Quantum Confinement and Electronic Properties of Rutile TiO2 Nanowires

The quantum confinement effect, electronic properties, and optical properties of TiO2 nanowires in rutile structure are investigated via first-principles calculations. We calculate the size- and shape-dependent band gap of the nanowires and fit the results with the function E-g = E-g(bulk) + beta/d(alpha). We find that the quantum confinement effect becomes significant for d < 25 angstrom, and a notable anisotropy exists that arises from the anisotropy of the effective masses. We also evaluate the imaginary part of the frequency-dependent dielectric function [epsilon(2)(omega)] within the electric-dipole approximation, for both the polarization parallel [epsilon(parallel to)(2)(omega)] and the perpendicular [epsilon 1/2(omega)] to the axial (c) direction. The band structure of the nanowires is calculated, with which the fine structure of epsilon(parallel to)(2)(omega) has been analyzed.

Single-mode condition for silicon rib waveguides with trapezoidal cross-section

Single-mode condition for silicon rib waveguides with trapezoidal cross-section was obtained using a numerical method based on imaginary-distance beam propagation method with non-uniform discretization. Both quasi-transverse-electric and quasi-transverse-magnetic modes were investigated. Simulated single-mode condition is given by a modified equation. Comparison with reported results shows that the Marcatili's method is in a better agreement with our results. (C) 2003 Elsevier B.V. All rights reserved.

Optical constants of cubic GaN/GaAs(001): Experiment and modeling

The optical constants epsilon(E)=epsilon(1)(E)+iepsilon(2)(E) of unintentionally doped cubic GaN grown on GaAs(001) have been measured at 300 K using spectral ellipsometry in the range of 1.5-5.0 eV. The epsilon(E) spectra display a structure, associated with the critical point at E-0 (direct gap) and some contribution mainly coming from the E-1 critical point. The experimental data over the entire measured spectral range (after oxide removal) has been fit using the Holden-Munoz model dielectric function [M. Munoz et al., J. Appl. Phys. 92, 5878 (2002)]. This model is based on the electronic energy-band structure near critical points plus excitonic and band-to-band Coulomb-enhancement effects at E-0, E-0 + Delta(0) and the E-1, E-1 + Delta(1), doublet. In addition to evaluating the energy of the E-0 critical point, the binding energy (R-1) of the two-dimensional exciton related to the E-1 critical point was estimated using the effective mass/k.p theory. The line, shape of the imaginary part of the cubic-GaN dielectric function shows excitonic effects at room temperature not withstanding that the exciton was not resolved. (C) 2003 American Institute of Physics.

Theoretical analysis and experimental study of Fourier transformation of Franz-Keldysh oscillations in GaAs

Fourier transformation (FT) has been used in the theoretical line shape analysis of Franz-Keldysh oscillations (FKOs) in detail by numerical simulations. FKOs from the surface-intrinsic-n(+) GaAs structure were obtained in photoreflectance (PR) measurements with various modulation light intensities and with different strengths of bias light illumination, which were used to change the static electric field in the intrinsic layer of the sample. The FT spectra of the PR spectra, including the real part, imaginary part, and the modulus, were very consistent with the theoretical line shapes. The ratio of the square root of the reduced mass (root mu (L)/root mu (H)) and the ratio of transition strength of the electron heavy hole to the electron light hole were obtained from the PT spectra. In addition, the electric field in the intrinsic layer of the sample without and with bias illumination and the modulation field induced by photomodulation were also obtained. (C) 2000 American Institute of Physics. [S0021-8979(00)02123-X].

Fourier transformation study of the Franz-Keldysh Oscillation in SIN+ GaAs structures

Fourier transformation (FT) method has been used in the theoretical lineshape analysis of the Franz-Keldysh Oscillation (FKO) in detail by numerical simulation. The FKO of a set of GaAs SIN+ samples was obtained in photoreflectance measurements. The FT spectra of a part of the samples,including of the real part,imaginary part, and mode of the FT,are well consistent with the theoretical lineshapes. The ratio of the square root of the reduced mass of the light hole (LH) to the heavy hole (HH), root mu(1)/root mu(h), obtained in the analysis was in the range of 0.805 to 0.816 for different samples. In addition,the built-in electric field F-1, and the modulation field delta F = F-1 - F-2 induced by photo-modulation were also obtained in the analysis. However,for a few samples great difference was found in the lineshape of the real part and imaginary part of their FT spectra from the theoretical lineshape. In this case the mode of the FT spectra still can be used to obtain useful information.

Dielectric relaxation of poled polymer DCNP/PMMA

We have prepared the polymer thin films of a 3-(1,1-dicyanothenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DChTP)/poly (methyl methacrylate) (PMMA) guest-host system by spin coating. In order to investigate their temporal and temperature stability, we have measured their dielectric relaxation spectra including the frequency dependence of the real and imaginary parts of dielectric constants. The investigated frequency ranged from 50 Hz to 10 MHz. The measured temperature range above the glass transition temperature T-g (95 degrees C) of the DCNP/PMMA system was from 95 degrees C to 1250C. By using the Adam-Gibbs model, the temperature dependence of the characteristic time tau above T-g was fitted, and the values of the characteristic times tau below T-g were estimated. The lifetimes of the polymer were evaluated by the Kohlrausch-Williams Watts (KWW) empirical decay model. (C) 2000 Elsevier Science B.V. All rights reserved.

Influence of dielectric properties of a substrate upon plasmon resonance spectrum of supported Ag nanoparticles

Plasmon resonance spectra of supported Ag nanoparticles are studied by depositing the particles on different substrates. It was found that the dielectric properties of the substrates have significant effects on the spectral line shape, except the resonance frequency. Beyond the plasmon resonance band, the spectral shape is mainly governed by the dielectric function, particularly its imaginary part, of the substrate. The plasmon resonance band, on the other hand, may be severely distorted if the substrate is absorbing strongly.

MODELING OF ELECTRON-TUNNELING TIMES IN ASYMMETRIC DOUBLE QUANTUM-WELLS

A scattering process modeled by an imaginary potential V(I) in the wide well of an asymmetric double quantum well structure (DQWS) is used to model the electron tunneling from the narrow well. Taking V(I) approximately -5 meV, the ground resonant level lifetimes of the narrow well in the DQWS are in quantitative agreement with the experimental resonance and non-resonance tunneling times. The corresponding scattering time 66 fs is much faster than the intersubband scattering time of LO-photon emission.

COMPARISONS OF PHASE TIMES WITH TUNNELING TIMES BASED ON ABSORPTION PROBABILITIES

The times spent by an electron in a scattering event or tunnelling through a potential barrier are investigated using a method based on the absorption probabilities. The reflection and transmission times derived from this method are equal to the local Larmor times if the transmission and reflection probability amplitudes are complex analytic functions of the complex potential. The numerical results show that they coincide with the phase times except as the incident electron energy approaches zero or when the transmission probability is too small. If the imaginary potential covers the whole space the tunnelling times are again equal to the phase times. The results show that the tunnelling times based on absorption probabilities are the best of the various candidates.

Synthesis, structural and electrical characterizations of Sr2Fe1-xMxNbO6 (M = Zn and Cu) with double perovskite structure

Sr2Fe1-xZnxNbO6-x/2 (0 <= x <= 0.5) and Sr2Fe1-xCuxNbO6-x/2 (0.01 <= x <= 0.05) with the double perovskite structure have been synthesized. The crystal structures at room temperature were determined from Rietveld refinements of X-ray powder diffraction data. The plots of the imaginary parts of the impedance spectrum, Z '', and the electric modulus, M '', versus log (frequency), possess maxima for both curves separated by less than a half decade in frequency with associated capacities of 2 nF. The enhancement of the overall conductivity Of Sr2Fe1-xMxNbO6-x/2 (M = Cu and Zn) is observed, as increases from 2.48 (3) x 10(-4) S/cm for Sr2FeNbO6 to 3.82 (5) x 10(-3) S/cm for Sr2Fe0.8Zn0.2NbO5.9 at 673 K. Sr2Fe0.8Zn0.2NbO5.9 is chemically stable under the oxygen partial pressure from 1 atm to 10(-22) atm at 873 K. The p and n-type electronic conductions are dominant under oxidizing and reducing conditions, respectively, suggesting a small-polaron hopping mechanism of electronic conduction.

Surface plasmon resonance studies on the electrochemical doping/dedoping processes of anions on polyaniline-modified electrode

The combination of in situ surface plasmon resonance (SPR) with electrochemistry was used to investigate the electrochemical doping/dedoping processes of anions on a polyaniline (PAn)-modified electrode. Electrochemical SPR characteristics of the PAn film before and after doping/dedoping were revealed. The redox transformation between the insulating leucoemeraldine, and the conductive emeraldine, corresponding to the doping/dedoping of anion, can lead to very distinct changes in both the resonance minimum angle and the shape of SPR curve. This is ascribed to the swelling/shrinking effect, and the change of the PAn film in the imaginary part of the dielectric constant resulted from the transition of the film conductivity. In situ recording the time evolution of reflectance change at a fixed angle permits the continuous monitoring of the kinetic processes of doping/dedoping anions. The size and the charge of anions, the film thickness, as well as the concentration of anions are shown to strongly influence the rate of ingress/egress of anions. The time differential of SPR kinetic curves can be well applied in the detecting electroinactive anion by flow injection analysis. The approach has higher sensitivity and reproducibility compared with other kinetic measurements, such as those obtained by amperometry.

In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Methods to study the ionic conductivity of polymeric electrolytes using a.c. impedance spectroscopy

Composite polymeric electrolytes of PEO-LiClO4-Al2O3 and PEO-LiClO4-EC were prepared and the ionic conductivity by a.c. impedance was calculated using four different methods, and three kinds of representations of a.c. impedance spectra were adopted. The first is based on the Nyquist impedance plot of the imaginary part (Z") versus the real part (Z') of the complex impedance. The second and the third correspond to the plots of imaginary impedance Z" as a function of frequency (f), and the absolute value (\Z\) and phase angle (theta) as a function of f, respectively. It was found that the values of the ionic conductivity calculated using the three representations of a.c. impedance spectra are basically identical.

A novel electrochemical SPR biosensor

In this paper, we demonstrate for the first time that upon electrochemical oxidation/reduction, the transition in the conductivity of polyaniline (PAn) film on gold electrode surface leads to a large change of surface plasmon resonance (SPR) response due to a change in the imaginary part of dielectric constant of PAn film. Based on the amplifying response of SPR to the redox transformation of PAn film as a direct result of the enzymatic reaction between horseradish peroxidase (HRP) and PAn in the presence of H2O2, a novel PAn-mediated HRP sensor has been fabricated. The electrochemical SPR biosensor, unlike a usual binding assay with SPR, can afford a larger SPR response, and can also be reused by reducing the PAn film electrochemically to its reduced state. This method opens up a new route to the fabrication of SPR biosensor. (C) 2001 Elsevier Science BN. All rights reserved.

Theoretical study on the mechanisms of some elementary reactions catalyzed by modified carbonyl cobalt

All structural geometries of intermediates, transition states and product are, optimized at HF/ LANL2DZ level under the effective core potential approximation. The potential energy profile for some elementary reactions of hydroformylation catalyzed by Co-2(CO)(6)(PH3)(2), consisting of carbonyl insertion, H-2 oxidative addition and aldehyde reductive elimination, are calculated, The transition states are further confirmed by having one and only one imaginary vibrational frequency, The activation energies of carbonyl insertion, H-2 oxidative addition and aldehyde reductive elimination are 54, 02, 134, 02 and 43. 44 kJ/mol, respectively.