Publications

A polycrystalline graphite target was irradiated using infrared (800 nm) femtosecond (120 fs) laser pulses of different energies. Increase of sp(3) bonds percentage and possible diamond crystal formation were investigated 'in-depth' and on the irradiated surfaces. Synchrotron X-ray diffraction pattern have shown the presence of a diamond peak in one of the irradiated zones while X-ray photoelectron spectroscopy investigations have shown an increasing tendency of the sp(3) percent in the low power irradiated areas and similarly 'in the depth' of the higher power irradiated zones. Multiple wavelength Micro-Raman investigations have confirmed this trend along with an 'in-depth' (but not on the surface) increase of the crystallite size. Based on the wavelength dependent photon absorption into graphite, the observed effects are correlated with high density photon per atom and attributed to the melting and recrystallization processes taking place tens of nanometers below the target surface. (c) 2015 Elsevier B.V. All rights reserved.

A combination of chemical and thermal annealing techniques was used to prepare an array of ZnO/Zn1-xMNxO/BaTiO3 nanorods. ZnO nanorod arrays were obtained by hydrothermal-electrochemical processes. The precursors for Zn1-xMnxO and BaTiO3, prepared by sol-gel technique were deposited by spin coating on the surface of ZnO nanorods. Each deposition stage was accompanied by thermal treatment stages. Scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and photoluminescence spectroscopy reveal the presence of a film of Zn1-xMnxO with wurtzite structure on the surface of ZnO nanorods. Transmission electron microscopy images demonstrate that a layer of BaTiO3 is deposited on the surface of each ZnO/Zn1-xMnxO core shell nanorod. BaTiO3 film onto the ZnO/Zn1-xMnxO core shell nanorods is also evidenced in Raman scattering by broadening of the Raman band situated in the spectral range 500-750 cm(-1). (C) 2015 Elsevier B.V. All rights reserved.

CoxFe3-xO4 (x=0.5-2.5) magnetic nanoparticles were synthesized via redox reaction between cobalt nitrate, iron nitrate and 1-4-butanediol using five Co/Fe molar ratios, followed by calcination at 1000 degrees C. Single phase nanoscaled cobalt ferrite was obtained at x=1.0 and at slight Co excess (x=1.5), while at high Co/Fe molar ratios (x=2.0 and x=2.5) the prevailing phase was CoO accompanied by CoFe2O4 traces. The highest values of coercive field and saturation magnetization were obtained for the sample at x=1.0, while the lowest values were obtained in the sample with the highest Co excess (x=2.5). The results indicated that the used synthesis route was suitable for the synthesis of cobalt ferrite with moderate saturation magnetization and high coercive field values. (C) 2015 Elsevier B.V. All rights reserved.

Light confinement in a two dimensional photonic crystal (2D PhC) with hexagonal symmetry is studied using infra-red reflectance spectromicroscopy and numerical calculations. The structure has been realized by laser ablation, using a pulsed laser (lambda = 775 nm), perforating an In-doped Ge wafer and creating a lattice of holes with well-defined symmetry. Correlating the spectral signature of the photonic gaps recorded experimentally with the results obtained in the finite difference time domain and finite difference frequency domain calculations, we established the relationship between the geometric parameters of the structure (lattice constants, shape of the hole) and its efficiency in trapping and guiding the radiation in a well-defined frequency range. Besides the gap in the low energy range of transversal electric modes, a second one is identified in the telecommunication range, originating in the localization of the leaky modes within the radiation continuum. The emerging picture is of a device with promising characteristics as an alternative to Si-based technology in photonic device fabrication with special emphasize in energy storage and conversion. (C) 2015 Elsevier B.V. All rights reserved.

Composite silk fibroin-poly(3-hydroxybutyric-acid-co-3-hydroxyvaleric-acid) (SF-PHBV) biodegradable coatings were grown by Matrix Assisted Pulsed Laser Evaporation on titanium substrates. Their physicochemical properties and particularly the degradation behavior in simulated body fluid at 37 degrees C were studied as first step of applicability in local controlled release for tissue regeneration applications. SF and PHBV, natural biopolymers with excellent biocompatibility, but different biodegradability and tensile strength properties, were combined in a composite to improve their properties as coatings for biomedical uses. FTIR analyses showed the stoichiometric transfer from targets to coatings by the presence in the spectra of the main absorption maxima characteristic of both polymers. XRD investigations confirmed the FTIR results showing differences in crystallization behavior with respect to the SF and PHBV content. Contact angle values obtained through wettability measurements indicated the MAPLE deposited coatings were highly hydrophilic; surfaces turning hydrophobic with the increase of the PHBV component. Degradation assays proved that higher PHBV contents resulted in enhanced resistance and a slower degradation rate of composite coatings in SBF. Distinct drug-release schemes could be obtained by adjusting the SF:PHBV ratio to controllably tuning the coatings degradation rate, from rapid-release formulas, where SF predominates, to prolonged sustained ones, for larger PHBV content. (C) 2015 Elsevier B.V. All rights reserved.

We report sub-diffraction limited patterning of Si substrate surfaces by laser-initiated liquid-assisted colloidal lithography. The technique involves exposing a two-dimensional lattice of transparent colloidal particles spin coated on the substrate of interest (here Si) immersed in a liquid (e.g. methanol, acetone, carbon tetrachloride, toluene) to a single picosecond pulse of ultraviolet laser radiation. Surface patterns formed using colloidal particles with different radii in the range 195 nm <= R <= 1.5 mu m and liquids with differing indices of refraction (n(liquid)) are demonstrated, the detailed topographies of which are sensitively dependent upon whether the index of refraction of the colloidal particle (n(colloid)) is greater or smaller than n(liquid) (i.e. upon whether the incident light converges or diverges upon interaction with the particle). The spatial intensity modulation formed by diffraction of the single laser pulse by the colloidal particles is imprinted into the Si substrate.

Ba0.95Ce0.05Ti0.9875O3 nanowires were fabricated by sol-gel method using as template a polycarbonate membrane with channels of 100 nm diameter. FE-SEM analyses showed that continuous gel wires of length up to 17 mu m and an average diameter of 81 nm, were obtained. After calcination at 700 degrees C for 1 h, these green 1D nanostructures were converted into well-crystallised wires with an average diameter of 59.7 nm, as high-resolution transmission electron microscopy and selected area electron diffraction indicated. The piezoelectric activity of the Ba0.95Ce0.05Ti0.9875O3 nanowires was investigated using piezoresponse force microscopy (PFM) correlated with atomic force microscopy. The results of PFM measurements indicated that the wires exhibit a significant fraction of ferroelectric domains larger than the grains size and a good piezoelectric response.

Epitaxial (1 - x)Ba(Ti0.8Zr0.2)TiO3 - x(Ba0.7Ca0.3)TiO3, x = 0.45 (BCZT 45), thin films have been deposited on (001) SrTiO3 (STO) and (001/100) SrLaAlO4 (SLAO) substrates by pulsed laser deposition. X-ray diffraction and high-resolution transmission electron microscopy (HRTEM) confirmed the epitaxial growth of the films. A high structural quality has been evidenced for the BCZT/STO films. Geometric phase analysis (GPA) associated with the HRTEM enabled us to obtain microstrain analysis and the in-plane and out-of-plane lattice parameter variation on different areas. Tetragonality ratio fluctuations at nanoscale level which are relevant for the existence of nanodomains have been evidenced on the BCZT/STO films. The in-plane dielectric constant has been measured on interdigital electrodes deposited by lift-off technique on the top of the films. High values of dielectric permittivity (>3000) combined with low dielectric loss (<0.01) are obtained for BCZT 45 film deposited on STO substrate, showing nearly constant values between 1 kHz and 10 MHz. The high dielectric permittivity of BCZT thin films was attributed to their high structural quality and to the loss of rotation stability of the polarization associated with the presence of nanodomains. This results into a divergence of fluctuations of polarization direction and a peak of dielectric susceptibility. The enhanced switching of such nanodomain configuration was probed by piezoforce microscopy, by writing and reading domains during topography scanning.

Ni-doped (CeO2-delta)-YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been synthesized by an original, facile and cheap approach based on Triton X100 nonionic surfactant as template and water as solvent at a strong basic pH value. Following the hydrothermal treatment under autogenous pressure (similar to 18 bars), Ni, Ce, Y, and Zr were well ordered as MA with nanocrystalline framework, assuring thermal stability. A comprehensive investigation of structure, texture, morphology, and surface chemistry was performed by means of a variety of complementary techniques (X-Ray Diffraction, XRD; Raman Spectroscopy, RS; Brunauer-Emmett-Teller, BET; Temperature-Programmed Reduction, TPR; Transmission Electron Microscopy, TEM and DF-STEM; X-ray Photoelectron Spectroscopy, XPS; Catalytic activity and selectivity). N-2 sorption measurements highlighted that the mesoporous structure is formed at 600 degrees C and remains stable at 800 degrees C. At 900 degrees C, the MA collapses, favoring the formation of macropores. The XRD and Raman Spectroscopy of all samples showed the presence of a pure, single phase with fluorite-type structure. At 900 degrees C, an increased tetragonal distortion of the cubic lattice was observed. The surface chemistry probed by XPS exhibits a mixture of oxidation states (Ce3+ + Ce4+) with high percentage of Ce3+ valence state similar to 35 % and (Ni3+ and Ni2+) oxidation states induced by the thermal treatment. These nanoparticles assembled into MA show high stability and selectivity over time in catalytic partial oxidation of methane (CPOM). These promising performances suggest an interesting prospect for introduction as anode within IT-SOFC assemblies.

Hypothesis: The MU [3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium-bromide] cell cytotoxicity indicator is photocatalytically reduced on the surface of TiO2 nanoparticles in phosphate-buffered-saline (PBS) environment. We hypothesize that specific phosphate adsorption may be used to modulate the efficiency of the TiO2 MU reaction through colloidal and semiconductor-liquid interface processes. Experiments: The TiO2 MU reaction kinetics was studied in PBS, with respect to photocatalyst and MIT concentrations and irradiation wavelength. The effects of PBS and electron scavengers (Fe3+ ions) on reaction efficiency and the role of colloidal surface charge in the photocatalytic process were investigated. The structural and spectroscopic characteristics of relevant TiO2-formazan systems were studied by X-ray diffraction, transmission electron microscopy and IR-spectroscopy. Findings: The reaction was pseudo-first order with respect to photocatalyst and showed a negative and fractional partial order with respect to MU. Formazan production rates were directly proportional to radiation wavelength and TiO2 concentration and inversely proportional to the MIT initial concentration. The addition of Fe3+ ions, as well as the absence of PBS, induced strong reaction inhibition. Reaction efficiency and catalyst Zeta potential were enhanced by Na2HPO4 (PBS component) and showed a maximum around the phosphate concentration 0.005 M. Findings: Structural/spectroscopic characterization confirmed the formation of amorphous MU-formazan on the surface of TiO2 and the TiO2-phosphate binding. (C) 2015 Elsevier Inc. All rights reserved.