National Institute Of Materials Physics - Romania

ZnO is a wide band-gap (ca. 3.4 eV) semiconductor, piezoelectric, pyroelectric, biocompatible, transparent in the visible spectrum and UV light emitting material. The fabrication in 2001 of the first nanobelts of semiconductor oxide materials lead to a rapid expansion of researches concerning one dimensional nanostructures (nanotubes, nanowires, nanobelts), given their possible application in optics, optoelectronics, piezoelectricity, catalysis. Researches carried on up to date evidenced the possibility to obtain an extraordinary variety of ZnO nanostructures, in function of the experimental parameters and the used growth methods. In this work we present morphostructural results on nanostructured ZnO layers obtained by electrochemical deposition. The films have been grown on gold covered glass plates and Si wafers, in various experimental conditions such as: nature of the wetting agents, electrical polarization of the substrate (continuous, pulsed). The influence of the growth conditions on the crystalline structure and morphology of the films is revealed by scanning and transmission electron microscopy studies. The films show a variety of growth morphologies, from entangled-wires-like to honeycomb-like layers. These large-specific-surface layers will be tested as nanostructured substrates for photovoltaic cells with improved efficiency.

Iron- and europium-doped (<= 1 at.%)TiO2 nanoparticles powders have been synthesized by a hydrothermal route at 200 degrees C, starting with TiCl4, FeCl3 center dot 6H(2)O and EuCl3 center dot 6H(2)O. The structure, morphology and optical peculiarities were investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS), Mossbauer spectroscopy and UV-vis measurements. The photocatalytic performance was analysed in the photodegradation reaction of phenol. Rietveld refinements of XRD patterns reveal that the as-prepared samples consist in iron- and europium-doped TiO2 in the tetragonal anatase structural shape, with particle size as low as 15 nm. By means of Mossbauer spectroscopy on both Fe-57 and Eu-151 isotopes as well as by EXAFS analyses, the presence of Fe3+ and/or Eu3+ ions in the nanosized powders has been evidenced. It was found that iron and europium ions can substitute for titanium in the anatase structure. From the UV-vis reflection spectra, by using the transformed Kubelka-Munk functions, the band gap energy (E-g) of the hydrothermal samples has been determined in comparison with that of Degussa P-25 photocatalyst. A decrease of E-g from 2.9eV found for Degussa photocatalyst to 2.8 eV for the titania doped with 1 at.% Fe has been evidenced, indicating a valuable absorption shift (similar to 20 nm) towards visible light region. However, the best photocatalytic activity in the photodegradation reaction of phenol was evidenced for the hydrothermal sample, TiO2: 1 at.% Fe, 0.5 at.% Eu, in both UV and visible light regions. The photocatalytic activities of iron-doped and iron-europium-codoped samples are high and practically the same only in visible light. The photocatalytic properties in Correlation with the structural and optical peculiarities of the hydrothermal samples are discussed. (C) 2008 Elsevier B.V. All rights reserved.

The nanostructure of Si-x(SiO2)(1-x) films deposited on quartz substrate, where x varies from 0 to 1, was determined by high-resolution transmission electron microscopy in the sample regions with x approximate to 0.1, 0.2. 0.5. and 0.75. In the Si-0.5(SiO2)(0.5) region, the formation of a Si nanocrystallite network was established. At high concentrations of Si nanocrystallites, nanotwins and stacking faults occurred in the crystallites. Large Si crystallites appeared at x >= 0.5 in the quartz Substrate under the interface, while the film presented nanopores over the interface. The mechanisms for the formation of the nanocrystallites were discussed and correlated with the film properties.

Despite many investigations already performed with respect to sintering stability and grain growth vs. annealing conditions in low yttrium doped alpha- Al2O3 (150 ppm) - some fundamental questions are still open. These questions concern mainly the influence of small level of impurities at grain boundary in the sintering behavior and grains growth of the materials, i.e. the microstructure function of the annealing time at annealing temperature of 1650 degrees C. The low yttrium doped alpha- Al2O3 (150 ppm) samples were sintered and annealed at high temperatures. Besides conventional micro structural studies, such as grain diameter and grain size functions of distribution of the annealing temperature were studied by electron microscopy investigations and statistical measurement. The implications of the different microstructures with respect to micro structural stability have discussed and compared to observations described in the literature.

N-doping is often used to improve the photocatalytic properties of TiO2, films in order to achieve visible light response. In this work, we study the effect of annealing treatment (temperature and atmosphere) on the structural and optical properties of undoped and N-doped TiO2, films by means of X-ray diffraction (XRD), Atomic Force Microscopy (AFM), Rutherford backscattering (RBS), X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE) and UV-VIS optical transmission spectroscopy. Porous five-layer TiO2, films were deposited by sol-gel method on quartz substrate and thermally treated in oxygen or NH3 flow at 500 and 600 degrees C. Significant doping effect was achieved after annealing at 600 degrees C in NH3 and a shift in optical bandgap value down to visible range (2.69 eV) was observed. (C) 2008 Elsevier B.V. All rights reserved.

Hydroxyapatite (HA) biocoatings were obtained using two different deposition methods: sol-gel and sputtering. A direct comparison of films obtained using different techniques is necessary because of possible formation of multi-phases and components in HA films. HA films were investigated using spectroscopic ellipsometry (SE) as a powerful method to evaluate composition and structural properties of the films. For both types of films, sputtering and sol-gel, a weak dispersion of the refractive index within the wavelength range 0.4-0.7 pm was found. This corresponds to a high energy bandgap and a high optical transparency in the UV-VIS range. The internal porosity varying in a wide range in the sol-gel films was evaluated using a modeling of SE data. Additionally to SE Studies, structural, chemical and optical characterizations of the Films were performed using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Two absorption bands observed in the wavelength ranges 550-600 cm(-1) and 1000-1200 cm(-1) can be attributed to the major absorption modes associated with HA in agreement with published data. Prom XPS analysis, the atom ratio Ca/P was found for sol-gel films close to the stoichiometric value 1.67. For sputtering films, a higher Ca/P ratio of about 2.1 was estimated. However, similar FTIR spectra have been recorded for both sputtering and sol-gel films. XRD Studies show also similar crystallization conditions by annealing at temperatures higher than 500 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

Nano-scale ordering may be revealed in transmission electron microscopy (TEM) by at least three techniques that will be presented in this work: selected area electron diffraction, conventional TEM and high-resolution TEM. Digital image processing is used to extract additional information from the high-resolution micrographs. The described methods are illustrated in a microstructural and compositional study of a 90%Pb(Mg1/3Nb2/3)O-3-10%PbTiO2 ceramic sample. High-resolution images reveal the presence of ordered compositional nano-domains, observable in two specific crystallographic orientations. Antiphase boundaries lying in the (111) planes separate them, while (100) and (111) facets separate the ordered domains from the disordered matrix.

In this work we report the synthesis and characterization of the polypyrrole - porous silicon nanocomposites. Our main goal is to control the growth of conducting polypyrrole into the alveolar pores of porous silicon, in order to get a functionalized nanocomposite with the required properties for application as electrode in microfluidic devices. Porous silicon was electrochemically etched from (100) p-type silicon wafers. Different silicon resistivities (from 1.8 to 11 Omega cm) and preparation conditions (different electrolyte concentrations and current densities) were used. The electrodeposition of polypyrrole into porous silicon was carried out galvanostatically, at a constant current density 2.5 mA/cm(2) from a solution containing acetonitrile, the monomer, pyrrole and p-toluensulfonic acid as electrolyte. The polymerization time was varied in order to investigate the growing process of polypyrrole into the pores. The morphology and of the as-prepared nanocomposites was investigated by SEM. The existence of PPY into porous silicon is evidenced by the EDX spectra of the nanocomposite. The electrical characterization evidences the relative contributions of the polypyrrole and the substrate resistivity, respectively.

Water-soluble gold nanoparticles, capped with captopril, have been synthesized and characterized. Their average size is 2.3 nm, with a spherical shape. These gold nanoparticles can be easily labeled with stable free radicals (4-amino-tempo) by a coupling reaction performed in the presence of 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ). Both synthesized and spin-labeled gold nanoparticles can be incorporated into much bigger (100 nm) silica nanoparticles using the Stober method, thus forming hybrid metal (gold)-inorganic (silica) nanoparticles. These hybrid silica nanoparticles (containing or not spin-labeled gold nanoparticles) can be easily spin-labeled with another stable free radical (4-isocyanato-tempo), leading to the formation of a double spin-labeled material. In this way, some stable free radicals are attached on the gold surface while others are attached on the silica surface. Three types of EPR spectra were recorded and discussed for the hybrid gold-silica nanoparticles: (1) where the spin labels are attached to the embedded gold nanoparticles, (2) where the spin labels are attached to the silica nanoparticles, and (3) in the case of the double spin labeled material where both gold and silica nanoparticles are spin-labeled. Influence of different solvents on the EPR spectra is also discussed.