulted in a down limit in the size of the metallic nanowires made by the combined nanolithography method. An extrapolation of the analyzed statistical data has indicated that, in this method, the minimum obtainable width and length of the metallic nanowires are about 55 nm and 2 μm, respectively.     

Bactericidal effects of Ag nanoparticles immobilized on surface of SiO2 thin film with high concentration

Bactericidal activity of high concentration Ag nanoparticles immobilized on surface of an aqueous sol–gel silica thin film was investigated against Escherichia coli and Staphylococcus aureus bacteria. Size of the surface nanoparticles was estimated in the range of 35–80 nm by using atomic force microscopy. Due to accumulation of the silver nanoparticles at near the surface (at depth of 6 nm and about 40 times greater than the silver concentration in the sol), the synthesized Ag–SiO₂ thin film (with area of 10 mm²) presented strong antibacterial activities against E. coli and S. aureus bacteria with relative rate of reduction of the viable bacteria of 1.05 and 0.73 h⁻¹ for initial concentration of about 10⁵ cfu/ml, respectively. In addition, the dominant mechanism of silver release in long times was determined based on water diffusion in surface pores of the silica film, unlike the usual diffusion of water on the surface of silver-based bulk materials. Therefore, the Ag nanoparticles embedded near the surface of the SiO₂ thin film can be utilized in various antibacterial applications with a strong and long life activity.     

Asymmetric distribution of surface second harmonic generation for thin silver films deposited on Si(111)

The asymmetric distributions of surface optical second harmonic generation (SHG) through azimuthally angular scans of (111) silicon wafers on which thin silver films were deposited, have been detected with different polarizations of output beams. On account of the inversion symmetry of silicon crystals, the SHG for the Ag/Si system is mainly contributed by the silver film and the silicon surface. In this work, we found that the interface strain implies an asymmetric intensity variation of SHG with respect to the surface azimuthal angles as an ultra thin Ag film is deposited on silicon wafers. This asymmetric behavior is prominent as the deposited silver layer is heated so that the continuous film aggregates to become granular nanoparticles. Similar changes of the surface asymmetric SHG are observed for a bare Si wafer imposed upon by an external force.     

Migration characterization of Ga and In adatoms on dielectric surface in selective MOVPE

Migration characterizations of Ga and In adatoms on the dielectric surface in selective metal organic vapor phase epitaxy(MOVPE) were investigated. In the typical MOVPE environment, the selectivity of growth is preserved for Ga N,and the growth rate of Ga N micro-pyramids is sensitive to the period of the patterned SiO2 mask. A surface migration induced model was adopted to figure out the effective migration length of Ga adatoms on the dielectric surface. Different from the growth of Ga N, the selective area growth of In Ga N on the patterned template would induce the deposition of In Ga N polycrystalline particles on the patterned SiO2 mask with a long period. It was demonstrated with a scanning electron microscope and energy dispersive spectroscopy that the In adatoms exhibit a shorter migration length on the dielectric surface.     

Electrical properties, structure, and surface morphology of poly(p-xylylene)–silver nanocomposites synthesized by low-temperature vapor deposition polymerization

The crystalline structure, surface morphology, electrical, and optical properties of thin films of nanocomposites consisting of silver nanoparticles embedded in poly(p-xylylene) matrix prepared by low-temperature vapor deposition polymerization were studied. Depending on the filler content, the average size of silver nanoparticles varied from 2 to 5 nm for nanocomposites with 2 and 12 vol.% of silver, correspondingly. The optical adsorption in the visible region due to surface plasmon resonance also exhibited a clear correlation from silver content, revealing a red shift of the adsorption peak with the increase of the metal concentration. The temperature dependences of the dc resistance of pure p-xylylene condensate and p-xylylene–silver cocondensates during polymerization as well as temperature dependences of the formed poly(p-xylylene)–silver nanocomposites were examined. The observed variation of the temperature dependences of electrical resistance as a function of silver concentration are attributed to different conduction mechanisms and correlated with the structure of the composites. The wide-angle X-ray scattering and AFM measurements consistently show a strong effect of silver content on the nanocomposite structure. The evolution of the size of silver nanoparticles by thermal annealing was demonstrated.     

ZnO nanowall networks grown on DiMPLA pre‐patterned thin gold films

ZnO nanowall networks grown by a high pressure pulsed laser deposition (PLD) technique on a pre‐patterned thin gold film are presented. The thin gold film on a c ‐plane oriented sapphire substrate was structured with diffraction mask projection laser ablation (DiMPLA). It is shown that only areas processed with the laser patterning technique reveal homogeneous growth of ZnO nanowall networks. Photoluminescence measurements prove the higher material quality of the pre‐patterned regions compared to the untreated ones. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)