National Institute Of Materials Physics - Romania

A two dimensional photonic crystal (2DPhC) with triangular symmetry is investigated using optical reflectivity measurements and numerical calculations. The system has been obtained by direct laser writing, using a pulsed laser (lambda = 775 nm), perforating an In-doped Ge wafer. A lattice of holes with well-defined symmetry has been designed. Analyzing the spectral signature of PBGs recorded experimentaly with finite difference time domain theoretical calculations one was able to prove the relation between the geometric parameters (hole format, lattice constant) of the system and its ability to trap and guide the radiation in specific energy range. It was shown that at low frequency and telecommunication ranges of transvelsal electric modes photonic band gap occur. This structure may have potential aplications in designing photonic devices with applications in energy storage and conversion as potential alternative to Si-based technology.

CuOx nanorods grown by calcination on a Cu plate and TiO2 successive layers were assembled by chemical means to obtain a broad band light captor. The synthesis of composite with complex architecture aimed at maximization of light absorption and at improvement of electron-holes separation of via the multiple n-p heterojunctions created at TiO2-CuOx boundaries, formed mostly by filling the pore network composite material with CuOx. Au nanoparticles were embedded into TiO2 matrix to enhance the light harvesting ability in visible domain via surface plasmon resonance (SPR) phenomenon and to help the photo-generated charge separation through the formation of Schottky barriers. Dual p-n semiconducting character of the composite was clearly evidenced by photoelectrochemical measurements. The composite material exhibited photoresponse even at wavelengths higher than 420 nm (in visible domain), both in cathodic and anodic regions. The enhanced light adsorption characteristics, the advancement in synthesis procedure of CuOx-Au_TiO2 composite material provide rationale for further development of novel light captor composites for photoenergy conversion. Other applications such electronics and gas sensors are envisaged. (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.

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.

The ability of photoelectron spectro-microscopy with sub-micrometer lateral resolution to identify ferroelectric domains by analysis of surface band bendings is demonstrated on lead zirco-titanate PZT(1 1 1) thin films grown by pulsed laser deposition. Conventional synchrotron radiation X-ray photoelectron spectroscopy allowed one to derive the surface composition of the sample and evidenced shifts toward higher binding energy when the sample is subject to intense soft X-ray beam. A basic model is developed which supposes that photogenerated carriers reduce the depolarization field, yielding a lower torque applied to the ferroelectric polarization. As a consequence, the out-of-plane component of the polarization increases. Domain migration during irradiation with soft X-ray is inferred from the relative amplitude of the components with different binding energy. When the flux density of soft X-ray is on the order of 1011 photons/(s mu m(2)), metal Pb clusters are formed at the surface on areas with the out-of-plane component of the polarization pointing outwards only. (C) 2015 Elsevier B.V. All rights reserved.

The compensation of the depolarization field in ferroelectric layers requires the presence of a suitable amount of charges able to follow any variation of the ferroelectric polarization. These can be free carriers or charged defects located in the ferroelectric material or free carriers coming from the electrodes. Here we show that a self-doping phenomenon occurs in epitaxial, tetragonal ferroelectric films of Pb(Zr0.2Ti0.8)O-3, consisting in generation of point defects (vacancies) acting as donors/acceptors. These are introducing free carriers that partly compensate the depolarization field occurring in the film. It is found that the concentration of the free carriers introduced by selfdoping increases with decreasing the thickness of the ferroelectric layer, reaching values of the order of 10(26) m(-3) for 10 nm thick films. One the other hand, microscopic investigations show that, for thicknesses higher than 50 nm, the 2O/(Ti+Zr+Pb) atomic ratio increases with the thickness of the layers. These results suggest that the ratio between the oxygen and cation vacancies varies with the thickness of the layer in such a way that the net free carrier density is sufficient to efficiently compensate the depolarization field and to preserve the outward direction of the polarization.

L-cysteine-thiolate monolayers spontaneously self-assembled on p- and n-GaAs(100) electrodes have been investigated by electrochemical impedance spectroscopy in H2SO4 solutions. On p-doped samples a potential-induced reversible proton transfer occurs within the L-cysteine-thiolate layer during both forward and backward potential scans; in contrast, on n-doped samples it is observed only in the reverse scan. The XPS data and the fractal analysis of the AFM images point to the field - dipole interactions operating distinctively in the L-cysteine-thiolate layer formed at p-and n-doped semiconducting substrates as the origin of the observed difference. The interaction of this small but highly polar molecule with the electrostatic field driven by the diffuse distribution of the excess charge in the semiconductor subsurface region both in equilibrium and under polarization conditions turned out to play a key role in determining the optimal orientation of the two polar groups. The latter one seems to be a prerequisite for the potential-induced internal proton transfer. (C) 2015 Elsevier Ltd. All rights reserved.

Hard carbon thin films were synthesized on Si (100) and quartz substrates by the Pulsed Laser Deposition (PLD) technique in vacuum or methane ambient to study their suitability for applications requiring high mechanical resistance. The deposited films' surface morphology was investigated by scanning electron microscopy, crystalline status by X-ray diffraction, packing and density by X-ray reflectivity, chemical bonding by Raman and X-ray photoelectron spectroscopy, adherence by pull-out measurements and mechanical properties by nanoindentation tests. Films synthesized in vacuum were a-C DLC type, while films synthesized in methane were categorized as a-C:H. The majority of PLD films consisted of two layers: one low density layer towards the surface and a higher density layer in contact with the substrate. The deposition gas pressure played a crucial role on films thickness, component layers thickness ratio, structure and mechanical properties. The films were smooth, amorphous and composed of a mixture of sp(3)-sp(2) carbon, with sp(3) content ranging between 50% and 90%. The thickness and density of the two constituent layers of a film directly determined its mechanical properties.

In the present study the formation of lithium cobaltite using a modified Pechini aqueous sol-gel process was investigated. The gelling processes in the lithium-cobalt-citric acid system in 1.1:1:1 molar ratio was performed at 80 A degrees C using aqueous solutions of 0.25 mol/dm(3) of Co(NO3)(2)center dot 6H(2)O with Li(NO3)center dot 6H(2)O or Co(CH3COO)(2)center dot 6H(2)O with Li(CH3COO)center dot 2H(2)O, respectively. The study of the mechanism of gelling of transition metal ion Co(II) in aqueous medium in the presence of lithium ions and citric acid as chelating agents was approached using mainly UV-Vis and FTIR spectroscopic methods. The UV-Vis spectroscopy indicated that the Co(II) ions are in a tetragonal distorted geometry characteristic to a D-4h group symmetry in the solutions in the early steps of the gels formation. After gelling at 80 A degrees C it was observed that the symmetry of the Co(II) ions becomes octahedral (O-h). From the FTIR spectra based on the frequency separation between the antisymmetric stretching nu(as)(COO-) and symmetric stretching nu(sym)(COO-) vibrations, it was identified that the carboxylic groups are bond as a bridging ligands. Using X-ray photoelectron spectroscopy it was identified that the cobalt is present in both final gels as Co(II) ions and the citrate ions are covalently bonded to the cobalt ions. The thermogravimetric/differential thermal analysis showed the thermal stability of the studied gels is higher in the low temperature range for the gels prepared using acetates. Based on the thermal analysis the Li-Co-CA gels were calcinated at 700 A degrees C for 6 h and for each gel a monophasic LiCoO2 was obtained.