SUBSTITUTIONAL DONOR RELATED STATES AND AU/GE/NI CONTACTS TO ALXGA1-XAS

Current-voltage measurements performed on bulk AlxGa1-xAs equipped with Au/Ge/Ni contacts reveal surprising deviations from ohmic behaviour when the temperature is lowered to that of liquid nitrogen. Significant differences are observed between samples with x = 0.3 (direct band-gap material) and x = 0.5 (indirect band-gap material). The dominant states of the donor atoms Si (doping) or Ge are found to be responsible for such behaviour. Evidence for the existence of an effective-mass X-valley metastable state is also presented.

Er3+ and Eu3+ containing transparent glass ceramics in the system PbGeO3-PbF2-CdF2

Glasses with composition 60PbGeO(3)-10PbF(2)-30CdF(2) (mol%) have been obtained in the bulk form with a high stability against crystallization. After doping them with 0.5 mol% of Er3+ or Eu3+ and appropriate heat treatment transparent glass ceramics could be obtained. Electronic spectroscopy, X-ray diffraction and transmission electron microscopy measurements have been made. beta-PbF2: Er3+/Eu3+ Single crystals, 5-10 nm in size, are detected in the otherwise transparent composite medium, the size of the particles and absence of clustering allowing for the increased transparency of the final materials. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Structural characterization of undoped and Sb-doped SnO2 thin films fired at different temperatures

SnO2 thin films were obtained by the sol-gel method starting from inorganic precursor solutions. In this work, we compare the structure of undoped and Sb-doped SnO2 films prepared by dip-coating. The films were deposited on quartz substrates and then fired at different temperatures ranging from 383 up to 1173 K. The density and the thickness of the films were determined by X-ray reflectivity (XRR) and their porous nanostructure was characterized by grazing-incidence small angle X-ray scattering (GISAXS). XRR results corresponding to undoped and Sb-doped samples indicate a monotonous decrease in film thickness when they are fired at increasing temperatures. At same time, the apparent density of undoped samples exhibits a progressive increase while for Sb-doped films it remains invariant up to 973 K and then increases for T = 1173 K. Anisotropic GISAXS patterns of both films, Sb-doped and undoped, fired above 573 K indicate the presence of elongated pores with their major axis perpendicular to the film surface. For all firing temperatures the nanopores in doped samples are larger than in undoped ones. This suggests that Sb-doping favours the pore growth hindering the film densification. At the highest firing temperature (1173 K) this effect is reversed.

Influence of strains and defects on ferroelectric and dielectric properties of thin-film barium-strontium titanates

Pristine, W and Mn 1% doped Ba(0.6)Sr(0.4)TiO(3) epitaxial thin films grown on the LaAlO(3) substrate were deposited by pulsed laser deposition (PLD). Dielectric and ferroelectric properties were determined by the capacitance measurements and X-ray diffraction was used to determine both residual elastic strains and defect-related inhomogeneous strains-by analyzing diffraction line shifts and line broadening, respectively. We found that both elastic and inhomogeneous strains are affected by doping. This strain correlates with the change in Curie-Weiss temperature and can qualitatively explain changes in dielectric loss. To explain the experimental findings, we model the dielectric and ferroelectric properties of interest in the framework of the Landau-Ginzburg-Devonshire thermodynamic theory. As expected, an, elastic-strain contribution due to the epilayer-substrate misfit has an important influence on the free-energy. However, additional terms that correspond to the defect-related inhomogeneous strain had to be introduced to fully explain the measurements.

A theoretical analysis on electronic structure of the (110) surface of TiO2-SnO2 mixed oxide

Mixed oxide compounds, such as TiO2-SnO2 system are widely used as gas sensors and should also provide varistor properties modifying the TiO2 surface. Therefore, a theoretical investigation has been carried out characterizing the effect of SnO2 on TiO2 addition on the electronic structure by means of ab initio SCF-LCAO calculations using all electrons. In order to take into account the finite size of the cluster, we have used the point charge model for the (TiO2)(15) cluster to study the effect on electronic structure of doping the TiO2 (110) Surface. The contracted basis set for titanium (4322/42/3), oxygen (33/3) and tin (43333/4333/43) atoms were used. The charge distributions, dipole moments, and density of states of doping TiO2 and vacancy formation are reported and analysed. (C) 2003 Elsevier B.V. All rights reserved.

A study on X-ray irradiation of composite polyaniline LB films

Composite Langmuir-Blodgett (LB) films from polyaniline and cadmium stearate have been irradiated with ionizing X-rays for various exposure times. In the initial stages of X-ray irradiation the absorption peak at 580 nm of an as-deposited film was seen to decrease with a concomitant increase in the absorption in the long wavelength region (700-1100 nm). Upon prolonging the irradiation, the absorption maximum shifted to 800 nm with the LB film color changing to green, characteristic of acid doped polyaniline. The changes in the Fourier transform infrared (FTIR) spectra upon irradiation are also similar to those observed upon acid doping of polyaniline. When compared with acid doping, two major differences were observed for the LB films exposed to X-rays. First, the packing order of the cadmium stearate domains in the composite LB films - as observed by X-ray diffraction - is not affected by the X-ray irradiation. In addition, no significant increase in the DC conductivity was noted after the X-ray exposure whereas similar LB films have their conductivity increased by an order of magnitude upon acid doping. These differences may be explained by considering that the inter-domain contribution to the conductivity is increased by the acid doping because the insulating cadmium stearate domains are destroyed, which does not occur with the X-ray irradiation. (C) 1998 Elsevier B.V. S.A. All rights reserved.

Yttrium oxysulfide nanosized spherical particles doped with Yb and Er or Yb and Tm: efficient materials for up-converting phosphor technology field

This work reports on the preparation, structural and luminescent studies of nanosized up-converter phosphors Y2O2S:Yb(4%), Er(0.1%) and Y2O2S:Yb(4%), Tm(0.1%),both from polymeric and basic carbonate precursors. The precursors were submitted to a sulphuration process that was previously developed for oxysulfide preparation from basic carbonate. From XRD data, all phosphors presented the oxysulfide phase and the mean crystallite size estimated from the Scherrer formula in the range of 15-20 nm. Polymeric precursor leads to the smallest crystallite size independent on the doping ion. SEM and TEM results confirmed that basic carbonate leads to spherical particles with narrow size distribution and mean diameter of 150 nm, and polymeric precursor smaller spherical particles with diameter between 20 and 40 nm. Up-conversion studies under 980 nm laser excitation showed that Er-doped phosphors present strong green emission related to H-2(11/2), S-4(3/2) --> I-4(15/2) Er transitions as well as the red ones, F-4(9/2) --> I-4(15/2). Tm-doped samples show strong blue emission assigned to (1)G(4) --> H-3(6) and also the red ones, related to (1)G(4) --> F-3(4). Therefore, the sulphuration method was successfully applied to prepare nanosized and nanostructured blue and green up-converter oxysulfide phosphors starting from basic carbonate and polymeric precursors. (C) 2003 Elsevier B.V. All rights reserved.

Study of potassium additive on the phase formation and ferroelectric properties of 0.9PMN-0.1PT ceramics

A recent and innovative method to include Ti into the columbite precursor has permitted to synthesize 0.9PMN-0.1PT powders with high homogeneity. The present work describes this methodology, named modified columbite method, showing that the reaction between MN(T)and PbO at 800 degrees C for 2 h results in perovskite single-phase. The crystal structure alterations in the columbite and perovskite phases obtained by this methodology and the effects of potassium doping were investigated by the Rietveld method. Changes in the powder morphology, density and weight loss during the sintering process were also studied. Conclusively, potassium does not affect significantly the perovskite amount, but reduces the particle and grain sizes. This dopant also changes the relaxor behavior of 0.9PMN-0.1 PT ceramic, reducing the dielectric loss and enhancing the diffuseness of the phase transition. (C) 2005 Published by Elsevier Ltd and Techna Gronp S.r.l.

Electro-optical properties of Er-doped SnO2 thin films

Photoconductivity of SnO2 sol-gel films is excited, at low temperature, by using a 266 nm line-fourth harmonic-of a Nd:YAG laser. This line has above bandgap energy and promotes generation of electron-hole pairs, which recombines with oxygen adsorbed at grain boundary. The conductivity increases up to 40 times. After removing the illumination on an undoped SnO2 film, the conductivity remains unchanged, as long as the temperature is kept constant. Adsorbed oxygen ions recombine with photogenerated holes and are continuously evacuated from the system, leaving a net concentration of free electrons into the material, responsible for the increase in the conductivity. For Er doped SnO2, the excitation of conductivity by the laser line has similar behavior, however after removing illumination, the conductivity decreases with exponential-like decay. (C) 2003 Elsevier Ltd. All rights reserved.

Planar waveguides based on nanocrystalline and Er3+ doped SnO2

Luminescent SnO2: x%mol Er3+ (x=0.1-2.0) thin films have been spin coated on borosilicate and silica substrates from water colloidal suspensions that could be prepared containing up to 40% in weight SnO2 nanocrystalline powders. High Resolution Transmission Electron Microscopy results show the well known SnO2 cassiterite structure and nanocrystallites around 10 nm in diameter, corroborating results from X-ray diffraction. Mono and multi layers have been prepared from the stable colloidal suspensions and films thickness was observed to increase linearly, up to 200 nm, with the colloidal suspensions nanoparticles amount. Excitation and emission spectra have been measured and Er3+ ions were found to be essentially incorporated into the cassiterite structure, substituting for Sn4+, for doping concentration lower than 0.05 mol%. Er3+ ions also appear segregated at the grains surface for higher doping concentration. The optical parameters (refractive index, thickness and propagating modes) of a waveguide sample were measured at 632.8 and 543.4 nm by the prism coupling technique. A monomodal waveguide was obtained with attenuation loss of 3.5 dB/cm along a 2.5 cm optical path.

Small-angle X-ray scattering study of gelation and aging of Eu3+-doped sol-gel-derived siloxane-poly(oxyethylene) nanocomposites

The aggregation, gelation, and aging of urea-cross-linked siloxane-poly(oxyethylene) nanohybrids [(U600)-n] containing two different amounts of europium triflate initially dissolved in an ethanol-water mixture were investigated by in situ small-angle X-ray scattering (SAXS). For both low (n = [O]/[Eu] = 80) and high (n = 25) europium contents, the SAXS intensity was attributed to the formation of siloxane clusters of about 8-11 Angstrom in size. Siloxane cluster formation and growth is a rapid process in hybrids with low Eu contents and slow in Eu-rich hybrids. An additional contribution to the scattering intensity at very low angles was attributed to the formation of a coarse structure level. At this secondary level, the structure can be described as a set of dense domains containing siloxane clusters embedded in a depleted matrix composed of unfolded polymer chains and solvent. By fitting a theoretical function for this model to the experimental SAXS curves, relevant structural parameters were determined as functions of time during the sol-gel transition and gel aging. For hybrids with low europium contents (n = 80), the size of the siloxane clusters remains essentially invariant, whereas the dense segregation domains progressively grow. In hybrids with high doping contents (n = 25), the preponderant structure variation during the first stages of the sol-gel transformation is the slow growth of siloxane clusters. For these hybrids, the segregation of siloxane clusters forming dense domains occurs only during advanced stages of the process.

INSULATOR-TO-METAL TRANSITION IN POLYTHIOPHENE

In the present work, the electronic structure of polythiophene at several doping levels is investigated by the use of the Huckel Hamiltonian with sigma-bond compressibility. Excess charges are assumed to be stored in conformational defects of the bipolaron type. The Hamiltonian matrix elements representative of a bipolaron are obtained from a previous thiophene oligomer calculation, and then transferred to very long chains. Negative factor counting and inverse iteration techniques have been used to evaluate densities of states and wave functions, respectively. Several types of defect distributions were analyzed. Our results are consistent with the following: (i) the bipolaron lattice does not present a finite density of states at the Fermi energy at any doping level; (ii) bipolaron clusters show an insulator-to-metal transition at 8 mol% doping level; (iii) segregation disorder shows an insulator-to-metal transition for doping levels in the range 20-30 mor %.

Acoustic measurement of the low-energy excitations in Nd2-xCexCuO4+delta

The complex dynamic Young's modulus of ceramic Nd2-xCexCuO4 with x = 0, 0.05 and 0.20 has been measured from 1.5 to 100 K at frequencies of 1 - 10 kHz. In the undoped sample the modulus starts decreasing below similar to 20 K, instead of approaching a constant value as in a normal solid. The modulus minimum has been interpreted in terms of paraelastic contribution from the relaxation of the Nd3+ 4f electrons between the levels of the ground state doublet, which is split by the interaction with the antiferromagnetically ordered Cu sublattice. The value of the splitting is found to be 0.34 meV, in excellent agreement with inelastic neutron scattering, infrared and specific heat experiments. With doping, the anomaly shifts to lower temperature and decreases in amplitude, consistently with a reduction of the local field from the Cu sublattice. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Characterization of BaTi1-xZrxO3 thin films obtained by a soft chemical spin-coating technique

Single-phase perovskite structure BaZrxTi1-xO3 (BZT) (0.05less than or equal toxless than or equal to0.25) thin films were deposited on Pt-Ti-SiO2-Si substrates by the spin-coating technique. The structural modifications in the thin films were studied using x-ray diffraction and micro-Raman scattering techniques. Lattice parameters calculated from x-ray data indicate an increase in lattice (a axis) with the increasing content of zirconium in these films. Such Zr substitution also result in variations of the phonon mode wave numbers, especially those of lower wave numbers, for BaZrxTi1-xO3 thin films, corroborate to the structural change caused by the zirconium doping. on the other hand, Raman modes persist above structural phase transition, although all optical modes should be Raman inactive in the cubic phase. The origin of these modes must be interpreted as a function of a local breakdown of the cubic symmetry, which could be a result of some kind of disorder. The BZT thin films exhibited a satisfactory dielectric constant close to 181-138, and low dielectric loss tan delta<0.03 at the frequency of 1 kHz. The leakage current density of the BZT thin films was studied at elevated temperatures and the data obey the Schottky emission model. Through this analysis the Schottky barrier height values 0.68, 1.39, and 1.24 eV were estimated to the BZT5, BZT15, and BZT25 thin films, respectively. (C) 2004 American Institute of Physics.

A theoretical analysis of the TiO2/Sn doped (110) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO2/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO2 is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sri, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices. (c) 2005 Elsevier B.V. All rights reserved.