A new molecular silver precursor for the preparation of thin conductive silver films

The synthesis and characterization of a new molecular silver precursor is reported. The presented complex [Ag(DioxoNic)₂]NO₃ (DioxoNic=(2,2-Dimethyl-1,3-dioxolan-4-yl)methyl nicotinate) can be obtained by the reaction of silver(I) nitrate and (2,2-Dimethyl-1,3-dioxolan-4-yl)methyl nicotinate in ethanol. The product crystallizes in the monoclinic space group P21/c (No. 14). Concentrated ethanolic solutions allow the fabrication of thin films via dip coating. Using UV-irradiation and subsequent moderate temperature treatment compact films of elemental silver can be obtained. The resulting silver films show excellent electrical properties with sheet resistances down to 0.7 Ω/sq at a film thickness of 25 nm corresponding to a specific electrical resistance of 1.75×10⁻⁸ Ωm very close to the value of bulk silver. For the potential application in optoelectronic devices, the complex was tested as an ink in a soft printing process for the preparation of patterned silver films.     

Preparation of triethylamine stabilized silver nanoparticles for low-temperature sintering

In this article, silver nanoparticles were synthesized by chemical reduction from silver nitrate using triethylamine as the protecting and reducing agents simultaneously. The average size of the silver nanoparticles was about 2.10–4.65 nm, which allowed low-temperature sintering of the metal. X-ray diffraction (XRD), thermogravimetric analysis (TGA), and energy dispersive spectrometric (EDS) analysis results indicate that silver nitrate has been converted to silver nanoparticles completely. Using a 20 wt% silver nanoparticles suspension with thermal treatment at 150 °C, silver films with a resistivity of 8.09 × 10⁻⁵ Ω cm have been produced, which is close to the resistivity of bulk silver.     

Morphology and size dependence of silver microstructures in fatty salts-assisted multiphoton photoreduction microfabrication

The morphology and size dependence of silver microstructures in a novel microfabrication process, fatty salts-assisted multiphoton photoreduction (MPR), were investigated by using the fatty salts with different carbon chain lengths (C _n : n=4,5,7,9) under varied powers and irradiation times of a femtosecond near-infrared laser with the wavelength of 800 nm. Not only the feature size of the silver structures was reduced but also the surface smoothness was improved by increasing the chain length of the fatty salts. The highest resolution of a silver line was obtained to be 285 nm, which exceeded the diffraction limit. The fatty salts-assisted MPR microfabrication approach would provide an efficient protocol for fabricating metallic micro/nanostructures with fine morphology and size and could play an important role in the fabrication of the metallic micro/nanostructures for applications in photonics and electronics as well as in sensors.     

Synthesis of dendritic silver nanostructures by means of ultrasonic irradiation

In this paper, a simple and effective route for the synthesis of silver dendritic nanostructures by means of ultrasonic irradiation has been developed. Well-defined silver dendritic nanostructures were obtained by sonicating the aqueous solution of 0.04 mol/L silver nitrate with 4.0 mol/L isopropanol as reducing agent and 0.01 mol/L PEG400 as disperser for 2 h. The effects of the irradiation time, the concentration of Ag⁺ and the molar ratio of PEG to AgNO₃ on the morphology of silver nanostructures were discussed. The structures of the obtained samples were characterized by transmission electron microscopy (TEM), selected area electron diffraction (SAED) and X-ray powder diffraction (XRD), and the chemical composition of the dendrites was examined by energy-dispersive X-ray spectrum (EDS).     

Growth process of nanostructured silver films pulsed laser ablated in high-pressure inert gas

The growth process of silver thin films deposited by pulsed laser ablation in a controlled inert gas atmosphere was investigated. A pure silver target was ablated in Ar atmosphere, at pressures ranging between 10 and 100 Pa, higher than usually adopted for thin film deposition, at different numbers of laser shots. All of the other experimental conditions such as the laser (KrF, wavelength 248 nm), the fluence of 2.0 J cm⁻², the target to substrate distance of 35 mm, and the temperature (295 K) of the substrates were kept fixed. The morphological properties of the films were investigated by transmission and scanning electron microscopies (TEM, SEM). Film formation results from coalescence on the substrate of near-spherical silver clusters landing as isolated particles with size in the few nanometers range. From a visual inspection of TEM pictures of the films deposited under different conditions, well-separated stages of film growth are identified.     

Fabrication of micro/nano crystalline ITO structures by femtosecond laser pulses

A method is proposed for the fabrication of micro/nano crystalline indium tin oxide (c-ITO) structures using a Ti:Sapphire laser with a repetition rate of 1 kHz and a wavelength of 800 nm. In the proposed approach, an amorphous ITO (a-ITO) thin film is transformed into a c-ITO micro/nano structure over a predetermined area via laser beam irradiation, and the residual a-ITO thin film is then removed using an etchant solution. The fabricated c-ITO structures are observed using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (TEM). The observation results show that the use of a low repetition rate laser induces a high thermal cycling effect within the ITO film and therefore prompts the formation of micro-cracks in the c-ITO structure. In addition, it is shown that as the laser power approaches the ablation threshold of the a-ITO thin film, nanogratings and disordered nanostructures are formed along the center lines of the c-ITO patterns formed using linearly polarized and circularly polarized laser beam irradiation, respectively. The nanogratings are found to have a period of approximately 200 nm (i.e. one-quarter of the irradiation wavelength), while the nanostructures have an average diameter of approximately 100–160 nm.     

Luminescence properties of femtosecond-laser-activated silver oxide nanoparticles embedded in a biopolymer matrix

Strong visible luminescence is observed from silver clusters generated by femtosecond-laser-induced reduction of silver oxide nanoparticles embedded in a polymeric gelatin matrix. Light emission from the femtosecond-laser-activated matrix areas considerably exceeds the luminescence intensity of similarly activated bare silver oxide nanoparticle films. Optical spectroscopy of the activated polymer films supports the assignment of the emissive properties to the formation of small silver clusters under focused femtosecond-laser irradiation. The size of the photogenerated clusters is found to sensitively depend on the laser exposure time, eventually leading to the formation of areas of metallic silver in the biopolymer matrix. In this case, luminescence can still be observed in the periphery of the metallic silver structures, emphasizing the importance of the organic matrix for the stabilization of the luminescent nanocluster structures at the metal–matrix interface. PACS 78.66.Qn; 78.20.-e; 78.40.-q; 78.67.Bf; 78.68.+m     

CO2 laser-induced crystallization of sol–gel-derived indium tin oxide films

Indium tin oxide (ITO) thin films prepared by the sol–gel method have been deposited by the dip-coating process on silica substrates. CO₂ laser is used for annealing treatments. The electrical resistivity of sol–gel-derived ITO thin films decreased following crystallization after exposure to CO₂ laser beam. The topological and electrical properties of the irradiated surfaces have been demonstrated to be strongly related to the coating solution and to the laser processing parameters. Optimal results have been obtained for 5 dip-coating layers film from 0.4 mol/l solution irradiated by 0.6 W/m² laser power density. In this case, homogeneous and optically transparent traces were obtained with a measured sheet resistance of 1.46×10² Ω/□.     

Photodissociation effects on pulsed laser deposited silver oxide thin films: surface‐enhanced resonance Raman scattering

Temporal Raman scattering measurements with 488, 532 and 632 nm excitation wavelengths and normal Raman studies by varying the power (from 30 W/cm² to 2 MW/cm²) at 488 nm were performed on silver oxide thin films prepared by pulsed‐laser deposition. Initially, silver oxide Raman spectra were observed with all three excitation wavelengths. With further increase in time and power, silver oxide photodissociated into silver nanostructures. High‐intensity spectral lines were observed at 1336 ± 25 and 1596 ± 10 cm⁻¹ with 488 nm excitation. No spectral features were observed with 633 nm excitation. Surface‐enhanced resonance Raman scattering theory is used to explain the complex behavior in the intensity of the 1336/1596 cm⁻¹ lines with varying power of 488 nm excitation. Copyright © 2011 John Wiley & Sons, Ltd.     

UV-induced synthesis,characterization and formation mechanism of silver nanoparticles in alkalic carboxymethylated chitosan solution

The silver nanoparticles (AgNPs) were synthesized in an alkalic aqueous solution of silver nitrate (AgNO₃)/carboxymethylated chitosan (CMCTS) with ultraviolet (UV) light irradiation. CMCTS, a water-soluble and biocompatible chitosan derivative, served simultaneously as a reducing agent for silver cation and a stabilizing agent for AgNPs in this method. UV–vis spectra and transmission electron microscopy (TEM) images analyses showed that the pH of AgNO₃/CMCTS aqueous solutions, the concentrations of AgNO₃ and CMCTS can affect on the size, amount of synthesized AgNPs. Further by polarized optical microscopy it was found that the CMCTS with a high molecular weight leads to a branch-like AgNPs/CMCTS composite morphology. The diameter range of the AgNPs was 2–8 nm and they can be dispersed stably in the alkalic CMCTS solution for more than 6 months. XRD pattern indicated that the AgNPs has cubic crystal structure. The spectra of laser photolysis of AgNO₃/CMCTS aqueous solutions identified the early reduction processes of silver cations (Ag⁺) by hydrated electron formed by photoionization of CMCTS. The rate constant of corresponding reduction reaction was 5.0 × 10⁹ M⁻¹ s⁻¹.     

Laser forward transfer of silver electrodes for organic thin-film transistors

Organic thin-film transistors (OTFTs) with top- and bottom-contact configurations were fabricated using silver nano-inks printed by laser forward transfer for the gate and source/drain electrodes with pentacene and poly-4-vinylphenol as the organic semiconductor and dielectric layers, respectively. The volume of the laser-printed Ag pixels was typically in the subpicoliter (0.2–0.4 pl) range. The top-contact OTFTs resulted in lower contact resistance compared to those obtained from the bottom-contact OTFTs, and showed improved overall device performance. The top-contact OTFTs exhibited field-effect mobilities of ∼0.16 cm² V⁻¹ s⁻¹ and on/off current ratios of ∼10⁵.     

Formation of silver nanoparticles with dielectric shell on the silver-containing glass during laser evaporation and ablation

We demonstrate a new method of silver nanoparticles formation on a silver-containing glass surface due to its irradiation by a pulsed CO₂ and YAG:Nd lasers. The particles are formed as a result of reduction of silver ions from the glass at the edges of a laser torch emerging during evaporation and ablation. The settled particles are then fixed on sample surface by a shell of glass dielectric components. The method allows creating plasmonic nanostructures on the glass surface for sensing applications.     

玻璃基底上不规则银纳米结构的生长及其光学性质的研究

以经过硅烷化后玻璃片为基底，之后吸附金纳米种子，采用柠檬酸钠为还原剂，在荧光灯照射条件下还原硝酸银，制备出基底表面具有银纳米粒子聚集结构的材料。采用透射电镜、扫描电镜和紫外可见分光光度计对产物的形貌和性质进行了表征，并考察银纳米粒子的形貌对其薄膜基底SERS活性的影响。结果表明：随着光照时间增加至16 h，金种子长大为平均粒径110 nm的不规则状多晶银纳米粒子，且出现双层粒子堆积。基底上纳米粒子的吸收光谱上出现了由银粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰：随着光照时间的变化，耦合峰在600～813 nm波段内移动。光照时间为12 h后得到的SERS活性基底具有最强的SERS信号。     

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.     

玻璃基底上不规则银纳米结构的生长及其光学性质的研究

以经过硅烷化后玻璃片为基底,之后吸附金纳米种子,采用柠檬酸钠为还原剂,在荧光灯照射条件下还原硝酸银,制备出基底表面具有银纳米粒子聚集结构的材料。采用透射电镜、扫描电镜和紫外可见分光光度计对产物的形貌和性质进行了表征,并考察银纳米粒子的形貌对其薄膜基底SERS活性的影响。结果表明：随着光照时间增加至16 h,金种子长大为平均粒径110 nm的不规则状多晶银纳米粒子,且出现双层粒子堆积。基底上纳米粒子的吸收光谱上出现了由银粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰：随着光照时间的变化,耦合峰在600～813 nm波段内移动。光照时间为12 h后得到的SERS活性基底具有最强的SERS信号。     

Influence of several factors on the growth of selenium nanowires induced by silver nanoparticles

This paper presents a study on the crystallization and growth mechanism of selenium nanowires induced by silver nanoparticles at ambient conditions with special reference to the effects of factors such as the shapes and size of silver nanoparticles, the induced reaction time, and the molar ratio of Ag⁰ to SeO₃²⁻ ions. The synthesis approach is conducted with no need of any stabilizers, and with no sonochemical process and/or templates. It is found that whether silver spherical particles or colloids can lead to the formation of nanowires with average diameter of 25 nm and lengths up to a few micrometers, and silver nanoplates lead to the formation of flat Se nanostructures. In particular, Au, Cu, Pt, and Pd particles cannot induce the growth of selenium nanowires in aqueous solution at room temperature. The results indicate that silver particles play a critical role in determining the growth of selenium nanowires. The lattice match between hexagonal-Se and orthorhombic- or trigonal-Ag₂Se particles is the major driving force in the growth of such nanostructures. The findings would be useful for design and construction of heterogeneous nanostructures with similar lattice parameter(s).     

The effect of the deposition parameters on size, distribution and antimicrobial properties of photoinduced silver nanoparticles on titania coatings

Controlled photodeposition of silver nanoparticles (AgNP) on titania coatings using two different sources of UV light is described. Titania (anatase) thin films were prepared by the sol-gel dip-coating method on silicon wafers. AgNPs were grown on the titania surface as a result of UV illumination of titania films immersed in aqueous solutions of silver nitrate. UV xenon lamp or excimer laser, both operating at the wavelength 351 ± 5 nm, was used as illumination sources. The AFM topography of AgNP/TiO₂ nanocomposites revealed that silver nanoparticles could be synthesized by both sources of illumination, however the photocatalysis carried out by UV light from xenon lamp illumination leads to larger AgNP than those synthesized using the laser beam. It was found that the increasing concentration of silver ions in the initial solution increases the number of Ag nanoparticles on the titania surface, while longer time of irradiation results the growth of larger size nanoparticles. Antibacterial tests performed on TiO₂ covered by Ag nanoparticles revealed that increasing density of nanoparticles enhances the inhibition of bacterial growth. It was also found that antibacterial activity drops by only 10-15% after 6 cycles compared to the initial use.     

Laser sintering of silver nanoparticle thin films: microstructure and optical properties

We present a method for the sintering of silver (Ag) nanoparticle thin films by millisecond pulsed laser irradiation. The microstructure of sintered thin films and sintering behaviors of nanoparticles were systematically investigated in this paper. Absorption spectra of sintered thin films showed blue-shifted surface plasmon resonances (SPR) from 500 nm to 480 nm and red-shifted from 480 nm to 550 nm when laser power was varied from 100 W to 140 W and from 140 W to 200 W, respectively. This indicates a new technique to control light absorption through joining nanoparticles with laser sintering. According to theoretical calculations based on a heat diffusion model, the melting temperature of these Ag nanoparticles was estimated to be 440 °C during laser irradiation.     

Enhanced electron field emission from dense Si nano-dots prepared by laser crystallization of ultrathin amorphous Si films

Dense Si nano-dots with a surface area density of >10¹⁰ cm^?2 were fabricated by excimer laser induced crystallization of 15 nm-thick amorphous Si thin films. The enhanced electron field emission characteristics were found from laser irradiated samples. The threshold electric field is as low as 9.8V/μm and the field enhancement factor can reach as large as 719, which is compatible with the other good cold cathode materials. The improvements in field emission behavior can be associated with the change in the surface morphology after laser irradiation as well as the enhanced internal electric field due to the formation of Si nano-dots within the films.     

The synthesis and kinetic growth of anisotropic silver particles loaded on TiO2 surface by photoelectrochemical reduction method

Silver nanorods with average diameters of 120-230 nm and aspect ratio of 1.7-5.0 were deposited on the surface of TiO₂ films by photoelectrochemical reduction of Ag⁺ to Ag under UV light. The composite films prepared on soda-lime glass substrates were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the TiO₂ film after UV irradiation in AgNO₃ solution is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. Other compounds cannot be found in the final films. The maximum deposition content of silver particles on the surface of TiO₂ film was obtained with the AgNO₃ concentration of 0.1 M. The kinetic growth rates of silver particles can be controlled by photocatalytic activity of TiO₂ films. The studies suggest that the growth rates of silver particles increase with the enhancement of photocatalytic activity of TiO₂ films. The maximum growth rate of silver particles loaded on TiO₂ films can be up to 0.353 nm min⁻¹ among samples 1#, 2# and 3#, while the corresponding apparent rate constant of TiO₂ is 1.751 × 10⁻³ min⁻¹.