Silver Films Research Articles

Fracture Mechanism of Sintered Silver Film Revealed by In Situ SEM Uniaxial Tensile Loading

Fracture Mechanism of Sintered Silver Film Revealed by In Situ SEM Uniaxial Tensile Loading

Cascaded dual-channel broadband SPR fiber optic sensor based on Ag/ZnO and Ag/TiO2/PDMS films structure

In order to broaden the bandwidth of SPR dual-channel sensors, this work proposes to tune the resonance wavelength range of the sensors using a cascade of ZnO and TiO2 films. The two oxides are transversely deposited on Ag-based no-core fiber to form a dual-channel sensor that can be used for refractive index (RI) and temperature measurements. Among them, Ag/ZnO is used for RI sensing and Ag/TiO2/PDMS is used for temperature sensing. The simulation and experimental results show that ZnO and TiO2 have the effect of broadening the resonance wavelength range by 44 nm and 72 nm, respectively. In addition, when the two oxides are added to the Ag-based sensor, the SPR valley is red-shifted, and the sensitivity is enhanced. The experimental results also show that the two oxides make the silver film less susceptible to oxidation and enhance the stability of the sensor. Numerical results show that the maximum RI sensitivity of the sensor is 4630 nm/RIU, and the temperature sensitivity is 5.8 nm/°C. The range of the object to be measured is 1.333–1.385, 0–50 °C. This ability to broaden the sensor bandwidth provides a new direction for designing and applying high-performance multi-channel SPR sensors.

Large Area Growth of Silver and Gold Telluride Ultrathin Films via Chemical Vapor Tellurization

Developing a method for the growth of ultrathin metal chalcogenides, potentially targeting the two-dimensional (2D) limit, has a pivotal impact on various nanotechnological device applications. Here, we employed a vapor deposition scheme, based on tellurization, to induce the heterogenous chemical reaction between solid Ag and Au precursors, in the form of ultrathin films, and Te vapors. We characterized the morphological and structural properties of the grown tellurides by using atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction techniques. The developed tellurization methodology provides a key advancement in the picture of growing ultrathin noble metal tellurides and holds great potential for applications in different technological fields.

Structure and Microchannel Catalytic Bed Performance of Silver Thin Films Prepared by Electroplating

The morphology of catalysts in microchannels plays a crucial role in the orbital maneuvering and networking applications of micro/nano satellites using hydrogen peroxide as a unit propellant. In this paper, a microfluidic reaction chip was designed and fabricated to detect the reaction rate of the catalytic decomposition of hydrogen peroxide solution by a microchannel catalytic bed. In addition, a silver thin film prepared by constant-current electroplating was used as a substrate for the microchannel catalyst. The results show that the ratio of surface area to area of silver film and the average particle size of silver particles have a significant positive correlation on the reaction rate of catalytic decomposition, while the thickness, silver content, and surface roughness of the silver film have no significant effect on the reaction rate of catalytic decomposition. The catalytic performance of the microchannel catalytic bed of silver thin film is greatly influenced by the conditions of electroplating, namely, the electroplating temperature (T), time (t), and current (I). And when I = 0.3 mA, t = 180 s, and T = 60 °C, the microchannel catalytic bed of the silver film prepared by electroplating reaches the optimal reaction rate for the catalytic decomposition of hydrogen peroxide solution. This study has the best process parameters for the design and optimization of heterogeneous catalysts applied to microfluidic reactors.

NEW HIGH-THROUGHPUT METHODS FOR ANTIBACTERIAL VALIDATION OF METALLIC THIN FILMS: DIFFERENT METALS FOR DIFFERENT MICROBIAL COMMUNITIES

Prosthetic joint infections represent complications connected to the implantation of biomedical devices, they have high incidence, interfere with osseointegration, and lead to a high societal burden. The microbial biofilm, which is a complex structure of microbial cells firmly attached to a surface, is one of the main issues causing infections. Biofilm- forming bacteria are acquiring more and more resistances to common clinical treatments due to the abuse of antibiotics administration. Therefore, there is increasing need to develop alternative methods exerting antibacterial activities against multidrug-resistant biofilm-forming bacteria. In this context, metal-based coatings with antimicrobial activities have been investigated and are currently used in the clinical practice. However, traditional coatings exhibit some drawbacks related to the insufficient adhesion to the substrate, scarce uniformity and scarce control over the toxic metal release reducing their efficacy. Here, we propose the use of antimicrobial silver-based nanostructured thin films to discourage bacterial infections. Coatings are obtained by Ionized Jet Deposition, a plasma-assisted technique that permits to manufacture films of submicrometric thickness having a nanostructured surface texture, allow tuning silver release, and avoid delamination. To mitigate interference with osseointegration, here silver composites with bone apatite and hydroxyapatite were explored. The antibacterial efficacy of silver films was tested in vitro against gram- positive and gram-negative species to determine the optimal coatings characteristics by assessing reduction of bacterial viability, adhesion to substrate, and biofilm formation. Efficacy was tested in an in vivo rabbit model, using a multidrug-resistant strain of Staphylococcus aureus showing significant reduction of the bacterial load on the silver prosthesis both when coated with the metal only (>99% reduction) and when in combination with bone apatite (>86% reduction). These studies indicate that IJD films are highly tunable and can be a promising route to overcome the main challenges in orthopedic prostheses.

Silver-coated hollow fiber surface plasmon resonance sensor for glucose detection with enhanced limit of detection.

A fiber-optic surface plasmon resonance (SPR) biosensor based on a silver-coated hollow fiber (HF) structure for glucose detection is presented. The sensor surface was immobilized with 4-mercaptophenylboronic acid (PMBA) acting as a glucose recognition monolayer. Then, gold nanoparticles (AuNPs) modified with 2-aminoethanethiol (2-AET) and PMBA were introduced onto the sensor surface after glucose was captured to enhance the wavelength shift of the SPR phenomenon excited by the light transmitted in the wall of the HF sensor. Instead of the conventional one-step sensitization pretreatment commonly used in the deposition process of silver films for fiber-optic SPR sensors, a sensitization-activation two-step activation method was adopted in the fabrication of the proposed sensor. Experiments for glucose detection were performed on the fabricated sensors in the concentration range of 1 nM-1 mM. Results showed that the sensor fabricated by the two-step activation method has a much larger shift of resonance wavelength than the sensor fabricated using the one-step sensitization method. The resonance wavelength shift was found to be linear to the logarithm of the concentration in the range of 1 nM-1 mM. The sensor achieved a limit of detection (LOD) of as low as 1 nM, which is at least an order of magnitude lower than that of other fiber-optic sensors for glucose detection reported previously. The presented HF glucose sensor has the potential for biosensing applications and provides a large reference value in the study of optical fiber SPR sensors for biosensing.

Easily constructed porous silver films for efficient catalytic CO2 reduction and Zn-CO2 batteries.

For the electroreduction of carbon dioxide into high value-added chemicals, highly active and selective catalysts are crucial, and metallic silver is one of the most intriguing candidate materials available at a reasonable cost. Herein, through a novel two-step operation of Ag paste/SBA-15 coating and HF etching, porous silver films on a commercial carbon paper with a waterproofer (p-Ag/CP) could be easily fabricated on a large scale as highly efficient carbon dioxide reduction reaction (CO2RR) electrocatalysts with a CO Faraday efficiency (FECO) as high as 96.7% at -1.0 V vs. the reversible hydrogen electrode (RHE), and it still reaches up to 90% FECO over applied potentials ranging from -0.8 to -1.1 V vs. the RHE. Meanwhile, the membrane electrode assembly (MEA) utilizing the p-Ag/CP catalyst has achieved a current density, FECO, and stability of ∼60 mA cm-2, >91%, and 11 h, respectively. Furthermore, the assembled aqueous Zn-CO2 battery using p-Ag/CP cathode yielded a peak power density of 0.34 mW cm-2, 75 charge-discharge cycles for 25 h, and 64% FECO at 2.5 mA cm-2. Compared with flat Ag/CP, the significant enhancement in the CO2RR activity of p-Ag/CP was mainly attributed to the distinctive porous structure and an improved three-phase boundary, which is capable of inducing the stabilization of *COOH intermediates, increased active specific surface areas, fast electron transfer kinetic and mass transportation. Further, theoretical calculations revealed that p-Ag/CP possessed an optimized energy barrier for *COOH intermediates.

Formation Mechanism of Nano Silver Film by Laser Action on Particle-Free Complexed Silver Ion Ink

Formation Mechanism of Nano Silver Film by Laser Action on Particle-Free Complexed Silver Ion Ink

Retracted: Wireless Network of Silver Film Lysozyme Aptasensor Based on Fractal Measurement

Retracted: Wireless Network of Silver Film Lysozyme Aptasensor Based on Fractal Measurement

Giant Raman radiation from molecules in a spherical metal shell

The work considers an electrodynamic model of radiation from molecules placed in a metal shell. The model qualitatively describes the enhancement of the surface-enhanced Raman scattering (SERS) signal from spherical nanoparticles coated with a thin silver film. The change in the SERS signal is calculated depending on the thickness of the metal nanolayer on top of the spherical particles. The radiating molecular dipole interacts with the metal shell and excites surface plasmons. Plasmonic oscillations reach a maximum when the frequency of the dipole is close to the plasmon resonance of the metal shell, and the dipole itself is close to the plasmonic shell. It has been theoretically shown that the intensity of secondary radiation generated by spherical nanoparticles coated with a silver film several nanometers thick can reach up to six or more orders of magnitude. The effect of a tenfold amplification of the SERS signal was experimentally demonstrated using the example of a large ensemble of single polystyrene microspheres with an average diameter of about 300 nm, coated with a silver nanolayer, which have characteristic Stokes frequencies of 1001 cm-1, 1602 cm-1. We believe that the tenfold enhancement of Raman scattering is due to the electromagnetic amplification mechanism.

Unconventional thickness dependence of electrical resistivity of silver film electrodes in substoichiometric oxidation states

The scaling down of metallic electrodes into ultrathin film geometries presents significant challenges in precisely controlling electrical resistivity. This difficulty stems from the rapid variation in resistivity with thickness, particularly near the percolation threshold. Currently, our understanding of the prediction of thickness-dependent resistivity in metallic film electrodes in volatile substoichiometric oxide (suboxide) states is limited. This study offers experimental and numerical evidence demonstrating a marked resistivity fluctuation spanning four to five orders of magnitude during the initial growth stages of suboxidized Ag film electrodes. These stages range from cluster coalescence to reaching the percolation threshold. The unusual resistivity change is attributed to the variation in suboxidation states with thickness, as well as the outward migration of interstitial O ions. These findings offer a crucial framework for controlling the electrical properties of thin metallic oxide films in extreme suboxidation states, extending beyond the conventional understanding applicable to thermodynamically stable metallic oxide phases.

Sensitive Determination of Carbendazim in Tobacco Leaves by Surface Enhanced Raman Spectroscopy (SERS) Using a Silica – Silver Nanoparticle Substrate and QuEChERs Pretreatment

A sensitive surface enhanced Raman spectroscopy (SERS) substrate based on SiO2@Ag core-shell with a QuEChERs pretreatment method were constructed for the determination of carbendazim residue in tobacco leaves. The SERS substrate was formed by self-assembly of monolayer homogeneous SiO2 nanospheres onto silicon wafer following by vacuum thermal evaporation of silver film. The QuEChERs pretreatment method was used to eliminate the interfering effects of pigments and organic acids in tobacco leaves. The results for carbendazim in tobacco leaves show the limit of detection (LOD) of the SERS substrate was 0.1 mg/kg and the recovery rate was from 82.56% to 95.93%. The proposed low-cost sensitive SERS substrates provide potential application for tobacco safety monitoring.

Unravelling the effect of nitrogen on the morphological evolution of thin silver films on weakly-interacting substrates

We study the effect of nitrogen on the morphological evolution of thin silver (Ag) films deposited on weakly-interacting amorphous carbon (a-C) and silicon oxide (SiOx) surfaces. Films are synthesized at a deposition rate of 0.1nm·s-1 by direct current magnetron sputtering (DCMS), high power impulse magnetron sputtering (HiPIMS), and electron-beam evaporation (EBE). We monitor growth in situ and in real time by measuring the evolution of film stress and optical properties, complemented by ex situ analyses of discontinuous-layer morphologies, film crystal structure, and film composition. We find that addition of molecular nitrogen (N2) to the plasmagenic gas (Ar) during DCMS and HiPIMS promotes a two-dimensional (2D) morphology. Concurrently, EBE-deposited films exhibit a significantly more pronounced three-dimensional morphological evolution, independently from the gas atmosphere composition. We argue that the 2D morphology in DCMS- and HiPIMS-grown films is enhanced due to incorporation of atomic nitrogen (N)—result of plasma-induced N2 dissociation—that hinders island reshaping during coalescence. This mechanism is not active during EBE due to the absence of energetic plasma electrons driving N2 dissociation. The overall results of the study show that accurate control of vapor-phase chemistry is of paramount importance when using gaseous species as agents for manipulating growth in weakly-interacting film-substrate systems.

Simple and additive-free synthesis of highly reflective thin silver films and their application on large-scale surfaces

There is a growing demand for highly reflective coatings especially on non-conducting surfaces for use in various industries. Additionally, focus is arising on green production and cost reduction in terms of energy, time, etc., which require detailed investigation of coating process parameters. Therefore, in this work, silver thin films with high reflectance were synthesized on glass substrates in short durations at room temperature by electroless plating (ELP) method in one-step and without using any additives. Effects of deposition time, concentration of the reactants (AgNO3, Glucose, NaOH), and also the surface pretreatment and activation steps were investigated in detail to improve the reflectance and structural properties of silver films. Contact angle measurements were realized to examine the effects of each surface modification step. Surfaces subjected to etching, sensitization and Ag activation were found to yield more homogeneously distributed nanoparticles in short deposition period. Scanning electron microscopy (SEM) also showed smaller-sized spherulite-shaped crystals, forming a close packed structure with an optimum film thickness of ∼110 nm. The continuity of the silver coatings on the surface was verified by the low sheet resistance of 0.18 Ωsq−1. Atomic force microscopy (AFM) analysis revealed a smoother film structure with an RMS of 10.7 nm after sensitization. X-ray diffraction analysis (XRD) and X-ray photoelectron spectroscopy analysis (XPS) analysis proved the growth of highly crystalline silver nanoparticles with high purity. All these morphological improvements led to high values of light (∼97%), near-infrared (99%) and solar (96%) reflectance for the coatings. Finally, based on the optimized concentrations and bath conditions, large-scale (700×500 mm2) first-surface mirrors were successfully produced (96.2%R and 0.25 Ωsq−1) by spray coating technique combined with ELP. Overall, the results indicate that the obtained films have potential usage in applications such as solar energy, electronics and aeronautics.

Solid Reservoir Reference Electrode

Potentiometric sensing requires a stable sensing electrode that is selectively responsive to an analyte, and a reference electrode (RE) that provides a stable and well-defined reference potential in a liquid electrolytic environment. In sensor applications where compactness and ease of integration are essential characteristics, pseudo-REs in the form of doped polymer semiconductors, bare metal films, or a bare chlorinated silver film are typically used. Bulk glass electrodes, such as the Ag/AgCl electrode, are incompatible with sensor integration.We report here a solid reservoir reference electrode (SRRE) that achieves the performance of traditional immersed wire Ag/AgCl REs in a compact, layered structure. The SRRE is a solid, layered analogue of the Ag/AgCl RE, with a chlorinated silver film as metallic electrode, a solid KCl layer serving as a saturated reservoir of chloride, and a porous polydimethylsiloxane (PDMS) layer acting as membrane for exchange of water and ions. We demonstrate two different method to fabricate the porous PDMS in figure A and B. The characteristics of the SRRE, including impedance, noise, and long-term drift, can be tuned by adjustment of the PDMS membrane permeance and KCl solid reservoir size.We have demonstrated temporal stability of the RE open circuit potential (OCP), with drift less than 0.37 mV over 17 hours in deionized water. When compared against bare chlorinated silver, the SRRE exhibits superior stability of OCP versus changes in electrolyte ion-concentration, including solutions of potassium chloride, sodium chloride and pH buffers. The ease of fabrication enables SRRE integration with graphene ion-sensitive field effect transistors (ISFETs) to achieve entirely solid-contact micro ion sensors. The solid-contact micro ion sensor can simultaneously measure pH and Na+, in volumes as low as 20 μL. Using the same layered structure, we further demonstrated fabricated electrocardiogram (ECG) and electroencephalogram (EEG) electrodes with significantly lower impedance and noise when compared to disposable gel electrodes. Finally, we have shown that the SRRE can function in non-aqueous solventssuch as acetonitrile, demonstrating the wide range of SRRE applications. Figure 1

ХІМІЧНЕ РІЗНОСТУПЕНЕВЕ ТРАВЛЕННЯ ПОВЕРХНІ ТОНКИХ ПЛІВОК СРІБЛА

Thin-film metal coatings are an important element of optoelectronic devices. In particular, such metal coatings are a defining component of the sensitive layer of various sensors in which the specified surface morphology of the metal coating determines the necessary optoelectronic properties, as is observed, for example, in the case of substrates for SERS (Enhanced Surface Raman Scattering) or SPR (Surface Plasmon Resonance). The highest technological interest for optoelectronic applications is caused by thin silver films due to their well-known remarkable properties, in particular, due to the high value of the extinction coefficient in such a film, as well as due to the presence of an intense narrow absorption band of surface plasmon resonance. In the presented publication original approaches to surface treatment of thin silver films with etching solutions containing compounds characterized by specific oxidative-reductive and complexative property as to silver have been considered. Comparative analysis of the obtained results concerning changes in mass and topography of silver electrodes allowed grounding the mixture choice for microstructural profiling (etching solution M) and nanopolishing (etching solution N) of thin silver film. The physicochemical mechanisms which cause the observed processes have been considered. The etching nature is shown to depend on the oxidation level of redox element involved to the etching solution. Also, it depends on the presence of water-soluble complexation ligands in the solution. The conception that etching composition contained component with intermediate oxidation level in redox element exposes a "softer" effect on the etching topography in thin silver film has been proposed. The considered condition determines the possibility for chemical nanopolishing of thin silver film. The study in surface structural changes has been an integral part of nanoscale research, therefore, the obtained results have a practical value in the nanostructure formation which is the main part in modern acoustics and optoelectronics.

Plasmon enhancement of photosensitivity of Ag–chalcogenide glass thin film structures

In this paper, we present the results of studying the features of plasmon- enhanced photostimulated diffusion of silver into thin films of chalcogenide glasses (ChG), in particular, As 2 S 3 and GeSe 2 . To ensure excitation of surface plasmon-polaritons (SPPs) at the interface between silver and ChG films, silver diffraction gratings with periods of 899 and 694 nm were used as substrates. The samples were exposed to the p-polarized radiation of a He-Ne laser (λ = 632.8 nm). The radiation of the same laser, attenuated by two orders of magnitude, was used to detect SPP, which enabled to study the kinetics of photostimulated processes in the thin-layer structure of Ag–ChG. It has been established that in the initial period of exposure, the SPP electromagnetic field significantly enhances the photostimulated flux of silver ions in ChG (by 2-3 times). The photodissolution kinetics of Ag in ChG is defined by the features of the granular structure of the investigated thin chalcogenide films. For the GeSe 2 film with the effective thickness 8 nm, the kinetics of the film refractive index increase caused by silver photodoping is well approximated by a logarithmic dependence. For the Ag–As 2 S 3 structure (the effective thickness of the As 2 S 3 film is 14.8 nm), this kinetics is closer to the linear one; moreover, for photodoping without SPP excitation, the kinetics is somewhat superlinear, while with plasmon excitation, it is sublinear. The main physical mechanism responsible for the acceleration of the process of photostimulated diffusion in the structure under study appears to be an accelerated generation of electron-hole pairs, which takes place in the ChG layer near the interface with the metal, where the SPP electromagnetic field strength is maximum, and/or plasmon- assisted hot carrier generation due to plasmon scattering on the surface of the metal film and subsequent internal photoemission of electrons from silver into chalcogenide.

Reusable Wrinkled Nanoporous Silver Film Fabricated by Plasma Treatment for Surface-Enhanced Raman Scattering Applications.

A nanoporous silver film (npAgF), a promising structure for surface-enhanced Raman spectroscopy (SERS), can be fabricated by using successive O2 and Ar plasma treatments on a planar silver film. The common dealloying method for producing an npAgF involves annealing at high temperatures to produce an alloy film, as well as harsh etching using corrosive chemicals. By contrast, the plasma-based method can be applied directly to various functional substrates to produce more sophisticated npAgF structures. Herein, we report a facile fabrication method for a wrinkled npAgF (w-npAgF) for SERS applications using a thermally contractible polystyrene substrate. The w-npAgF had 3D wrinkles of the nanoporous structure and showed approximately 8 times higher SERS enhancement than did the flat npAgF. Moreover, the w-npAgF could be reused for multiple SERS measurements of different molecules by mild O2 and Ar plasma treatments after each use, in which the O2 plasma effectively removed the adsorbed organic molecules and the Ar plasma reduced silver oxide to pristine silver for subsequent SERS measurements. The wrinkled nanoporous structure was maintained after multiple mild plasma treatments for reuse. The simplicity of plasma-based fabrication and high sensitivity of w-npAgFs are promising features for the green production of low-cost and reusable 3D SERS substrates.

Enhanced Broadband Light Harvesting in Ultrathin Absorbers Enabled by Epitaxial Stabilization of Silver Thin Film Mirrors.

Silver thin film mirrors are attractive candidates for use as specular back reflectors to enhance broadband light absorption via strong optical interference in ultrathin film semiconductor photoabsorbers. However, deposition of metal-oxide absorbers often requires exposure to high temperature in an oxygen atmosphere, conditions that cause thermal etching and degrade the specular reflectance of silver films. Here, we overcome this challenge and demonstrate that epitaxial growth of silver mitigates thermal etching under the high-temperature oxygen-containing environments that cause polycrystalline films to degrade. The degree of thermal etching resistance is related to the epitaxial film structure, where high-quality films completely prevent thermal etching, allowing for direct deposition of metal-oxide thin film photoabsorbers at elevated temperatures without any degradation of the optical properties of the silver layer. As a proof of concept for device applications, a metal-oxide photoanode for photoelectrochemical water splitting is fabricated by directly growing epitaxial SnO2 and Ti-doped α-Fe2O3 (hematite) thin films onto stabilized silver reflectors by pulsed laser deposition. The photoanode displays enhanced broadband light absorption due to strong interference effects enabled by the highly reflective silver film and demonstrates stable operation in a photoelectrochemical cell under conditions of water photo-oxidation in alkaline electrolyte.

Liquid crystal-embedded fiber optic fabry perot temperature sensor based on Vernier effect

An optical temperature sensing method with ultra-high sensitivity and a wide measurement range is proposed. The performance enhancements come from the high thermos-optical coefficient of liquid crystal (LC) material, and the Vernier effect produced by LC birefringence characteristics. This paper proposes and demonstrates a method to enhance the measurement range of the LC temperature sensor. A miniature LC temperature sensor was made by using an optical fiber Fabry-Perot interferometer (FPI). To compensate for and attenuation of LC and improve the contrast of the FPI, silver films are coated on one end of the optical fiber. Due to the high birefringence of the LC in the interferometer, a Vernier spectrum can be observed in the reflection. The temperature measurement range of 20–32 °C and the temperature sensitivity of the Vernier peaks of a sensor sample is about 42.18 nm/°C, which is much higher than the sensitivity of the cascaded FBG in structure. The limited measurement range is due to the free spectral range (FSR) limitation. In this context, the FBG peak can be used as a temperature reference while switching the adjacent Vernier peaks. Hence, this LC temperature sensor exhibits high sensitivity as well as a wide measuring range, which would broaden the application scope of the LC temperature sensors.