Time evolution of Ag-Cu and Ag-Pd core-shell nanoclusters

The possibility of obtaining core-shell nanoparticles by depositing adatoms of a different element B above a cluster of an element A (system B/A) is studied by Molecular Dynamics simulations. We consider the four cases Ag/Cu, Cu/Ag, Ag/Pd and Pd/Ag, which present very different behaviours, and investigate whether it is possible to build up of well-defined core-shell structures.     

Controlled synthesis of CdS nanowires using diamines

We demonstrate a new, simple, inexpensive process and systemic control over CdS nanowires using sulfur powders and organic diamines without any catalysts, surfactants, and templates under atmospheric benchtop conditions. By changing the kinds of amines and reaction temperatures can result in control of the shape and size of the nanocrystals, which are moderately monodispered with unique forms.     

Non-crystalline structures in the growth of silver nanoclusters

The growth of nanometer-size free Ag clusters is studied by Molecular Dynamics simulations. The morphology transition from the icosahedron at the magic size of N = 55 atoms to the Marks truncated decahedron at N = 75 is analyzed in details, in order to single out kinetic trapping and entropic effects. At very low T, the cluster is kinetically trapped in an icosahedral structure. At intermediate T the transition takes place sharply at N≃ 65. At higher T, the transition is smeared out and finally, around 550 K no transition is found because the 75 decahedron is melted. Received 28 November 2000     

Temperature dependence of photoluminescence from mono-dispersed Si nanoparticles

The temperature dependence of photoluminescence (PL) from mono-dispersed Si nanoparticles was studied from 4 to 300 K. Si nanoparticles produced by pulsed laser ablation in He background gas were sorted into the 6 nm size range by a differential mobility analyzer (DMA). The spread of the size distribution was narrowed to a geometrical standard deviation _g = 1.05. On decreasing the temperature from 300 to 4 K, the intensity of the PL spectra increased gradually, peaked at about 60 K, and then decreased rapidly. The temperature dependences of the intensity and the full width at half maximum (FWHM) on the PL spectra are discussed in terms of radiative and nonradiative decay rates.     

Size dependence of the plasmon peak position in electron stimulated photon emission spectra of Ag clusters supported on amorphous carbon film

The plasmon energy of Ag clusters produced on an amorphous carbon substrate by gas-aggregation technique has been measured. It has been determined from the plasmon peak position in the light emission spectrum obtained during bombardment of Ag clusters by low-energy electrons. For Ag cluster films with maximum of the cluster size distribution at 30, 8 and 2.5 nm, the plasmon energy comprised 3.76, 4.13 and 4.28 eV (the wavelength was 330, 300 and 290 nm), respectively. The blue shift of the plasmon energy is probably related to the effect of confounding of collective and single-particle excitations.     

Fabrication and structural characterization of nanocomposites consisting of Ni nanoparticles dispersed in polyimide films

Formation and structure of composite layer consisting of polyimide films containing Ni nanoparticles were investigated. The preparation method relies on KOH treatment on polyimide film to form carboxyl acid groups and adsorption of Ni ions by ion exchange followed by hydrogen reduction. The amount of Ni ions adsorbed in polyimide films were found to be systematically controlled by changing initial KOH concentration, subsequent ion exchange time, pH and temperature. Cross-sectional TEM observation revealed that Ni nanoparticles with 3-5 nm in diameter were homogeneously dispersed in the surface modified polyimide layer after heat treatment above 250 ^°C in H₂ atmosphere. The size and distribution of the Ni nanoparticles were strongly dependent on the heat treatment temperature, indicating that this method allows microstructural tuning of metal/polymer nanocomposites.     

Vibrational spectroscopy of large water clusters of known size

The structure of large water clusters of known size distributions 〈n〉 = 20-2000 is investigated by vibrational spectroscopy of the OH stretch mode. The water clusters are predissociated by a pulsed tunable infrared optical parametrical oscillator (OPO) in the frequency range 2800-3800 cm^-1. Their fragments are detected off-axis by electron impact ionization and mass analyzed by a quadrupole mass spectrometer. The largest ion signal stems from the neutral water hexamer fragment. The ion yield is investigated at certain wavelengths while the size of the clusters is varied, and for certain sizes complete absorption spectra of the OH stretch motion are measured. Fingerprints of the different coordination types of the water molecules in the clusters are found and it turns out that our method is especially sensitive to amorphous structures with frequencies shifting in the range of 3300-3400 cm^-1.     

Electronic properties of transition-metal-atom doped Si cage clusters

We present a density-functional study of electronic structures of convex-caged Si clusters doped with transition-metal (TM) atoms. First, we show the reason for their peculiar geometries in terms of interplay among the electron orbitals of Si and TM atoms. Then we describe the potential ability of the clusters to serve as charge sources to other objects such as Si crystal surfaces. Millennium Research for Advanced Information Technology (MIRAI) Project.     

Melting, freezing and nucleation in nanoclusters of potassium chloride

Molecular dynamics simulations of the melting, freezing and nucleation are presented for unconstrained nanoclusters of KCl with a number of ions between 512 and 10648. The maximum extent of the probed liquid supercooling is analysed to the light of theoretical predictions and compared with experimental data. The fraction of the solid-like ions in the supercooled liquid is used as an indicator of heterogeneities within the liquid. Induced nucleation by seeding the supercooled liquid indicates that solid-liquid coexistence is stable, and sustained during the lifetime of the clusters, relatively to the supercooled liquid. A phenomenological analysis on the relaxation times of the crystal growth process is made. Critical nuclei sizes computed from the effectiveness of the seeds in the heterogeneous nucleation of the supercooled liquid, and from the residual crystallites in clusters not totally melted, are presented as a function of the temperature. The behavior of the systems is followed through various properties such as liquid and solid molar fractions, enthalpies of melting, heat capacities, self-diffusion coefficients and relaxation times related to the freezing process. The consistency of the simulation results for the heterogeneous nucleation is assessed by means of a classical nucleation model, from which an estimate of the interfacial surface tension is also worked out and compared with experimental data.     

Effect of epitaxial strain on the atomic structure of Pd clusters on MgO(100) substrate

Morphology and atomic structure of supported Pd clusters on MgO(100) substrate are investigated theoretically using a mixed approach: a semi-empirical potential for the metal bonding within the cluster and a potential fitted to ab initio calculations for the metal-oxide interaction. We find that the clusters adopt a truncated pyramidal morphology in agreement with experimental results. The detailed study of the epitaxial relation as a function of cluster size shows the existence of a critical size around 3 nm where elastic strain due to the misfit between the substrate and the deposit is released by the introduction of interfacial dislocations.     

Silver diffusion and precipitation of nanoparticles in glass by ion implantation

Silver particles in soda-lime glass, less than 10 nm in size, were prepared by ion implantation. The implantation dose was in the range of 0.5 to 2×10¹⁶ Ag ions/cm² and the beam current density was varied from 0.5 to 2A/cm². Here, the beam current density strongly influences ion diffusion and particle precipitation as well as compressive stress generation around the particles due to thermal effects resulting from the deceleration of silver ions. Stress relaxation can be achieved by increased dose rates or thermal processing at elevated temperatures. Based on RBS and HREM results, a possible route to homogeneous distribution of Ag nanoparticles within the glass is discussed with respect to their interesting optical properties.     

Photoemission spectra of deuterated silicon clusters: experiment and theory

We compare experimentally measured and ab initio computed photoelectron spectra of negatively charged deuterated silicon clusters ( , 4m10, 0n2) produced in a plasma environment. Based on this comparison, we discuss the kinetics and thermodynamics of the cluster formation and the effect of deuterium on the geometrical and electronic structure of the clusters.     

Novel synthesis, structure and catalysis of inverted core/shell structured Pd/Pt bimetallic nanoclusters

The catalytic properties of Pd-core/Pt-shell (inverted core/shell) structured bimetallic nanoclusters, synthesized by a successive addition method using sacrificial hydrogen, were investigated for hydrogenation of methyl acrylate. Partial deposition of Pt atoms on the surface of Pd nanoclusters can enhance the catalytic activity of the Pd atoms remaining in the surface of the inverted core/shell structured Pd/Pt bimetallic nanoclusters. Received 29 November 2000     

Energetics and electronic properties of BN nanocones with pentagonal rings at their apexes

The geometric structures, energetics and electronic properties of the recently discovered BN nanocones are investigated using first-principles calculations based on the density-functional theory. We have proposed one particular structure for BN nanocones associated with the 240^° disclination, derived by the extraction of four 60^° segments, presenting as characteristic four pentagons at the apex and termination in two atoms. The cones are simulated by three clusters containing 58 B plus N atoms and additional 12 H atoms to saturate the dangling bonds at the edge. The most stable configuration is obtained when the two terminating atoms are one B and one N. For the cases where the two terminating atoms are of the same kind, the tip with B atoms is determined to have lower binding energy than with N atoms. The local densities of states of these BN nanocones are investigated and sharp states are found in the regions close (below and above) to the Fermi energy. Received 14 October 2002 / Received in final form 6 December 2002 Published online 11 February 2003 RID="a" ID="a"e-mail: ppiquini@smail.ufsm.br     

Silicon-riched-oxide cluster assembled nanostructures formed by low energy cluster beam deposition

Free beam of silicon oxide nanoclusters is produced by a gas aggregation source from SiO precursor. Due to the disproportionation reaction during the condensation of SiO vapor the generated clusters are Si-riched. The clusters are collimated to be a fine beam and deposited on the substrate at room temperature. The microstructures of the cluster-based nanofilm are characterized by TEM. It is shown that with appropriate impacting parameters, Si-riched oxide nanofilms assembled from uniformly distributed isolated clusters can be obtained. And the clusters can self-organize into partially densely ordered packing within local domains. XPS spectra are taken to analyze the chemical components of the nanofilms. Photoluminescence from the Si-riched oxide nanofilms has also been observed.     

Surface-enhanced luminescence from Eu 3+ complex nearby Ag colloids

The effect of colloidal dispersion of silver on the luminescent properties of Eu (III) complex with pyridine-3,5-dicarboxylic acid (PyDC) was investigated. The luminescence from Förster type europium complex was enhanced several times with the presence of Ag colloid and the enhancement factor showed Ag concentration dependence. The observed enhancement effect was discussed in view of surface-enhancement effect and optical absorption due to surface plasmon resonance, both arising from excitation of surface plasmon polariton. The coordination structure around Eu (III) ion was also affected with the presence of Ag colloid, which induced the change in the intensity ratio between two emission bands of ⁵ D ₀ ⁷ F ₁ and ⁵ D ₀ ⁷ F ₂ transitions of Eu (III) ion.     

Preparation of Cu 2 O nanoparticles dispersed in NH 2 -terminated polyethyleneoxide matrix

Small Copper (I) oxide, Cu₂O, nanoparticles dispersed in diamine-terminated polyethyleneoxide (PEO-NH₂) matrix have been successfully prepared by vacuum evaporation of copper onto the molten PEO-NH₂. The obtained composite were characterized by TEM, electron diffraction, TG-DTA and FT-IR spectroscopy. The stable composite, in which the Cu₂O nanoparticles are stabilized through interaction between NH₂ chain end groups of PEO molecules and Cu₂O nanoparticles was obtained when the samples were heat-treated at 110 ^° C. The mean size of the Cu₂O nanoparticles increased from 2.5 to 3.5 nm in diameter upon increasing the amount of initial Cu deposition. The obtained composite material having a waxy texture was soluble in many solvents without aggregation and can be handled as a simple chemical compound for starting material in various applications. Received 29 November 2000     

Formation and stability of large B 6 O clusters with icosahedral structure

In this paper, the formation and the stability of large B₆O icosahedral particles was discussed on the basis of elastic deformation theory. Our calculation illustrate the stability of macroscopic Mackay packing B₆O icosahedral particles at high pressure. The transition pressure from rhombohedral structure of B₆O particles to macroscopic B₆O icosahedral ones was calculated to be 6 GPa, which is in good agreement with the experimental data (4.0-5.52 GPa). The maximum diameter of B₆O icosahedral particles at low pressure is estimated to be 200-300 nm. Received 30 November 2000     

Production of gold nanoparticles-polymer composite by quite simple method

Recently, production methods of metal nanoparticles have been investigated extensively, not only for a research use in laboratory, but also for an industrial use. However, it is difficult to obtain metal nanoparticles in high amounts and concentrations with simple methods. In this study, a gold nanoparticle-polymer composite was prepared with a simple procedure using a gold salt and a melted polymer. The composite, which is in a wax state at room temperature, was highly soluble in water and lower alcohols, moreover the composite was melted at about 50 ^°C.