National Institute Of Materials Physics - Romania

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.

A series of niobium-modified aluminum hydroxide fluorides (denoted Nb@AIF(3)), prepared via a fluorolytic sol gel synthesis was investigated for the catalytic one-pot conversion of cellulose to lactic acid. The structure of the new acid catalysts is the result of the dispersion of niobium fluoride in an aluminum hydroxide fluoride matrix. The calcination of the catalysts at a relatively low temperature (350 degrees C) stabilized this structure. Catalytic performances in terms of lactic acid yields are directly correlated with the niobium content.

This work is focusing on generation, time evolution, and impact on the electrical performance of silicon diodes impaired by radiation induced active defects. n-type silicon diodes had been irradiated with electrons ranging from 1.5 MeV to 27 MeV. It is shown that the formation of small clusters starts already after irradiation with high fluence of 1.5 MeV electrons. An increase of the introduction rates of both point defects and small clusters with increasing energy is seen, showing saturation for electron energies above similar to 15 MeV. The changes in the leakage current at low irradiation fluence-values proved to be determined by the change in the configuration of the tri-vacancy (V-3). Similar to V-3, other cluster related defects are showing bistability indicating that they might be associated with larger vacancy clusters. The change of the space charge density with irradiation and with annealing time after irradiation is fully described by accounting for the radiation induced trapping centers. High resolution electron microscopy investigations correlated with the annealing experiments revealed changes in the spatial structure of the defects. Furthermore, it is shown that while the generation of point defects is well described by the classical Non Ionizing Energy Loss (NIEL), the formation of small defect clusters is better described by the "effective NIEL" using results from molecular dynamics simulations. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Atomic intermixing processes in relation to structural aspects and phase formation in Be based thin films subjected to different annealing treatments simulating the case of re-deposited layered structures on plasma facing components in nuclear fusion devices are reported. Accordingly, bilayers of Be/W and Be/C have been deposited on Si(001) substrates with Fe buffer layers. The Fe films have been prepared by radiofrequency sputtering and further processed by annealing in hydrogen atmosphere at 300 degrees C, for 90 min, at a pressure of 10 bars of H-2. After the Be/W and Be/C bilayer deposition by means of thermionic vacuum arc method, annealing in vacuum at 600 degrees C, for 10 min has been applied to the complex structures. The influence of annealing on the phase composition and atomic intermixing processes in the complex structures has been studied by means of X-ray photoelectron spectroscopy (XPS) and conversion electron Mossbauer spectroscopy (CEMS). The layered structures present an oxidation gradient with oxide phases in the uppermost layers and non-oxidized phases in the lower layers, as observed from the XPS data. The CEMS results revealed that the as-deposited structures contain a main metallic Fe phase and secondary superparamagnetic Fe oxide phases at the Fe/Be interface, while annealed samples present a large contribution of Fe-Be and Fe-C mixtures. The annealing treatment induces considerable atomic interdiffusion, strongly dependent on the nature of the upper layer. In the case of Be/W system, the annealing provides a much rougher Be/W interface, while in case of the Be/C structure, the annealing treatment only homogenize the structure over the whole depth. (C) 2014 Elsevier B.V. All rights reserved.