National Institute Of Materials Physics - Romania

Pure and europium (Eu3+) doped cerium dioxide (CeO2) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of similar to 250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce4+ sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 degrees C, a remarkable high surface area of similar to 120 m(2) g (-1) is preserved whereas an enrichment of the surface Ce4+ relative to Ce3+ ions and relative strong europium emission with a lifetime of similar to 1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.

Rolled-up nanostructures formed from lattice mismatched III-V heterojunction films by taking advantage of a strain-induced self-rolling mechanism represent a useful type of building blocks for nanotechnology, with possible applications in high-speed microelectronic and optoelectronic devices. This work investigated the effect of illumination on the hydrofluoric acid etching of AlAs sacrificial layers with systematically varied thicknesses in order to release and roll up MBE grown InGaAs/GaAs bilayers. Based on this "etch suppression effect" (ESE), we propose an illumination-assisted technique that offers an advantage over other methods of rolling up nano-objects on a substrate from inherently strained films because it allows control over the positioning of rolled-up micro- and nanotubes independently from lithographic methods. For thicknesses of AlAs below 10 nm, we found two etching regimes for the area under illumination: one at low illumination intensities, in which the etching and releasing proceeds as expected and one at higher intensities in which the etching and any releasing are completely suppressed. The "etch suppression" area is well defined by the illumination spot, which can be used to realize well-controlled heterogeneously etched regions on the same sample.

The Pd-TPPTS complex (TPPTS - trisodium salt of 3,3',3 ''-phosphanetriyl benzenesulfonic acid) and PdCl42- salt heterogenised onto Zn2AlNO3 layered double hydroxide (LDH) using an ion-exchange procedure, have been shown to be efficient green catalysts in the cycloisomerisation reaction of acetylenic carboxylic acids to the corresponding 5-membered heterocycles.

ZnO:Co thin films are prepared by electrochemical deposition at different overpotentials and investigated by scanning electron microscopy, optical spectroscopy, and cathodoluminescence, X-ray photoelectron spectroscopy and Kerr magnetometry (MOKE). An increase of structural disorder and crystallite reorientation are observed for cobalt-doped samples. MOKE magnetometry revealed room-temperature ferromagnetic behavior only for ZnO: Co deposited at -850 mV. These are the samples with the lower cobalt content and lowest structural perturbation of the ZnO matrix by cobalt. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

A genuine GaAs surface was covered with a relatively thick layer (similar to nm) of native oxide pinning the surface Fermi level within the band gap of semiconductor. The method presented in this work is related to the sulphur passivation by treating n-GaAs in sulphide solutions (e.g. pure ammonium sulphide and sulphur monochloride) that combines both chemical and electronic passivation by reducing the surface state density. The presence of the covalent bonds As-S and Ga-S was putted into evidence by XPS analysis. It is presented the independence of XPS measurements on n-GaAs substrate orientation for (100) and (110) planes. At the surface of n-GaAs it is developed an adherent layer of sulphur compound as a result of chemical interaction of sulphur ions with n-GaAs surface.

A new analytical approximation of the diffraction peak size profile due to the lognormal distribution of spherical crystallites is derived. In comparison with the existing approximation constructed with the condition of conserving the volume-averaged column length of the exact profile [Popa & Balzar (2002). J. Appl. Cryst. 35, 338-346], the new approximation conserves both volume- and area-averaged column lengths. Moreover, it is a better approximation for large distribution dispersions. Like the old approximation, the present one is appropriate for implementation in the whole powder pattern fitting codes, Rietveld included.

Short time spark plasma sintering at 1200 degrees C for 10 min and under a uniaxial pressure of 95 MPa followed by annealing at 1100 degrees C for 5 h is proposed for synthesis of high density (99%) Ba(Ti0.87Sn0.13)O-3 ceramic. Starting powder of 450 nm was obtained by co-precipitation, while the average grain size in the sintered ceramic was of 580 nm. X-ray diffraction analysis of the as prepared Ba(Ti0.87Sn0.13)O-3 samples indicated the presence of single phase BaTi0.87Sn0.13O3 developed in the BaTiO3 cubic structure. Samples have high relative dielectric constant of 5680 and low dissipation factor (tan delta = 0.009) at Curie temperature of 57 degrees C and 1 kHz, good tunability and ferroelectric properties. Remarkable is that these results are from some points of view different than for the conventionally processed samples with similar stoichiometry. Some ideas in this regard are presented and this suggests that SPS can be useful for expanded possibilities in the control of the properties. (C) 2010 Elsevier B.V. All rights reserved.

Li-N-H and Li-Si-N-H composites have been synthesized by ball milling starting from lithium amide, lithium hydride and silicon powders. Hydrogen sorption behaviour was investigated for the Si-containing composites and a Li-N-H reference sample. The as-milled Si-containing sample showed the presence of the constituent powders but after few absorption-desorption cycles an important amount of Li(2)SiN(2) appeared in both de-hydrogenated and re-hydrogenated composites. This phase was present in higher amount in the de-hydrogenated sample than in the re-hydrogenated one. The presence of this phase was also confirmed by XPS measurements. Li-N-H and Li-Si-N-H composites in de-hydrogenated state also contained lithium imide. X-ray diffraction data indicated a reversible hydrogen generating reaction between lithium amide, lithium hydride and silicon to produce Li(2)SiN(2). lithium imide and hydrogen. The plateau pressure of Li-N-Si-H system is twice the one for Li-N-H at the same temperature (about 265 degrees C), as shown by pressure-composition isotherms in desorption mode. For the first time it has been observed a thermodynamic destabilization of Li-N-H by mixing it with Si. (C) 2010 Elsevier B.V. All rights reserved.

The etherification of biomass-based alcohols with various linear alpha-olefins under solvent-free conditions was followed in a space- and time-resolved manner on 9 mu m large H-Beta zeolite crystals by confocal fluorescence microscopy. This allowed us to visualize the interaction with the substrate and distribution of the coke products into the catalyst at the level of an individual zeolite crystal during the etherification process. The spectroscopic information obtained on the micrometer-scale zeolite was in line with the results obtained with bulk characterization techniques and further confirmed by the catalytic results obtained both for micrometer-scale and nanoscale zeolites. This allowed us to explain the influence of the substrate type (glycerol, glycols, and alkenes) and zeolite properties (Si/Al ratio and particle size) on the etherification activity. The etherification of the biomass-based alcohols takes place mainly on the external surface of the zeolite particles. The gradual blockage of the external surface of the zeolite results in a partial or total loss of etherification activity. The deactivation could be attributed to olefin oligomerization. The high conversions obtained in the etherification of 1,2-propylene glycol with long linear alkenes (up to 80%) and the pronounced deactivation of the zeolite observed in the etherification of glycerol with long linear alkenes (max. 20% conversion) were explained by the spectroscopic measurements and is due to differences in the adsorption, i.e., in the center of the zeolite particle for glycerol and on the external surface in the case of glycols.