Vibrational properties of nanometric AB(2) ionic clusters

A broad survey of harmonic dynamics in AB(2) clusters with up to N = 3000 atoms is performed using a simple rigid ion model, with ionic radii selected to give rutile as the ground state structure for the corresponding extended crystal. The vibrational density of states is already close to its bulk counterpart for N similar to 500, with characteristic differences due to surfaces, edges and vertices. Two methods are proposed and tested to map the cluster vibrational states onto the rutile crystal phonons. The net distinction between infrared (IR) active and Raman active modes that exists for bulk rutile becomes more and more blurred as the cluster size is reduced. It is found that, in general, the higher the IR activity of the mode, the more this is affected by the system size. IR active modes are found to spread over a wide frequency range for the finite clusters. Simple models based on either a crude confinement constraint or surface pressure arguments fail to reproduce the results of the calculations. The effects of the stoichiometry and dielectric properties of the surrounding medium on the vibrational properties of the clusters are also investigated.

Anisotropic optical properties of arrays of gold nanorods embedded in alumina

A series of thin films comprising gold nanorods embedded in an alumina matrix have been fabricated with lengths ranging from 75 to 330 nm. Their optical properties, expressed in terms of extinction - In(T), where T is optical transmittance, have been measured as a function of wavelength, rod length, angle of incidence, and incident polarization state. The results are compared to a Maxwell-Garnett based theory modified to take into account the strongly anisotropic nature of the medium. Transverse and longitudinal plasmon resonances are observed. The interaction between the nanorods leads to the splitting of the longitudinal resonance with the longer-wavelength resonance being forbidden for direct optical observations. The shorter-wavelength resonance related to the symmetric coupling between longitudinal plasma excitations in the nanorods depends on rod length, polarization state, and angle of incidence of the probing light. The impact of electron confinement on the optical properties of the gold rods is also seen and may be incorporated into the Maxwell-Garnett theory by restricting the mean free path of the conduction electrons to produce excellent agreement between observations and the complete theory. Annealing experiments that modify the physical structure of the gold confirm this conclusion.

Measurement and interpretation of the mid-infrared properties of single crystal and polycrystalline gold

The contribution of electron-phonon scattering and grain boundary scattering to the mid-IR (lambda = 3.392 mum) properties of An has been assessed by examining both bulk, single crystal samples-Au(1 1 1) and Au(1 1 0)-and thin film, polycrystalline An samples at 300 K and 100 K by means of surface plasmon polariton excitation. The investigation constitutes a stringent test for the in-vacuo Otto-configuration prism coupler used to perform the measurements, illustrating its strengths and limitations. Analysis of the optical response is guided by a physically based interpretation of the Drude model. Relative to the reference case of single crystal Au at 100 K (epsilon = - 568 + i17.5), raising the temperature to 300 K causes increased electron-phonon scattering that accounts for a reduction of similar to40 nm in the electron mean free path. Comparison of a polycrystalline sample to the reference case determines a mean free path due to grain boundary scattering of similar to 17 nm, corresponding to about half the mean grain size as determined from atomic force microscopy and indicating a high reflectance coefficient for the An grain boundaries. An analysis combining consideration of grain boundary scattering and the inclusion of a small percentage of voids in the polycrystalline film by means of an effective medium model indicates a value for the grain boundary reflection coefficient in the range 0.55-0.71. (C) 2005 Elsevier B.V. All rights reserved.

Relative energetics and structural properties of zirconia using a self-consistent tight-binding model

We describe an empirical, self-consistent, orthogonal tight-binding model for zirconia, which allows for the polarizability of the anions at dipole and quadrupole levels and for crystal field splitting of the cation d orbitals, This is achieved by mixing the orbitals of different symmetry on a site with coupling coefficients driven by the Coulomb potentials up to octapole level. The additional forces on atoms due to the self-consistency and polarizabilities are exactly obtained by straightforward electrostatics, by analogy with the Hellmann-Feynman theorem as applied in first-principles calculations. The model correctly orders the zero temperature energies of all zirconia polymorphs. The Zr-O matrix elements of the Hamiltonian, which measure covalency, make a greater contribution than the polarizability to the energy differences between phases. Results for elastic constants of the cubic and tetragonal phases and phonon frequencies of the cubic phase are also presented and compared with some experimental data and first-principles calculations. We suggest that the model will be useful for studying finite temperature effects by means of molecular dynamics.

The effect of flexoelectricity on the dielectric properties of inhomogeneously strained ferroelectric thin films

Recent experimental measurements of large flexoelectric coefficients in ferroelectric ceramics suggest that strain gradients can affect the polarization and permittivity behaviour of inhomogeneously strained ferroelectrics. Here we present a phenomenological model of the effect of flexoelectricity on the dielectric constant, polarization, Curie temperature (T-C), temperature of maximum dielectric constant (T-m) and temperature of the onset of reversible polarization (T-ferro) for ferroelectric thin films subject to substrate-induced epitaxial strains that are allowed to relax with thickness, and the qualitative and quantitative predictions of the model are compared with experimental results for (Ba0.5Sr0.5)TiO3 thin films on SrRuO3 electrodes. It is shown that flexoelectricity can play an important role in decreasing the maximum dielectric constant of ferroelectric thin films under inhomogeneous in-plane strain, regardless of the sign of the strain gradient.

Effect of quantization of vibrations on the structural properties of crystals

We study the structural effects produced by the quantization of vibrational degrees of freedom in periodic crystals at zero temperature. To this end we introduce a methodology based on mapping a suitable subspace of the vibrational manifold and solving the Schrödinger equation in it. A number of increasingly accurate approximations ranging from the quasiharmonic approximation (QHA) to the vibrational self-consistent field (VSCF) method and the exact solution are described. A thorough analysis of the approximations is presented for model monatomic and hydrogen-bonded chains, and results are presented for a linear H-F chain where the potential-energy surface is obtained via first-principles electronic structure calculations. We focus on quantum nuclear effects on the lattice constant and show that the VSCF is an excellent approximation, meaning that correlation between modes is not extremely important. The QHA is excellent for covalently bonded mildly anharmonic systems, but it fails for hydrogen-bonded ones. In the latter, the zero-point energy exhibits a nonanalytic behavior at the lattice constant where the H atoms center, which leads to a spurious secondary minimum in the quantum-corrected energy curve. An inexpensive anharmonic approximation of noninteracting modes appears to produce rather good results for hydrogen-bonded chains for small system sizes. However, it converges to the incorrect QHA results for increasing size. Isotope effects are studied for the first-principles H-F chain. We show how the lattice constant and the H-F distance increase with decreasing mass and how the QHA proves to be insufficient to reproduce this behavior.

Barrier height variations and interface properties of PtSi/Si structures

To study some of the interfacial properties of PtSi/Si diodes, Schottky structures were fabricated on (100) crystalline silicon substrates by conventional thermal evaporation of Pt on Si followed by annealing at different temperatures (from 400 degrees C to 700 degrees C) to form PtSi. The PtSi/n-Si diodes, all yielded Schottky barrier (SB) heights that are remarkably temperature dependent. The temperature range (20-290 K) over which the I-V characteristics were measured in the present study is broader with a much lower limit (20 K), than what is usually reported in literature. These variations in the barrier height are adequately interpreted by introducing spatial inhomogeneity into the barrier potential with a Gaussian distribution having a mean barrier of 0.76 eV and a standard deviation of 30 meV. Multi-frequency capacitance-voltage measurements suggest that the barrier is primarily controlled by the properties of the silicide-silicon interface. The forward C-V characteristics, in particular, show small peaks at low frequencies that can be ascribed to interface states rather than to a series resistance effect.

Large-scale density functional calculations of the surface properties of the Wigner crystal

The surface properties of the jellium model have been investigated by large supercell computations in the density functional theory-local spin-density (DFT-LSD) approach for planar slabs with up to 1000 electrons. A wide interval of densities has been explored, extending into the stability range of the Wigner crystal. Most computations have been carried out on nominally paramagnetic samples with an equal number of spin-up and spin-down electrons. The results show that within DFT-LSD spontaneous spin polarization and charge localization start nearly simultaneously at the surface for r(s) similar to 20, then, with decreasing density, they progress toward the center of the slab. Electrons are fully localized and spin polarized at r(s) = 30. At this density the charge distribution is the superposition of disjoint charge blobs, each corresponding to one electron. The distribution of blobs displays both regularities and disorder, the first being represented by well-defined planes and simple in-plane geometries, and the latter by a variety of surface defects. The surface energy, surface dipole, electric polarisability, and magnetization pattern have been determined as a function of density. All these quantities display characteristic anomalies at the density of the localization transition. The analysis of the low-frequency electric conductivity shows that in the fluid paramagnetic regime the in-plane current preferentially flows in the central region of the slab and the two spin channels are equally conducting. In the charge localized, spin-polarized regime, conductivity is primarily a surface effect, and an apparent asymmetry is observed in the two spin currents.

Linear and nonlinear properties of Rao-dust-Alfven waves in magnetized plasmas

The linear and nonlinear properties of the Rao-dust-magnetohydrodynamic (R-D-MHD) waves in a dusty magnetoplasma are studied. By employing the inertialess electron equation of motion, inertial ion equation of motion, Ampere's law, Faraday's law, and the continuity equation in a plasma with immobile charged dust grains, the linear and nonlinear propagation of two-dimensional R-D-MHD waves are investigated. In the linear regime, the existence of immobile dust grains produces the Rao cutoff frequency, which is proportional to the dust charge density and the ion gyrofrequency. On the other hand, the dynamics of amplitude modulated R-D-MHD waves is governed by the cubic nonlinear Schrodinger equation. The latter has been derived by using the reductive perturbation technique and the two-timescale analysis which accounts for the harmonic generation nonlinearity in plasmas. The stability of the modulated wave envelope against non-resonant perturbations is studied. Finally, the possibility of localized envelope excitations is discussed. (C) 2004 American Institute of Physics.

Correlation Between the Electrical and Optical Properties of an Atmospheric Pressure Plasma During Siloxane Coating Deposition

The effect of varying process parameters on atmospheric plasma characteristics and properties of nanometre thick siloxane coatings is investigated in a reel-to-reel deposition process. Varying plasma operation modes were observed with increasing applied power for helium and helium/oxygen plasmas. The electrical and optical behaviour of the dielectric barrier discharge were determined from current/voltage, emission spectroscopy and time resolved light emission measurements. As applied power increased, multiple discharge events occurred, producing a uniform multi-peak pseudoglow discharge, resulting in an increase in the discharge gas temperature. The effects of different operating modes on coating oxidation and growth rates were examined by injecting hexamethyldisiloxane liquid precursor into the chamber under varying operating conditions. A quenching effect on the plasma was observed, causing a decrease in plasma input power and emission intensity. Siloxane coatings deposited in helium plasmas had a higher organic component and higher growth rates than those deposited in helium/oxygen plasmas.

Precipitation, microstructure and mechanical properties of low nickel maraging steel

A maraging steel with a composition of Fe–12·94Ni–1·61Al–1·01Mo–0·23Nb (wt-%) was investigated. Optical, scanning electron and transmission electron microscopy and X-ray diffraction analysis were employed to study the microstructure of the steel after different aging periods at temperatures of 450–600°C. Hardness and Charpy impact toughness of the steel were measured. The study of microstructure and mechanical properties showed that nanosized precipitates were formed homogeneously during the aging process, which resulted in high hardness. As the aging time is prolonged, precipitates grow and hardness increases. Fractography of the as forged steel has shown mixed ductile and brittle fracture and has indicated that the steel has good toughness. Relationships among heat treatment, microstructure and mechanical properties are discussed. Further experiments using tensile testing and impact testing for aged steel were carried out.

Structural and magnetic properties of sol-gel Co2xNi0.5-xZn0.5-xFe2O4 thin films

Nanocrystalline Co2xNi0.5-xZn0.5-xFe2O4 (x = 0-0.5) thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology as well as magnetic and microwave absorption properties of the films calcined at 1073 K were studied using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. All films were uniform with out microcracks . The Co content in the Co-Ni-Zn films resulted in a grain size ranging from 15 to 32 nm while it ranged from 33 to 49 nm in the corresponding powders. Saturation and remnant magnetization increased with increase in grain size, while coercivity demonstrated a drop due to multidomain behavior of crystallites for a given value of x. Saturation magnetization increased and remnant magnetization had a maximum as a function of grain size in dependent of x. In turn, coercivity increased with x independent of grain size. Complex permittivity of the Co-Ni-Zn ferrite films was measured in the frequency range 2-15 GHz. The highest hysteretic heating rate in the temperature range 315-355 K was observed in CoFe2O4. The maximum absorption band shifted from 13 to 11GHz as cobalt content increased from x = 0.1 to 0.2.

Preparation, structural characterization, semiconductor and photoluminescent properties of zinc oxide nanoparticles in a phosphonium-based ionic liquid

A convenient microwave method in preparation of zinc oxide nanoparticles (ZnONPs) using an ionic liquid, trihexyltetradecylphosphonium bis{(trifluoromethyl)sulfonyl}-imide, [P-66614][NTf2], as a green solvent is described in this paper. To the best of our knowledge, there is no report for synthesizing any nanoparticle using this ionic liquid. Trihexyltetradecylphosphonium bis{(trifluoromethyl)sulfonyl}-imide has low interface tension and thus it can enhance the nucleation rate, which is favorable to the formation of smaller ZnONPs. The fabricated ZnONPs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis spectroscopy. The XRD pattern reveals that the ZnONPs have hexagonal wurtzite structure. The strong intensity and narrow width of ZnO diffraction peaks indicate that the resulting nanoparticles are of high crystallinity. The synthesized ZnONPs show direct band gap of 3.43 eV. The UV-vis absorption spectrum of ZnONPs dispersed in ethylene glycol at room temperature revealed a blue-shifted onset of absorption. (C) 2011 Elsevier Ltd. All rights reserved.