National Institute Of Materials Physics - Romania

A numerical extension of the simple Stoner-Wohlfarth model to the case of bi-dimensional angular distributions of easy axis is provided. The results are particularized in case of step-like, Gaussian-like and user defined distributions. In spite of its simplicity, the model can be applied to magnetically textured thin films and multilayers with in-plane magnetic anisotropy, independently on the texture source. Exemplifications are provided for a simple ferromagnetic textured FeCo film as well as for a FeMn/FeCoi CufFeCo spin valve structure. (C) 2015 Elsevier B.V. All rights reserved.

Spherical aberration corrected transmission electron microscopes offer unprecedented capabilities in materials structural characterization down to atomic resolution. Electron energy loss spectroscopy (EELS) - spectrum imaging (SI) and annular bright field (ABF) imaging allow to simultaneously identify both the position and nature of the atomic species in a crystalline material. These techniques, along with conventional high-resolution transmission electron microscopy are particularly useful in heterostructures interfaces like epitaxial multilayers characterization, for identifying possible atomic interdiffusion at sub-nanometric scale. This paper presents the structural and compositional microanalysis down to atomic resolution of an epitaxial BaTiO3/SrRuO3/SrTiO3 ferroelectric heterostructure using complex complementary analytical electron microscopy techniques. The atomic arrangement of both heavy and light atomic species across the interfaces in the BaTiO3/SrRuO3/SrTiO3 heterostructures is revealed. (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.

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.

Interfaces formed by gold and copper on single crystal layers of (0 0 1) PbZr0.2Ti0.8O3 (PZT) produced by pulsed laser deposition and exhibiting outwards polarization are analyzed by X-ray photoelectron spectroscopy. The stoichiometry of the layers reproduces reasonably that of the PZT target. The band bending occurring at the interface between PZT and the metals is investigated by analyzing the core level shifts as function on the metal deposition. It is found that for Au/PZT(0 0 1) the gold layer is not continuous and the observed band bendings can be attributed to a Schottky mechanism, whereas for Cu/PZT(0 0 1) the copper layer is continuous; in this latter case, the observed band bendings towards higher energies (lower binding energies) can be attributed to a concomitant bending due to the Schottky effect together with the disappearance of the initial bending due to the outwards polarization of the samples. Metal Pb is observed to segregate only in the case of Cu/PZT(0 0 1), therefore the surface self-reduction might also be connected to the presence of a metal with lower work function, which for larger coverage forms a continuous metal layer, able to provide electrons to the surface. High resolution transmission electron spectroscopy yielded the disappearance of the tetragonal distortion in the case of Cu/PZT(0 0 1), in line with the assumption of disappearance of the polarization-induced band bending. (C) 2015 Elsevier B.V. All rights reserved.

A comprehensive study of optical transitions in direct-bandgap Ge0.875Sn0.125 group IV alloys via photo-luminescence measurements as a function of temperature, compressive strain and excitation power is performed. The analysis of the integrated emission intensities reveals a strain-dependent indirect-to-direct bandgap transition, in good agreement with band structure calculations based on the 8-band k.p and deformation potential methods. We have observed and quantified Gamma valley-heavy hole and Gamma valley-light hole transitions at low pumping power and low temperatures in order to verify the splitting of the valence band due to strain. We will demonstrate that the intensity evolution of these transitions supports the conclusion about the fundamental direct bandgap in compressively strained GeSn alloys. The presented investigation, thus, demonstrates that direct-bandgap group IV alloys can be directly grown on Ge-buffered Si(001) substrates despite their residual compressive strain.

Electrical properties of ferroelectric capacitors based on PbZr0.52Ti0.48O3 thin films grown by pulsed laser deposition on silicon substrate with SrTiO3 buffer layer grown by molecular beam epitaxy were studied. A SrRuO3 layer was deposited as bottom electrode also by pulse laser deposition and Pt, Ir, Ru, SrRuO3 were used as top contacts. Electrical characterization comprised hysteresis and capacitance-voltage measurements in the temperature range from 150 K to 400 K. It was found that the macroscopic electrical properties are affected by the electrode interface, by the choice of the top electrode. However, even for metals with very different work functions (e.g. Pt and SrRuO3) the properties of the top and bottom electrode interfaces remain fairly symmetric suggesting a strong influence from the bound polarization charges located near the interface. (C) 2015 Elsevier B.V. All rights reserved.

Although impurity doping of nanocrystals is essential in controlling their physical properties for various applications, the doping mechanism of ultrasmall, colloidal II-VI semiconductor nanocrystals, corresponding to the initial stages of growth, is not yet understood. In this study the concentrations of Mn2+ ions in the core, on the surface, and as an agglomerated separate phase in 2.9 nm cubic ZnS nanocrystals, prepared by a surfactant-assisted liquid liquid synthesis within 20 to 20 000 ppm nominal impurity concentration range, have been determined by quantitative multifrequency electron paramagnetic resonance. The unexpected strong decrease in the core doping efficiency with the nominal concentration increase, in contrast to the small variation of the doping efficiency for the surface-bound Mn2+ ions, and the sizable core doping efficiency observed for 1.8 nm nanocrystals were explained with the extended lattice defect assisted mechanism of incorporation. According to this mechanism, which is not size or shape limited, being active from the initial growth stages, the incorporation of Mn2+ ions takes place at surface sites with high binding energy on dislocation steps formed by the emerging stacking defects. High resolution transmission electron microscopy confirms the presence of such stacking defects in a large proportion of the investigated cubic ZnS nanocrystals, ensuring the operation of the proposed doping mechanism.