Debye temperature decrease, residual resistivity increase and electron-phonon coupling constant increase as crystallite size decreases have been found from electrical resistivity in temperature range 5 K to 300 K of well-characterized Ag nanoparticles synthesized with oleylamine, trioctylphosphine and/ polyvinylpyrrolidone with Scherrer sizes ranging from 15.1 nm to 33.4 nm. Notably, about 36 % reduction in Debye temperature in 15.1 nm compared to bulk Ag is found. Remarkably, usual phonon drag peak found in Seebeck coefficient for bulk Ag turned into dips or phonon drag minima in these NPs that gradually gets suppressed and shifted towards lower temperature with decrease in crystallite size in oleylamine and trioctylphosphine-induced NPs. Contrastingly, it appears at higher temperature in trioctylphosphine-induced nanoparticles. A broad hump between 125 K to 215 K, a slope change near 270 K in resistivity and an additional dip-like feature near 172 K in Seebeck coefficient are seen in oleylamine-polyvinylpyrrolidone-induced nanoparticles with different shapes. They are attributed to spatial confinement of electrons and phonons, varying barrier heights, different charge-transfer mechanisms among metal nanoparticles and surfactant/s, enhanced disorders (grain boundaries, increase in fraction of surface atoms, surfactant matrix and other defects), leading to modifications in their overall electron and phonon interactions. Finally, their thermoelectric power factor has also been assessed.
It was recently suggested that molecular junctions would be excellent elements for efficient and high-power thermoelectric energy conversion devices. However, experimental measurements of thermoelectric conversion in molecular junctions have indicated rather poor efficiency, raising the question of whether it is indeed possible to design a setup for molecular junctions that will exhibit enhanced thermoelectric performance. Here we suggest that hybrid single-molecule nanoparticle junctions can serve as efficient thermoelectric converters. The introduction of a semiconducting nanoparticle introd…
The observation of intense visible fluorescence from silver and iron nanoparticles in different solution phases and surface capping is reported here. Metallic silver and iron nanoparticles were obtained by exploding pure silver and iron wires in pure water. Bovine serum albumin protein adsorption on the silver nanoparticles showed an enhanced fluorescence. The presence of poly-vinyl pyrrolidone polymer in the exploding medium resulted in a stabilized growth of iron nanoparticles with enhanced fluorescence intensity. The fluorescence was found to be surface /interface dependant. The fluorescenc…
We report the enhancement of the optical second harmonic signal in non-centrosymmetric semiconductor CdS quantum dots, when they are placed in close contact with isolated silver nanoparticles. The intensity enhancement is about 1000. We also show that the enhancement increases when the incoming laser frequency $ω$ is tuned toward the spectral position of the silver plasmon at $2ω$, proving that the silver nanoparticle modifies the nonlinear emission.
Raza et al. recently observed the extraordinarily large energy blueshifts of localized surface plasmon resonances and additional surface plasmon resonances in silver nanoparticles encapsulated in silicon nitride, which are not fully understood yet. By using the quantum model consisting of two subsystems respectively for describing the center of mass and intrinsic motions of conduction electrons of a metallic nanosphere and a coupling occurred between the center of mass and conduction electrons outside the metallic nanosphere, we firstly deduced the general energy and line broadening size-depen…
We present a simple method to prove the presence of an organic shell around silver nanoparticles. This method is based on the comparison between optical extinction measurements of isolated nanoparticles and Mie calculations predicting the expected wavelength of the Localized Surface Plasmon Resonance of the nanoparticles with and without the presence of an organic layer. This method was applied to silver nanoparticles which seemed to be well protected from oxidation. Further experimental characterization via Surface Enhanced Raman Spectroscopy (SERS) measurements allowed to identify this prote…
In the present work, the formation of silver and copper nanostructures on highly oriented pyrolytic graphite (HOPG) modified with self-assembled gold nanoparticles (Au NPs) is demonstrated. Surface patterning with nanometer resolution was achieved. Different methods such as field emission scanning electron microscopy (FEGSEM), energy dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS) were used to illustrate a selective deposition of silver and copper on Au NPs. The mechanism of silver and copper ions reduction on Au NP with $n$-dodecanethiol coating is discussed.
Terahertz time domain spectroscopy has been used to study low frequency confined acoustic phonons of silver nanoparticles embedded in poly(vinyl alcohol) matrix in the spectral range of 0.1 to 2.5 THz. The real and imaginary parts of the dielectric function show two bands at 0.60 THz and 2.12 THz attributed to the spheroidal and toroidal modes of silver nanoparticles, thus demonstrating the usefulness of terahertz time domain spectroscopy as a complementary technique to Raman spectroscopy in characterizing the nanoparticles.
A numerical method for calculation electronic structure of a nanosystem composed of a pseudoisocyanine (PIC) molecule assembled on a silver nanoparticle is developed. The electronic structure of the silver nanoparticle containing 125 atoms is calculated within the local density version of the density functional method. A model of an Ag atom embedded in the center of a spherical jellium cluster is used. The host electron Green function is calculated by means of the spherically symmetric expansion. The principal theoretical tool is the scattering theory using the Green function method. The molec…
We show that silver nanoparticles, which are deposited on a terahertz-receiving antenna, can be sintered by intense terahertz pulse irradiation. The conductance of the silver nanoparticles between the antenna electrodes is measured under the terahertz pulse irradiation. The dispersant materials surrounding the nanoparticles are peeled off, and conduction paths are created. We reveal that, during sintering, quantum point contacts are formed, leading to quantized conductance between the electrodes with the conductance quantum, which reflects the formation of atomically thin wires. The terahertz …
For the first time in the world behavioral functions of laboratory mammals exposed to silver nanoparticles were studied with the regard to age. Silver nanoparticles coated with polyvinylpyrrolidone with the size of 8.7 nm were used in the present research as a potential xcenobiotic. Elder mice adapted to the xcenobiotic better than younger animals. Younger animals demonstrated more drastic anxiety than the elder ones. Thus, it is concluded that adaptive homeostasis non-linearly changes with the age. Presumably, it may improve during the prime of life and start to decline just after certain sta…
The influence of the daily prolonged administration of silver nanoparticles on cognitive functions of model mammals was studied. The accumulation of silver in whole brain, hippocampus, cerebellum, cortex and residual part of mice brain was investigated by highly precise and representative Neutron Activation Analysis and the histological studies were conducted in the present research. Some of the main results of the comprehensive study are the description of the biokinetics of silver in the hippocampus, cerebellum and cortex, the finding of the jump increase of silver in the hippocampus and cer…
Reflection of near-infrared light is important for preventing heat transfer in energy saving applications. A large-area, mass-producible reflector that contains randomly distributed disk-shaped silver nanoparticles and that exhibits high reflection at near-infrared wavelengths was demonstrated. Although resonant coupling between incident light and the nanostructure of the reflector plays some role, what is more important is the geometrical randomness of the nanoparticles, which serves as the origin of a particle-dependent localization and hierarchical distribution of optical near-fields in the…
We numerically simulate, using finite-difference time-domain, the optical properties of silver nano discs deposited on the front surface of silicon solar cells. We explore the effect of each of the parameters of such a system, in order to draw some general design rules for the subsequent fabrication of such structures.
Individual highly pure single crystalline silver nanowires (Ag NWs) were investigated with regard to the electrical conductivity $σ$, the thermal conductivity $λ$ and the Seebeck coefficient $S$ as function of the temperature $T$ between $1.4\,\mathrm{K}$ and room temperature (RT). Transmission electron microscopy was performed subsequently to the thermoelectric characterization of the Ag NWs, so that their transport properties can be correlated with the structural data. The crystal structure, surface morphology and the rare occurrence of kinks and twinning were identified. The thermoelectric …
In electron energy-loss spectroscopy (EELS) of individual silver nanoparticles encapsulated in silicon nitride, we observe besides the usual dipole resonance an additional surface plasmon (SP) resonance corresponding to higher angular momenta. We even observe both resonances for nanoparticle radii as small as 4 nm, where previously only the dipole resonance was assumed to play a role. Electron beams positioned outside of the particles mostly excite the dipole mode, but the higher-order resonance can even dominate the dipole peak when exciting at the particle surface, the usual choice for maxim…
In this work, we report X-ray photoelectron (XPS) and valence band (VB) spectroscopy measurements of surfactant-free silver nanoparticles and silver/linear carbon chains (Ag@LCC) structures prepared by pulse laser ablation (PLA) in water. Our measurements demonstrate significant oxidation only on the surfaces of the silver nanoparticles with many covalent carbon-silver bonds but only negligible traces of carbon-oxygen bonds. Theoretical modeling also provides evidence of the formation of robust carbon-silver bonds between linear carbon chains and pure and partially oxidized silver surfaces. A …
We study the magneto-optical response of noble metal nanoparticle clusters. We consider the interaction between the light-induced dipoles of particles. In the presence of a magnetic field, the simplest achiral cluster, a dimer, exhibits circular dichroism (CD). The CD of a dimer depends on the directions of the magnetic field and the light wave vector. The CD of a populous cluster weakly depends on the magnetic field. Upon scattering from the cluster, an incident linearly polarized light with polarization azimuth $φ$, becomes elliptically polarized. The polarization azimuth rotation and ellipt…
Parity is a ubiquitous notion in science and serves as a fundamental principle for describing a physical system. Nanometer-scale metal objects are predicted to show dramatic differences in physical properties depending on the electron-number parity. However, the identification of the electron-number parity effects in real metal nanoparticles has remained elusive because of the variations in various features of nanoparticles. Here we report the nuclear magnetic resonance (NMR) detection of the dynamic effect of the electron-number parity in silver nanoparticles. With theoretical modeling of the…
We study the optical responses of metal nanoparticle chains. Multiple scattering calculations are used to study the extinction cross sections of silver nanosphere chains of finite length embedded in a glass matrix. The transmission and reflection coefficients of periodic 2D arrays of silver nanospheres are also calculated to understand the interaction between nanoparticle chains. The results are in agreement with recent experiments. The splitting of plasmon-resonance modes for different polarizations of the incident light are explored. Results on the effect of disorder are also presented.
We study the surface plasmon (SP) resonance energy of isolated spherical Ag nanoparticles dispersed on a silicon nitride substrate in the diameter range 3.5-26 nm with monochromated electron energy-loss spectroscopy. A significant blueshift of the SP resonance energy of 0.5 eV is measured when the particle size decreases from 26 down to 3.5 nm. We interpret the observed blueshift using three models for a metallic sphere embedded in homogeneous background material: a classical Drude model with a homogeneous electron density profile in the metal, a semiclassical model corrected for an inhomogene…
Bimetallic plasmonic nanoparticles enable tuning of the optical response and chemical stability by variation of the composition. The present numerical simulation study compares Ag-Au alloy, Ag@Au core-shell, and Au@Ag core-shell bimetallic plasmonic nanoparticles of both spherical and anisotropic (nanotriangle and nanorods) shapes. By studying both spherical and anisotropic (with LSPR in the near-infrared region) shapes, cases with and without interband transitions of Au can be decoupled. Explicit comparisons are facilitated by numerical models supported by careful validation and examination o…
Compacted pellets of nanocrystalline nickel (NC-Ni) of average particle size ranging from 18 to 33 nm were prepared using a variety of surfactants. They were characterized well and were studied on the influence of the surfactants on the electrical resistivity and thermopower in the temperature range 5 to 300 K. It was found that the type of the surfactant used dominates over the average particle size in their electrical transport and the detail transport behaviors have been discussed. Moreover, the observed thermopower and resistivity features were contrasting compared to what are normally see…
We study the blueshift of the surface plasmon (SP) resonance energy of isolated Ag nanoparticles with decreasing particle diameter, which we recently measured using electron energy loss spectroscopy (EELS). As the particle diameter decreases from 26 down to 3.5 nm, a large blueshift of 0.5 eV of the SP resonance energy is observed. In this paper, we base our theoretical interpretation of our experimental findings on the nonlocal hydrodynamic model, and compare the effect of the substrate on the SP resonance energy to the approach of an effective homogeneous background permittivity. We derive t…
The evidence of strong coupling between plasmons and molecular excitons for plasmonic nanoparticle (NP) dimers exhibiting ultra-sensitive surface enhanced resonant Raman scattering is the observation of anti-crossing in the coupled resonance. However, it is not easy to experimentally tune plasmon resonance of such dimers for the observation. In this work, we theoretically investigate the anti-crossing properties of the dimers coated by the thin dye films with thicknesses greater than 0.1 nm and gap distances larger than 1.2 nm according to the principles of classical electromagnetism. The plas…
The "metallic" temperature variation of the electrical resistivity of chemical nano gold-silver coatings with a silver content of 6.6 % at. up to 13.1 % at. determined in the temperature range 4.2-300 K. Features of low-temperature measurements of the resistance of nano-coatings were found and explained. The possibility of the appearance of superconductivity in them is discussed.
A composite material is considered which consists of conducting nanoparticles separated by tunneling dielectric barriers. The influence of the phonon thermal conductivity of dielectric matrix on the thermoelectric figure of merit of this composite material is theoretically in-vestigated. The range of values and barrier parameters that can lead to the thermoelectric figure of merit greater than unity is estimated. The influence of space charge and nonlinearity of current-voltage relations of tunneling barrier are also discussed.
Realizing strong light-matter interactions between individual 2-level systems and resonating cavities in atomic and solid state systems opens up possibilities to study optical nonlinearities on a single photon level, which can be useful for future quantum information processing networks. However, these efforts have been hampered by the unfavorable experimental conditions, such as cryogenic temperatures and ultrahigh vacuum, required to study such systems and phenomena. Although several attempts to realize strong light-matter interactions at room-temperature using so-called plasmon resonances h…
Quantum nanosystems involve the coupled dynamics of fermions or bosons across multiple scales in space and time. Examples include quantum dots, superconducting or magnetic nanoparticles, molecular wires, and graphene nanoribbons. The number (10^3 to 10^9) of electrons in assemblies of interest here presents a challenge for traditional quantum computations. However, results from deductive multiscale analysis yield coarse-grained wave equation that capture the longer-scale quantum dynamics of these systems; a companion short-scale equation is also developed that allows for the construction of ef…
Plasmonic color printing with semicontinuous metal films is a lithography-free, non-fading, and environment-friendly method of generation of bright colors. Such films are comprised of metal nanoparticles, which resonate at different wavelengths upon light illumination depending on the size and shape of the nanoparticles. To achieve an experimentally demonstrated structure that was optimized in terms of broader color range and increased stability, variable Ag semicontinuous metal films were deposited on a metallic mirror with a sub-wavelength-thick dielectric spacer. Femtosecond laser post-proc…
We image the field enhancement at Ag nanostructures using femtosecond laser pulses with a center wavelength of 1.55 micrometer. Imaging is based on non-linear photoemission observed in a photoemission electron microscope (PEEM). The images are directly compared to ultra violet PEEM and scanning electron microscopy (SEM) imaging of the same structures. Further, we have carried out atomic scale scanning tunneling microscopy (STM) on the same type of Ag nanostructures and on the Au substrate. Measuring the photoelectron spectrum from individual Ag particles shows a larger contribution from higher…
We present a study of the morphology and the thermoelectric properties of short-pulse laser-sintered (LS) nanoparticle (NP) thin films, consisting of SiGe alloy NPs or composites of Si and Ge NPs. Laser-sintering of spin-coated NP films in vacuum results in a macroporous percolating network with a typical thickness of 300 nm. The Seebeck coefficient is independent of the sintering process and typical for degenerate doping. The electrical conductivity of LS films rises with increasing temperature, best described by a power-law and influenced by two-dimensional percolation effects.
We provide a microscopic approach to describe the onset of radial oscillation of a silver nanoparticle. Using the Heisenberg equation of motion framework, we find that the coupled ultrafast dynamics of coherently excited electron occupation and the coherent phonon amplitude initiate periodic size oscillations of the nanoparticle. Compared to the established interpretation of experiments, our results show a more direct coupling mechanism between the field intensity and coherent phonons. This interaction triggers a size oscillation via an optically induced electron density gradient occurring dir…
