Ag Nanostructures Research Articles

Diffusive ex situ galvanic growth of metal nanocrystals on transmission electron microscopy grid

The uniform modification of commercial and standardized objects features considerable potential, as in the case of dip-pen lithography, biosensor kits, and disposable electrodes. In this study, we devised a dense nanoparticle array formation using the metallic mesh of a transmission electron microscopy (TEM) grid, which was formerly solely employed as a sampling stage. Incompletely oxidized cationic species generated from the galvanic replacement reaction of the metallic support mesh at the opposite side of the carbon layer diffused to the exposed top side and led to ex situ nanostar formation. A uniform nanoparticle array was obtained by immersion in an aqueous solution of replacing metal cations without reducing agents or surface energy-controlling compounds. Moreover, the array density was exclusively regulated by the incubation time. The straightforward nanoparticle array formation was successfully extended to various metal mesh TEM grids and different transition metal cations capable of spontaneous redox reactions. Cu mesh TEM grid and Mo grids could be utilized as sacrificial templates, and the growth of Au, Pd, Pt, Ag, and Rh nanostructures was confirmed.

Surface plasmons on silver gratings transform pyrolytic carbon into luminescent graphitized carbon dots.

Plasmonic catalysis holds the promise of opening new reaction pathways that are inaccessible thermally or via direct UV-vis electronic transitions. Here, energetic carriers produced via the decay of surface plasmons excited by visible light at 532nm (2.33eV, green) on a Ag-grating-bearing pyrolytic carbon residue drive its transformation into light-emitting graphitized carbon dots. The pyrolytic carbon residue is detectable via high-magnification surface-enhanced Raman scattering but cannot be directly observed using optical, electron, atomic force, or helium ion microscopy. When a Ag-grating-bearing pyrolyzed residue is introduced into a high-purity O2-depleted gas environment (Ar, N2, and CO2) and excited with 532nm light, bright yellow luminescence emerges and is readily observed. Light emission is not observed without the pyrolytic carbon, without the excitation of plasmons, or in air or an Ar/O2 gas mixture. This process, driven by visible light and a nanostructured Ag surface bearing pyrolytic carbon, will be of interest to researchers involved in plasmonic catalysis, catalytic processes involving carbon, and luminescent plasmonic surfaces.

Chiral Nanostructured Ag Films for Multicarbon Products from CO2 Electroreduction.

The formation of multicarbon products from CO2 electroreduction is challenging on materials other than Cu-based catalysts. Ag has been known to be a typical metal catalyst, producing CO in CO2 electroreduction. The formation of C2+ products by Ag has never been reported because the carbon-carbon (C-C) coupling is an unfavorable process due to the high reaction barrier energy of *OCCO. Here, we propose that the chirality-induced spin polarization of chiral nanostructured Ag films (CNAFs) can promote the formation of triplet OCCO by regulating its parallel electron spin alignment, and the helical lattice distortion of nanostructures can decrease the reaction energy of *OCCO, which triggers C-C coupling and promotes subsequent *OCCO hydrogenation to facilitate the generation of C2+ products. The CNAFs with helically lattice-distorted nanoflakes were fabricated via electrodeposition using phenylalanine as the symmetry-breaking agent. C2+ products (C2H4, C2H6, C3H8, C2H5OH, and CH3COOH) with a Faradaic efficiency of ∼4.7% and a current density of ∼22 mA/cm2 were generated in KHCO3 electrolytes under 12.5 atm of CO2 (g). Our findings propose that the chiral nanostructured materials can regulate the multifunctionality of catalytic performance in the catalytic reactions with triplet intermediates and products.

Thermal decomposition temperature-dependent bonding performance of Ag nanostructures derived from metal–organic decomposition

In wide-bandgap semiconductor power device packaging, die bonding refers to attaching the die to substrate. Thereby, the process temperature of Ag sintering for the die bonding should be low to prevent damage to fragile dies. Herein, an organic-free strategy using Ag nanostructures derived from the thermal decomposition of metal–organic decomposition (MOD) was proposed to achieve low-temperature bonding. Significant effects on bonding performance were determined by the thermal decomposition temperature, which in turn determined the organic content and sintering degree of Ag nanostructures. At a low thermal decomposition temperature of 160 °C, incomplete decomposition resulted in high organic content in the Ag nanostructures, causing large pores inside the Ag joints owing to the generation of gaseous products. Owing to the Ag particles with naked surfaces and wide size distribution, the Ag nanostructure obtained at 180 °C showed an excellent bonding performance, resulting in a high shear strength of 31.1 MPa at a low bonding temperature of 160 °C. As the thermal decomposition temperature was 200 °C, sintering among Ag particles increased the particle size, resulting in a reduction of surface energy and driving force for sintering. We think that uncovering this underlying mechanism responsible for the bonding performance will promote the application of Ag MOD in the die bonding of WBG power devices.Graphical abstract

Substrate-Dependent Sintering Mechanism of Ag Nanostructures Derived from Ag-Based Complex

Substrate-Dependent Sintering Mechanism of Ag Nanostructures Derived from Ag-Based Complex

Fabrication of Three-Dimensional Dendritic Ag Nanostructures: A SERS Substrate for Non-Invasive Detection.

This paper discusses the fabrication of three-dimensional dendritic Ag nanostructures, showcasing pronounced Localized Surface Plasmon Resonance (LSPR) effects. These nanostructures, employed in surface-enhanced Raman scattering (SERS), function as sensors for lactic acid in artificial sweat. The dendritic structures of the silver nanoparticles (AgNPs) create an effective SERS substrate, with additional hotspots at branch junctures enhancing LSPR. We achieve differential LSPR effects by varying the distribution and spacing of branches and the overall morphology. Adjustments to electrodeposition parameters, such as current and plating solution protective agents on an anodized aluminum oxide (AAO) base, allow for precise control over LSPR intensities. By pre-depositing AgNPs, the electron transmission paths during electrodeposition are modified, which leads to optimized dendritic morphology and enhanced LSPR effects. Parameter optimization produces elongated rods with main and secondary branches, covered with uniformly sized, densely packed, non-overlapping spherical AgNPs. This configuration enhances the LSPR effect by generating additional hotspots beyond the branch tips. Fine-tuning the electrodeposition parameters improved the AgNPs' morphology, achieving uniform particle distribution and optimal spacing. Compared to non-SERS substrates, our structure amplified the Raman signal for lactic acid detection by five orders of magnitude. This method can effectively tailor SERS substrates for specific analytes and laser-based detection.

Optimized green synthesis of biocompatible Ag nanostructures using Artemisia Indica leaf extract: a promising avenue for biomedical applications

Optimized green synthesis of biocompatible Ag nanostructures using Artemisia Indica leaf extract: a promising avenue for biomedical applications

Flexible transparent conductors with a percolated Ag nanostructure and its application as efficient self-bias plasmonic photodetector

A percolated silver (Ag) nanostructured-based transparent conductor has been deposited by physical vapor deposition (PVD) technique where lateral growth of Ag has been enhanced by a pre-deposited Ag-TiO2 thin film. This Ag-TiO2 film has embedded Ag nanoparticles (NPs) within TiO2 thin film which is grown in a low temperature (100 °C) solution processed technique. This process includes Li4Ti5O12 (LTO) thin film deposition by a sol–gel method followed by ion-exchange (Li+ → Ag+) process to yield an Ag-TiO2 thin film. The percolated Ag network has appeared as soon film mass-thickness reaches close to 10 nm, resulting in an abrupt drop of electrical resistivity of the film. This percolated Ag nanostructured thin film (10 nm Ag/Ag-TiO2/plastic) has resistivity of ∼50 Ω/□ and an average visual transmittance of >70 % up to 450 nm. In higher wavelength range, transparency gradually reduces, and it reaches to ∼50 % at 600 nm which is mostly due to the plasmon absorption of this film. By utilizing its combined optical transparency and surface plasmon absorption, this film has been used to develop plasmonic hot electron photodetectors where Ag-thin film works as transparent electrode as well as plasmon induced photo-excited hot electron generation. Device has been fabricated on a heavily doped n type Si (n++-Si) with a metal–semiconductor-metal (M−S−M) device geometry. External quantum efficiency (EQE) data reveal that photocurrent of this device is mostly generated in the plasmonic absorption region with a peak detectivity of 2.84 × 1012 Jones at 510 nm under −3V external bias. Besides, the device shows fast response with a response time of ∼25 ms.

Green-synthesized Ag hierarchical assemblies for SERS detection of rhodamine dye

This study presents a simple benchtop synthetic protocol for the fabrication of silver (Ag) hierarchical structures in aqueous media using environmentally friendly and inexpensive reagents under mild experimental conditions. Natural organic acids that are known to be present in plants were employed as reducing and morphology-directing reagents. SEM and TEM imaging revealed that the products are three-dimensional hierarchical structures that were formed from self-assembly of smaller nanoparticles. They are generally spherical in shape, measure around 1.5 to 5 μm in size, and possess highly roughened surfaces due to the interstitial gaps between their nanoparticle subunits. Their hierarchical architecture allows for strong absorption of light in a broad range of wavelengths that extends to the near-infrared region. In addition, their surface morphology has an abundance of hot spot regions, which are capable of inducing strong SERS enhancement effects. The green-synthesized Ag nanostructures showed remarkable SERS activity when used as substrates for the detection of rhodamine 6G dye, a highly toxic water contaminant, even at a concentration as low as 10–8 M. Overall, this study does not only provide a greener approach to Ag hierarchical structures, but also demonstrates the immense potential of these nano-assembled architectures in the sensitive detection of organic dye pollutants.

Anisotropic growth of Ag nanonails induced by plasmon-mediated chemical reactions in cross-shaped nanocavity array

The Ag nanonail rooted in Au cross-channel nanocavity is fabricated by plasmon-mediated chemical reactions (PMCRs). The Au cross-channel nanocavity is prepared based on two-dimensional polystyrene (PS) nanosphere template through wet etching, and the shape of Au cross-channel nanocavity changes from trapezoidal to triangular, depending on the wet etching time. The growth of Ag nanostructures in Au channels by PMCRs indicates the morphology of Ag nanostructures has changed from Ag nanoparticles to nanonails, which is regulated by the shape of Au nanocavities and the exciting light polarization. The hotspots distributions results in the anisotropic growth of Ag nanostructures induced by PMCRs, which leading to the different Ag nanostructures depending on the shape of Au nanocavity and light polarization, as confirmed by FDTD simulations. In comparison with others reports, our nanocavity provide more parameters to control the shapes of Ag nanostructures, the nanocavity shape, the light polarization and the growth time. Our work provides a profound insight into the construction of periodic nanostructures and reconstruction of hotspots.

A first principles study of the oxygen reduction reaction mechanism on porous Ag and Ag-TM nanostructure

Porous Ag has good electron conductivity and is one of the typical oxygen reduction reaction(ORR) catalysts. In order to investigate the mechanism of porous Ag for ORR, the relaxed structure and detailed partial density of states are determined using density-functional theory. Among multiple possible active sites, the overpotential of porous Ag is 0.50 V, which is better than that of Ag (111) at 0.62 V. After doping Pt and Pd, the overpotentials are 0.47 V and 0.49 V, respectively. Furthermore, the introduction of a transition metal has led to changes in the charge distribution on the catalyst surface, which has resulted in improved catalytic performance. By investigating the synergistic effects between doped transition metals and ORR intermediates, this can facilitate the development of catalysts with higher activity and better stability.

Ag-deposited nanostructured Boehmite substrates for the detection of explosives with surface enhanced Raman spectroscopy

We propose aluminum oxide (Boehmite) sputter-deposited with Ag substrates for Surface-Enhanced Raman Spectroscopy (SERS). These substrates are cost-effective and easily fabricated by heating aluminum in an aqueous environment to create Boehmite, followed by Ag sputtering. The metal deposition is optimized, resulting in random arrays of Ag nanostructures with a diameter of ∼100 nm and a spacing of <100 nm leading to significant enhancement of the Raman signal. The performance and sensitivity of the substrates are initially tested with the use of Crystal Violet analyte which results in limits of detection close to 10−10M. These substrates are used for the rapid detection of four different explosive compounds: Nitroglycerin (NG), Picric Acid (PA), Cyclotrimethylene trinitramine (RDX) and 2,4,6-Trinitrophenylmethylnitramine (Tetryl). A series of Raman spectra are collected for these four selected explosives on the fabricated substrates and principal component analysis (PCA) was used for proper evaluation and identification of the corresponding measured spectra.

Combined Electrochemical Deposition and Photo-Reduction to Fabricate SERS-Active Silver Substrates: Characterization and Application for Malachite Green Detection in Aquaculture Water.

This research introduces a novel approach using silver (Ag) nanostructures generated through electrochemical deposition and photo-reduction of Ag on fluorine-doped tin oxide glass substrates (denoted as X-Ag-AgyFTO, where 'X' and 'y' represent the type of light source and number of deposited cycles, respectively) for surface-enhanced Raman spectroscopy (SERS). This study used malachite green (MG) as a Raman probe to evaluate the enhancement factors (EFs) in SERS-active substrates under varied fabrication conditions. For the substrates produced via electrochemical deposition, we determined a Raman EF of 6.15 × 104 for the Ag2FTO substrate. In photo-reduction, the impact of reductant concentration, light source, and light exposure duration were examined on X-Ag nanoparticle formation to achieve superior Raman EFs. Under optimal conditions (9.0 mM sodium citrate, 460 nm blue-LED at 10 W for 90 min), the combination of blue-LED-reduced Ag (B-Ag) and an Ag2FTO substrate (denoted as B-Ag-Ag2FTO) exhibited the best Raman EF of 2.79 × 105. This substrate enabled MG detection within a linear range of 0.1 to 1.0 µM (R2 = 0.98) and a detection limit of 0.02 µM. Additionally, the spiked recoveries in aquaculture water samples were between 90.0% and 110.0%, with relative standard deviations between 3.9% and 6.3%, indicating the substrate's potential for fungicide detection in aquaculture.

High performance of UV photodetectors by integration of plasmonic Ag nanoparticles on GaN

High-performance ultraviolet photodetectors have attracted much attention due to their various potential applications from household to universal. On basis of this, in this work, a high – performance and photoresponse enhancement UV photodetector based on Ag NPs/GaN heterojunction was demonstrated. By incorporating of Ag nanoparticles, light confinement determined by Ag nanostructure offers an effective approach to break through the limitation of the light-mater interaction within the photoactive layers of photodetector. Various size and elemental composition of Ag NPs are fabricated on GaN lead to significant enhancement of photocurrent in UV photodetector. Consequently, an outstanding photoresponsivity of 89 A/W, external quantum efficiency of 2.8 × 103% at low bias voltage of 0.3 V were achieved. The improve photo-response of the Ag NPs-decorated GaN-based photodetector is attributed to the simultaneous effect of strong plasmon absorption, increased injection of hot electrons into the conduction band of GaN. This study will open up the direction to fabricate the high-performance UV photodetector.

Polydopamine-mediated facile Silver grown on ZnO Thin Films as High Performance SERS Substrates for R6G Detection

Surface-enhanced Raman spectroscopy (SERS) is a widely known technique that uses plasmonic structures (silver, gold, etc.) to detect low-concentration molecules. However, the limited number of metallic elements with plasmonic properties leads to limitations in their application. The qualitative detection method of SERS holds considerable promise in providing novel platforms for diverse applications, owing to its utilization of hybrid structures. Mussel-inspired polydopamine offers a promising avenue for the fabrication and integration of hybrid structures suitable for the SERS platform. Here, sputtered ZnO thin films were modified with Ag Nanostructures using polydopamine to fabricate a homogeneous Ag@ZnO hybrid high-performance SERS substrate. Ag/ZnO hybrid nanostructures were analyzed by FESEM and XRD to investigate their morphological and structural characterizations. SERS measurements were performed for all silver growth times to understand the effect of the silver growth process and hybrid structure synergy on SERS performance. The Ag@ZnO hybrid structure, cultivated with 24-hour silver growth, exhibited remarkable detectability even at an ultra-low R6G concentration of 10 pM

Physical and sensing characterization of nanostructured Ag doped TiO2 thin films

On glass substrates, silver (Ag) doped Titanium dioxide (TiO2) films at varied levels of concentrations (0, 2, and 4) % wt were synthesized by chemical spray pyrolysis (CSP). As per the X-ray diffraction pattern, the only phases present in the sample were anatase and rutile TiO2. Using AFM, it was discovered that the TiO2 thin films were smooth and compact; however, the surface roughness increases as the dopant amount decreases. SEM images display TiO2 films. Surface transformation is evident with uniform spherical nanograins after Ag doping. The optical characteristics of wavelength range (300-900) nm have been investigated using absorbance and transmittance spectra. The results revealed that the films have a 65-75 % transmittance in VIS-NIR spectra for all films. The allowable direct electronic transitions have (3.15-3.25) eV energy gaps. At 250 ppm, the NH3 gas sensor exhibited increased resistance, indicating heightened sensitivity. Sensitivity decreases with concentration increases to 0 %, 2 %, and 4 % of Ag for NH3 gas. Reduction observed: 18.4% to 4.6% (50 ppm), 20.7% to 6.8% (150 ppm), and 25.9% to 8.2% (250 ppm).

Seed-Mediated Electrodeposition of Silver Nanowires and Nanorods.

Here, we compare the amount and morphology of silver (Ag) nanostructures electrodeposited at varied potentials and times in the presence of cetyltrimethylammonium bromide (CTAB) onto glass/indium tin oxide (glass/ITO) electrodes functionalized with mercaptopropyltrimethoxysilane (MPTMS) and coated or not coated with 4 nm average diameter Au nanoparticle (Au NP) seeds. There is a significantly larger amount of Ag deposited on the seeded electrode surface compared to that in the nonseeded electrode at potentials of -150 to -300 mV (vs Ag/AgCl) since the Au NP seeds act as catalysts for Ag deposition. At more negative overpotentials of -400 to -500 mV, the amount of Ag deposited on both electrodes is similar because the deposition kinetics are fast enough on glass/ITO that the Au seed catalyst does not make as big of a difference. Ag nanorods (NRs) and nanowires (NWs) form on the seeded surfaces, especially at more positive potentials, where deposition primarily occurs on the Au seed catalysts. Deposition of Ag onto the Au seeds appears as a separate peak in the voltammetry. This procedure mimics the seed-mediated growth of Ag NRs observed in solution in the presence of CTAB using ascorbic acid as a reducing agent. The yield, length, and aspect ratio of the Ag NRs/NWs depend on the deposition time and potential with the average length ranging from 300 nm to 3 μm for times of 30-120 min and potentials of -150 to -200 mV. The electrochemical seed-mediated growth of Ag NRs/NWs across electrode gaps could find use for resistive and surface-enhanced Raman-based sensing and molecular electronic applications.

Selective Flocculation and H2O2-Free Oxidative Etching-Based Synthesis of Highly Monodisperse Ag Nanospheres for Uniform Quantum Dot Photoluminescence-Enhancing Plasmonic Cavity Applications.

Ag nanoparticles have garnered significant attention for their excellent plasmonic properties and potential use as plasmonic cavities, primarily because of their intrinsically low ohmic losses and optical properties in the visible range. These are particularly crucial in systems involving quantum dots that absorb light at low wavelengths, where the need for a high threshold energy of interband transitions necessitates the incorporation of Ag nanostructures. However, the synthesis of Ag nanoparticles still encounters challenges in achieving structural uniformity and monodispersity, along with chemical stability, consequentially inducing inconsistent and poorly reliable optical responses. Here, we present a two-step approach for synthesizing highly uniform spherical Ag nanoparticles involving depletion-induced flocculation and Cu(II)-mediated oxidative etching. We found that the selective flocculation of multitwinned Ag nanocrystals significantly enhances the uniformity of the resulting Ag nanostructures, leaving behind only single-crystalline and single-twinned nanostructures. Subsequent oxidative etching, in which cupric ions are directly involved in the reaction, was designed based on Pourbaix diagrams to proceed following thermodynamically favorable states and circumvent the generation of reactive chemical species such as H2O2. This leads to perfectly spherical shapes of final Ag nanoparticles with a synthetic yield of 99.5% and additionally reduces the overall reaction time. Furthermore, we explore the potential applications of these monodisperse Ag nanospheres as uniform plasmonic cavities. The fabricated Ag nanosphere films uniformly enhanced the photoluminescence of InP/ZnSe/ZnS quantum dots, showcasing their capabilities in exhibiting consistent plasmonic responses across a large area.

Synthesis and Reduction Processes of Silver Nanowires in a Silver(I) Sulfamate-Poly (Vinylpyrrolidone) Hydrothermal System.

Silver (Ag) nanowires, as an important one-dimensional (1D) nanomaterial, have garnered wide attention, owing to their applications in electronics, optoelectronics, sensors, and other fields. In this study, an alternative hydrothermal route was developed to synthesize Ag nanowires via modified reduction of Ag+. Silver sulfamate plays an important role in the formation of Ag nanowires via controlled release of free Ag+. Results of controlled experiments and characterizations such as UV-vis spectroscopy, FTIR, XPS, and 1H NMR revealed that sulfamic acid does not function as a reductant, supporting by the generation of free Ag+ instead of Ag nanostructures in hydrothermally treated silver sulfamate solution. The initial reduction of Ag+ was induced by the combination of poly (vinylpyrrolidone) (PVP) end group and degradation products. This phenomenon was supported by abundant free Ag+ in the mixed preheated silver sulfamatic and preheated PVP aqueous solutions, indicating a second and distinct Ag+ autocatalytic reduction. Thus, the roles of different reagents and Ag+ reduction must be studied for nanomaterial syntheses.

Preparation of Tunable Cu−Ag Nanostructures by Electrodeposition in a Deep Eutectic Solvent

AbstractThe green transition requires new, clean, inexpensive, and sustainable strategies to prepare controllable bimetallic and multimetallic nanostructures. Cu−Ag nanostructures, for example, are promising bimetallic catalysts for different electrocatalytic reactions such as carbon monoxide and carbon dioxide reduction. In this work, we present the one‐step preparation method of electrodeposited Cu−Ag with tunable composition and morphology from choline chloride plus urea deep eutectic solvent (DES), a non‐toxic and green DES. We have assessed how different electrodeposition parameters affect the morphology and composition of our nanostructures. We combine electrochemical methods with ex‐situ scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), and X‐ray photoelectron spectroscopy (XPS) to characterize the nanostructures. We have estimated the electrochemically active surface area (ECSA) and roughness factor (R) by lead underpotential deposition (UPD). The copper/silver ratio in the electrodeposited nanostructures is highly sensitive to the applied potential, bath composition, and loading. We observed that silver‐rich nanostructures were less adherent whereas the increase in copper content led to more stable and homogenous films with disperse rounded nanostructures with tiny spikes. These spikes were more stable when the deposition rate was fast enough and the molar ratio of Cu and Ag was no greater than approximately two to one.