Refractive Index Sensitivity Analysis of Ag, Au, and Cu Nanoparticles

The localized surface plasmon resonance (LSPR) spectrum of noble metal nanoparticles is studied by quasi-static approximation. Taking the sensitivity of LSPR shape to the size and shape of nanoparticle along with surrounding refractive index, parameters like refractive index sensitivity and sensing figure of merit have been determined. In the present analysis from the sensing relevant parameters, it is concluded that Ag represents a better sensing behavior than Au and Cu over the entire visible to infrared regime of EM spectrum.     

DNA Detection Based on Localized Surface Plasmon Resonance Spectroscopy of Ag@Au Biocomposite Nanoparticles

Noble metal nanoparticles (NPs) have attracted much attention due to their unique physical and chemical properties such as tunable surface plasmonics, high-efficiency electrochemical sensing, and enhanced fluorescence. We produced two biosensor chips consisting of Ag@Au bimetallic nanoparticles (BNPs) on a carbon thin film by simple RF-sputtering and RF-plasma-enhanced chemical vapor co-deposition. We deposited Au NPs with average size of 4 nm (Au₁ NPs) or 11 nm (Au₂ NPs) on a sensor chip consisting of Ag NPs with mean size of 15 nm, and we investigated the effect of shell size (Au NPs) on the chemical activities of the resulting Ag@Au₁ BNPs and Ag@Au₂ BNPs. We estimated the average size and morphology of Ag@Au BNPs by scanning electron microscopy (SEM) and atomic force microscopy (AFM) images. X-ray diffraction (XRD) patterns revealed that Ag NPs and Au NPs had face-centered cubic (FCC) structure. We studied aging of the biosensor chips consisting of Ag@Au BNPs by localized surface plasmon resonance (LSPR) spectroscopy for up to 3 months. UV–visible aging of the prepared samples indicated that Ag@Au₁ BNPs, which corresponded to Ag NPs covered with smaller Au NPs, were more chemically active than Ag@Au₂ BNPs. Furthermore, we evaluated changes in the LSPR absorption peaks of Ag@Au₁ BNPs and bare Ag NPs in the presence of a DNA primer decamer at fM concentrations, to find that Ag@Au₁ BNPs were more sensitive biosensor chips within a short response time as compared to bare Ag NPs.

     

Exploring Indian Rosewood as a promising biogenic tool for the synthesis of metal nanoparticles with tailor-made morphologies

Stem bark extracts of Indian Rosewood, a traditionally used Indian medicinal plant, were used as highly efficient multifunctional green chemicals/biogenic agents in the rapid synthesis of stable, monometallic Ag and Au nanoparticles and their corresponding bimetallic alloy nanoparticles with interesting shapes and morphological characteristics. We determined that the high efficiency of these extracts is due to the presence of complex multifunctional molecules, such as polyphenolics and hydroxyflavonoids, which are involved in the reduction of Au^III and Ag^I ions to zerovalent metallic nanoparticles and the stabilization of their corresponding nanoparticles.     

Vapor Phase Deposition, Structure, and Plasmonic Properties of Polymer-Based Composites Containing Ag–Cu Bimetallic Nanoparticles

Nanocomposite (NC) thin films with noble metal nanoparticles embedded in a dielectric material show very attractive plasmonic properties due to dielectric and quantum confinement effects. For single component nanoparticles (NPs), the plasmon resonance frequency can only be tuned in a narrow range. Much interest aroused in bimetallic nanoparticles (BNPs), however many wet chemical approaches do not allow large variation of the NP alloy composition and filling factor. Here, we report a vapor phase co-deposition method to produce polymer–metal NCs with embedded Ag_1 − x Cu _x alloy particles. The method allows production of NPs with controlled alloy composition (x), metal filling (f) and nanostructure in a protecting Teflon AF matrix. The nanostructure size and shape were characterized by transmission electron microscope. Energy dispersive X-ray spectroscopy was used to determine x and f. The optical properties and the position of surface plasmon resonances were studied by UV–Vis spectroscopy. The plasmon resonances can be tuned over a large range of the visible spectrum associated with the change in x, f, and nanostructure. For low filling factors and small particle sizes, only one resonance peak was observed. This is attributed to enhanced miscibility at the nanoscale. Double plasmon resonances were seen for larger particle sizes in accord with phase separation expected from the bulk phase diagram and were explained in terms of the formation of core-shell structures with Cu core and Ag shell. Changes upon annealing at 200 °C are also reported.     

Investigation on Optical Properties of Ag–Au Alloy Nanoparticles

The outstanding chemical stability of Au and intense localized surface plasmon resonance of Ag make it possible to obtain a nanostructure with a good balance of good chemical stability and optical response. In this paper, we investigated the relationship between optical properties and the composition and size of Ag–Au alloy nanoparticle with numerical calculation by applying experimental data. Simplified empirical formulas are proposed through numerical simulation. The properties of extinction efficiency and the relative contribution of scattering and absorption efficiency to the extinction efficiency have been researched in detail. The calculated result and experimental data has been compared, and good agreement is obtained. Our work contributes greatly to catalysis application of Au–Ag alloy NPs in specific regions.     

Correlated Optical Spectroscopy and Electron Microscopy Studies of the Slow Ostwald-Ripening Growth of Silver Nanoparticles under Controlled Reducing Conditions

Metallic nanoparticles display distinct localized surface plasmon resonance (LSPR) properties that depend on their size, shape, and composition and that can be monitored to characterize their growth. Utilizing LSPR properties, we report the first investigation of ambient temperature formation of trioctylamine (TOA)-stabilized spherical silver nanoparticles (AgNPs) of ～3.0-nm diameter by mild reduction of AgClO₄ with the weak reducing agent heptamethyltrisiloxane in organic solvent. The appropriate choice of experimental conditions caused slow reduction, which allowed the study of the nanoparticle growth process by time-resolved UV–visible spectroscopy and transmission electron microscopy (TEM). The linear nanoparticle growth kinetics from 50 min to end of the reaction derived from LSPR changes, the absence of a bimodal size distribution during the initial stage of the reduction process from TEM analysis, and the single crystallinity of the resulting AgNPs suggested a diffusion-controlled Ostwald-ripening growth process. It was also found that in addition to its stabilizing ability, TOA acted as a catalyst and facilitated Ag⁺ reduction. Furthermore, a modest increase in reaction temperature caused a substantial enhancement in the AgNP formation rate, and low concentration of stabilizing ligand yielded an increase in size and dispersity.     

Synthesis of a novel pyridine-diamino bridged diphosphine ligand and its macrocyclic metal complexes

A novel long chain diphosphine ligand with a pyridine-diamino bridge, 2,6-bis(N-benzyl-N-diphenylphosphinomethylamino)pyridine (PNP1), was prepared conveniently using the Mannich reaction of HPPh₂ with paraformaldehyde and 2,6-bis(N-benzylamino)pyridine in high yield. Reactions of the ligand with metal complexes, M(COD)Cl₂ (M = Pd, Pt), M(CH₃CN)₄ClO₄ (M = Cu, Ag) and M(CO)₆ (M = Mo, W) afforded the corresponding 10-numbered monometallic macrocyclic complexes with an uncoordinated pyridyl bridge. The monometallic chelate PdCl₂(PNP1) continued to react with Ag⁺ or Cu⁺ giving the μ-Cl bridged bicyclic metallic complex (μ-Cl)₂[PdCl(PNP1)]₂. The diphenylphosphine group coordinated with metal ion in cis-form in all the 10-numbered macrocyclic metal complexes. Ligand PNP1 and another known analogous 2,6-bis(N-diphenylphosphinoamino)pyridine (PNP2) reacted with Au(SMe₂)Cl giving the corresponding bimetallic Au₂Cl₂(PNP1) and Au₂Cl₂(PNP2), respectively. The latter bimetallic complexes continued to react with Ag⁺ and diphosphine ligand to give the corresponding bimetallic macrocyclic complexes Au₂(ligand)₂(ClO₄)₂. All the complexes were characterized and the structures of some complexes were confirmed by X-ray single crystallography determination.     

Rational Selection of Nanorod Plasmons: Material, Size, and Shape Dependence Mechanism for Optical Sensors

The localized surface plasmon resonance dependence on surrounding medium refractive index of Ag, Al, Au, and Cu nanoparticles is examined by electrodynamic approach. The refractive index sensitivity and sensing figure of merit (FOM) dependence of selected metal nanoparticles with similar geometry shows that although, sensing relevant parameters are shape (i.e., aspect ratio), and material dependent below the width 20 nm, but above this size these parameters are material independent under similar geometrical conditions. We have concluded that at optimum size, however, Al shows much higher refractive index sensitivity (RIS) in comparison to Au, Cu, and Ag, but FOM is higher for Ag in comparison to other metals. The observed sensing behavior is expected due to parameters like surface scattering, dynamic depolarization, radiation damping, and interband transitions, which may influence the nanorod plasmons.     

Photovoltaic Materials and Devices Based on the Alloyed Kesterite Absorber (AgxCu1–x)2ZnSnSe4

The photovoltaic absorber Cu₂ZnSn(S_xSe_1–x)₄ (CZTSSe) has attracted interest in recent years due to the earth‐abundance of its constituents and the realization of high performance (12.6% efficiency). The open‐circuit voltage in CZTSSe devices is believed to be limited by absorber band tailing caused by the exceptionally high density of Cu/Zn antisites. By replacing Cu in CZTSSe with Ag, whose covalent radius is ≈15% larger than that of Cu and Zn, the density of I–II antisite defects is predicted to drop. The fundamental properties of the mixed Ag‐Cu kesterite compound are reported as a function of the Ag/(Ag + Cu) ratio. The extent of band tailing is shown to decrease with increasing Ag. This is verified by comparing the optical band gap extrapolated from transmission data with the position of the room‐temperature photoluminescence peak; these values converge for the pure‐Ag compound. Additionally, the pinning of the Fermi level in CZTSSe, attributed to heavy defect compensation and band tailing, is not observed in the pure‐Ag compound, offering further evidence of improved electronic structure. Finally, a device efficiency of 10.2% is reported for a device containing 10% Ag (no antireflection coating); this compares to ≈9% (avg) efficiency for the baseline pure‐Cu CZTSe.     

Surface Plasmon-Enhanced Spontaneous Emission from InGaN/GaN Multiple Quantum Wells by Indium Nanoparticles Fabricated Using Nanosphere Lithography

Economic nanofabrication of Ag, Al, Au nanotriangle arrays and In nanoparticle arrays are demonstrated using nanosphere lithography. The sizes of the nanoparticles are precisely tuned when nanospheres with different diameters are used. Localized surface plasmon resonances (LSPR) of the nanoparticle arrays are observed to be strongly dependent on their sizes and the LSPR of In nanoparticle arrays with various sizes cover the whole visible spectrum. By placing In nanoparticle arrays near the InGaN/GaN multiple quantum wells (MQWs), enhanced spontaneous emission is observed when the LSPR of the In nanoparticles matches the emission wavelength of InGaN/GaN MQWs.     

Preliminary results on the photoluminescence and optically stimulated luminescence in Cu‐doped and Ag‐doped ZnB2X4 (B = Li,Na, K: X = Cl,Br) compounds

Photoluminescence, and optically stimulated luminescence in ZnB₂X₄ (B; Li,Na,K: X; Cl,Br) compounds doped with Cu⁺ or Ag⁺ were studied. Double humped emission bands attributable to the activators were observed in all the samples. The observed photoluminescence of Cu⁺ and Ag⁺ could be identified with 3d⁹4s¹?3d¹⁰ and 4d⁹5s¹?5d¹⁰ transitions respectively. The longer wavelength band (400–500 nm range) could be attributed to the Cu⁺ or Ag⁺ ion replacing alkali ion at the octahedral alkali site whereas short wavelength band (340–400 nm range) is attributed to a Cu or Ag ion at tetrahedral zinc site. The short wavelength band was found to be intense compared with long wavelength and gave an indication that most of the Cu or Ag ions prefered a tetrahedral Zn site compared with the octahedral alkali site. All the samples exhibit optically stimulated luminescence (OSL). The sensitivity was found to be lattice dependent. The lowest sensitivity of about 1% compared with Al₂O₃:C was observed in lithium lattices whereas highest the sensitivity of about 290% was observed in the case of Cu‐doped ZnNa₂Br₄.     

Optimization of Carbon‐ and Binder‐Free Au Nanoparticle‐Coated Ni Nanowire Electrodes for Lithium‐Oxygen Batteries

A Au nanoparticle‐coated Ni nanowire substrate without binder or carbon is used as the electrode (denoted as the Au/Ni electrode) for Li‐oxygen (Li‐O₂) batteries. A minimal amount of Au nanoparticles with sizes of <30 nm on a Ni nanowire substrate are coated using a simple electrodeposition method to the extent that maximum capacity can be utilized. This optimized, one body, Au/Ni electrode shows high capacities of 921 mAh g^?1_Au, 591 mAh g^?1_Au, and 359 mAh g^?1_Au, which are obtained at currents of 300 mAg^?1_Au, 500 mAg^?1_Au, and 1000 mAg^?1_Au respectively. More importantly, the Au/Ni electrode exhibits excellent cycle stability over 200 cycles.     

Resonant Broadband Field Enhancement in Cylindrical Plasmonic Structure Surrounded by Perovskite Environment

We demonstrate the optical response of metal nanoparticles and their interaction with organic-inorganic perovskite (methyl ammonia lead halide (CH₃NH₃PbI₃)) environment using discrete dipole approximation (DDA) simulation technique. Important optical properties like absorption, scattering, and electric field calculations for metal nanoparticle using different geometry have been analyzed. The metal nanoparticles embedded in the perovskite media strongly support surface plasmon resonances (SPRs). The plasmonic interaction of metal nanoparticles with perovskite matrix is a strong function of MNP’s shape, size, and surrounding environment that can manipulate the optical properties considerably. The cylindrical shape of MNPs embedded in perovskite environment supports the SPR which is highly tunable to subwavelength range of 400–800 nm. Wide range of particle sizes has been selected for Ag, Au, and Al spherical and cylindrical nanostructures surrounded by perovskite matrix for simulation. The chosen hybrid material and anisotropy of structure together make a complex function for resonance shape and width. Among all MNPs, 70-nm spherical silver nanoparticle (NP) and cylindrical Ag NP having diameter of 50 nm and length of 70 nm (aspect ratio 1.4) generate strong electric field intensity that facilitates increased photon absorption. The plasmonic perovskite interaction plays an important role to improve the absorption of photon inside the thin film perovskite environment that may be applicable to photovoltaics and photonics.

     

Antireflection TiO x Coating with Plasmonic Metal Nanoparticles for Silicon Solar Cells

It is known that the light scattering from the metal particles deposited on the surfaces of cells can be used for increasing light trapping in the solar cells. In this work, plasmonic structures are composite materials that consisted of silver nanoparticles embedded in dielectric films of TiO _x —used as cell antireflection coating. The films are deposited by sol–gel method using spin-on technique. Microstructure of prepared samples is analyzed by SEM observation. Good homogenity and particles density was obtained by this simple, cheap, and short time-demanding method. We demonstrate that due to light scattering by metal particles, the plasmonic-ARC layer is more effective than TiO _x layer without Ag nanoparticles. Implementation of nanoparticles on bare cell surface was carried out too. The influence of the plasmonic structures on the silicon solar cells parameters is presented as well. We announce about 5 % additional growth in short circuit current for cells with nanoparticles.     

A comparative theoretical study of the catalytic activities of Au<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> and AuAg<Superscript>-</Superscript> dimers for CO oxidation

The detailed mechanisms of catalytic CO oxidation over Au₂^- and AuAg^- dimers, which represent the simplest models for monometal Au and bimetallic Au-Ag nanoparticles, have been studied by performing density functional theory calculations. It is found that both Au₂^- and AuAg^- dimers catalyze the reaction according to the similar mono-center Eley–Rideal mechanism. The catalytic reaction is of the multi-channel and multi-step characteristic, which can proceed along four possible pathways via two or three elementary steps. In AuAg^-, the Au site is more active than the Ag site, and the calculated energy barrier values for the rate-determining step of the Au-site catalytic reaction are remarkably smaller than those for both the Ag-site catalytic reaction and the Au₂^- catalytic reaction. The better catalytic activity of bimetallic AuAg^- dimer is attributed to the synergistic effect between Au and Ag atom. The present results provide valuable information for understanding the higher catalytic activity of Au-Ag nanoparticles and nanoalloys for low-temperature CO oxidation than either pure metallic catalyst.     

Elucidation of the molecular and electronic structures of some magic silver clusters Ag<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 8, 18, 20)

Density functional theory (DFT) calculations were carried out to explore the geometric, spectroscopic, and electronic properties of three magic silver clusters Ag_n (n?=?8, 18, and 20) in detail. The computed results show that the global minima of these clusters are compact, near-spherical structures, while other low-lying isomers exhibit oblate or prolate shapes. Vertical ionization energies for the low-lying isomers were also computed and assigned with respect to available experimental values. Although several isomers were predicted to have similar energies, their electronic and vibrational signatures were quite distinctive, meaning that they could be used as fingerprint signals to distinguish between isomers. In addition, the electronic structures of these systems were explored using the phenomenological shell model. Calculations for the coinage metal clusters M₂₀ (M?=?Cu, Ag, Au) indicated that the structures and properties of the Ag cluster are similar to those of the Cu cluster in that both Cu₂₀ and Ag₂₀ prefer a compact structure whereas Au₂₀ prefers to adopt a tetrahedral form.

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Graphical abstract Shell Orbitals of Ag₈ Cluster

     

Influence of SiO<Subscript>2</Subscript> Spacer Layer Thickness on Performance of Plasmonic Textured Silicon Solar Cell

We investigated the effect of SiO₂ spacer layer thickness between the textured silicon surface and silver nanoparticles (Ag NPs) on solar cell performance using quantum efficiency analysis. Separation of Ag NPs from high index silicon with SiO₂ layer led to modified absorption and scattering cross-sections due to graded refractive index medium. The forward scattering from Ag NPs is very sensitive to SiO₂ layer thickness in plasmonic silicon cell performance due to the evanescent character of generated near-fields around the NPs. With the optimized ～30–40 nm SiO₂ spacer layer, we observed an enhancement of solar cell efficiency from ～8.7 to ～10 %, which is due to the photocurrent enhancement in the off-resonance surface plasmon region. We also estimated minority carrier diffusion lengths (L _eff) from internal quantum efficiency data, which are also sensitive to SiO₂ spacer layer thickness. We observed that the L _eff values are enhanced from ～356 to ～420 μm after placing Ag NPs on ～40 nm spacer layer due to improved forward (angular) scattering of light from the Ag NPs into silicon.     

Electronic, magnetic and optical properties of Cu, Ag, Au-doped Si clusters

The structural, optical and magnetic properties of Cu, Ag, Au-doped Si₇ Clusters have been systematically investigated using density functional theory calculations. The global optimized structures of Cu, Ag, Au-doped Si clusters are predicted to have a lower HOMO–LUMO gap and higher magnetic moment. M-doping (M?=?Cu, Ag, Au) in Si cluster widens a range of adsorption wavelength, especially Au-doping. The characteristics in electronic density of states (DOSs) show that C_5v-Si₆Cu has a big asymmetrical spin-up and spin-down. The average atomic moment is 0.428 mμ_B per atom for the Si₆Cu cluster with C_5v symmetry, while the average paramagnetic moment is 0.143 mμ_B per atom for other M-doped (M?=?Cu, Ag, Au) Si₇ clusters.     

Plasmon Responses in the Sodium Tungsten Bronzes

The sodium tungsten bronzes (Na _x WO₃) are vividly coloured metallic materials where the optical behaviour can be attributed to the bulk plasma frequency occurring in the visible part of the spectrum. A combination of density functional theory (DFT) calculations and experimental electron energy-loss spectroscopy (EELS) was used to assess their bulk and surface plasmon responses. It was observed that Na _x WO₃ can sustain strong localised surface plasmon resonances (LSPR) with an energy that can be tuned by changing the Na content. They have a stronger plasmonic response when compared to Au and do not suffer from the atmospheric corrosion of Ag, giving them good potential for plasmonic applications.     

Photoreduction of Silver Salts Using Au Nanoparticles to Form a Core-Shell-Type Nanostructure: Insight into the Reaction Mechanism

In this paper, we highlight the formation of Ag/Au core-shell nanoparticles at room temperature by using a low-power laser. We have investigated the plasmon-induced reduction of Ag⁺ ions on bare Au nanoparticles synthesized by laser ablation technique, and citrate-capped Au nanoparticles synthesized by chemical method. It is demonstrated that citrate plays an important role for the reduction of silver ions. The citrate gets oxidized by the ‘hot’ holes produced due to the surface plasmon resonance (SPR) of the Au nanoparticles which then reduces the Ag⁺ ions to Ag. The importance of excitation laser wavelength is also demonstrated to facilitate the reduction process.