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.     

Preparation and properties of nano-sized Ag and Ag2S particles in biopolymer matrix

Silver (Ag) and silver sulfide (Ag₂S) nanoparticles were synthesized in a sago starch matrix. The resulting nanocomposites were investigated using structural, optical and thermal methods. XRD spectra of the nanocomposites confirmed the presence of nanostructured silver (cubic phase) and silver sulfide (monoclinic phase) in the matrix. TEM micrographs showed that the nanoparticles are mostly spherical in shape. Analyzes of the optical properties of the silver nanocomposite aqueous dispersions/solutions of various concentrations were carried out. The results and the theoretical considerations suggested that at high concentrations there is a release of silver nanoparticles from the composite in the water environment. Further dilution produces homogeneous solution in which silver nanoparticles are capped with starch macromolecules. TGA analysis revealed reduced thermal stability of the nanocomposites with respect to pure starch matrix.     

Excitonic absorption of spherical PbS nanoparticles in zeolite A

We report the optical and structural properties of PbS nanoparticles in zeolite A. The samples were obtained by sulfidation of the Pb²⁺ ion-exchanged zeolite in a thiourea solution at 50 °C. The optical properties of the samples were studied by diffuse reflectance spectroscopy. Their crystalline structure and morphology were studied by electron diffraction and by transmission and scanning electron microscopy. The results show that the nanoparticles are not inside the zeolite cages but outside, embedded in the zeolite matrix. Exciton absorption peaks at much higher energy than the fundamental absorption edge of bulk PbS indicate quantum confinement effects in the spherical shape nanoparticles as a consequence of their small size.     

An estimate of shape-distribution of small CdS particles with luminescence spectra

The luminescence spectra of CdS particles obtained by sedimentation method are studied. The comparison of measured and calculated photoluminescence spectra was used as the base of the method defining the shape distribution of the particles. For this purpose one can use the symmetry rule for absorption and luminescence spectra. Absorption spectra were calculated via dissipative function in terms of local field theory. The experimental spectra of the photoluminescence were measured during the process of sedimentation in the CdS nano-composite powder. The modification of luminescence spectra detected during sedimentation time is associated with changing the dimension and shape distributions of CdS suspension. As a result, the particles shape distribution was estimated for sizes less then 1 μm.     

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.     

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.     

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.     

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.     

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     

Third-order nonlinear optical response of Au:SiO 2 thin films: Influence of gold nanoparticle concentration and morphologic parameters

We report a study on the third-order nonlinear optical properties of nanocomposite thin films composed of gold particles embedded in a silica host matrix. Samples of various metal volume fractions, ranging from 8 to 35%, are synthesized by the sputtering technique. Some of them are annealed. Nonlinear optical measurements, which are performed by using the z-scan technique, reveal both a very large nonlinear absorption and a weak nonlinear refraction close to the surface plasmon resonance frequency of the particles. We especially study the effect of the metal concentration and the influence of thermal treatment on the real and imaginary components of the third-order nonlinear susceptibility. Our results reveal that, as the metal concentration reaches a few percent, the mutual electromagnetic interactions between particles greatly enlarge the nonlinear optical response of the material and can not be neglected in the theoretical analysis. Moreover, the thermal treatment leads, for a given concentration, to a significant increase of the nonlinear response, which is ascribed to a modification of the material morphology. We finally point out that the material nonlinear properties are very sensitive to the incident wavelength through the local field enhancement phenomenon. Received 12 December 2001     

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     

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.     

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.     

Dispersion and alignment of carbon nanotubes in polycarbonate

Dispersion and alignment of carbon nanotubes in thermoplastic polymers such as polycarbonate have been studied. Dispersion was accomplished by mixing in a conical twin-screw extruder and alignment was carried out using a fiber-spinning apparatus. The effects of mixing time and fiber draw rates on dispersion and alignment were investigated. Uniform dispersions were produced with relatively short residence times in the extruder. Excellent alignment of carbon nanotubes in nanocomposite filaments was obtained when the fiber draw rate was greater than 70 m/min. The ability to closely control the dispersion and alignment of carbon nanotubes in polymers is expected to lead to the development of nanocomposites with desirable electronic and structural properties. Received: 7 January 2002 / Accepted: 11 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-508/233-5521, E-mail: Michael.Sennett@natick.army.mil     

Titania from nanoclusters to nanowires and nanoforks

A novel method - inverse microemulsion has been developed not only for synthesizing low cost TiO₂ nanoclusters but also for the first time preparing titania nanowires and nanoforks with rutile structure of single crystal. With two microemulsion systems, spherical TiO₂ nanoclusters of 5 nm in average diameter are produced. These nanoclusters are amorphous and turned into anatase at an annealing temperature lower than 750 ^°C, and changed into rutile when annealed at higher temperature. When three microemulsions with TiCl₄, ammonia and NaCl as aqueous phase, are used, the precursor powder containing Ti(OH)₄/NaCl with molar ratio of 1000 are annealed at 750 ^°C and then TiO₂ rutile nanowires with 22 nm in thickness and 4 m in length are formed. At the same time two kinds of nanoforks with defined boundary structures are constructed: one is a bent wire composed of two straight whiskers related by twinning on a (101) plane with the angle of 114^° between the two legs, and the other by twinning on a (301) planes with the angle of 55^° between the legs. Screw dislocations and a periodic structure are found in (301) twin boundary, while edge dislocations are observed in (101) twin boundaries.The experiments demonstrate that the titania rutile nanowires are formed through solid state phase transformation and sodium chloride play an important role in the process.     

Phase behavior of organic-inorganic crystal

We have investigated the structure and phase behavior of nonmolecularly layered silver stearate by means of temperature-dependent diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. Upon heating the sample, remarkable spectral changes took place. The first phase transition took place that might be associated with a premelting event characterized by the formation of gauche conformers at 390-420 K. A second phase transition took place in which silver nanoparticles with a size of ∼4 nm were formed by thermal decomposition of silver stearate at 520-550 K. These silver nanoparticles, derivatized by stearate, were readily spread as a monolayer at air/water interface, and could be packed in 3-D assemblies by the Langmuir-Blodgett method. Received 29 November 2000     

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.     

Molecular dynamics simulations of the freezing of gold nanoparticles

A set of molten gold clusters, each with 1157 gold atoms, was studied by molecular dynamics simulations as the clusters underwent freezing at three different temperatures. Most of the clusters attained an icosahedral structure upon freezing, a structure found to be stable to mild annealing. Other structures observed were imperfect truncated decahedral, truncated octahedral and hexagonal close packed structures. The role of kinetics in the process of cluster solidification is discussed. Received 6 November 2000