National Institute Of Materials Physics - Romania

The chemical modification of the niobium (Nb) surface after irradiation with femtosecond laser pulses was investigated by scanning electron microscopy coupled with energy dispersive spectroscopy, atomic force microscopy, grazing incidence X-ray diffraction, and micro-Raman spectroscopy. The physical-chemical analyses indicated that the laser treatment results in oxidation of the Nb surface, as well as in the formation of Nb hydrides. Remarkably, after the samples' washing in ethanol, a strong Surface-Enhanced Raman Scattering (SERS) signal originating from the toluene residual traces was evidenced. Further, it was observed that the laser irradiated Nb surface is able to provide a SERS enhancement of similar to 1.3 x 10(3) times for rhodamine 6G solutions. Thus, for the first time it was shown that Nb/Nb oxide surfaces could exhibit SERS functionality, and so one can expect applications in biological/biochemical screening or for sensing of dangerous environmental substances. (C) 2015 AIP Publishing LLC.

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.

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.

Bioactive glasses are currently considered the suitable candidates to stir the quest for a new generation of osseous implants with superior biological/functional performance. In congruence with this vision, this contribution aims to introduce a reliable technological recipe for coating fairly complex 3D-shaped implants (e.g. dental screws) with uniform and mechanical resistant bioactive glass films by the radio-frequency magnetron sputtering method. The mechanical reliability of the bioactive glass films applied to real Ti dental implant fixtures has been evaluated by a procedure comprised of "cold" implantation in pig mandibular bone from a dead animal, followed by immediate tension-free extraction tests. The effects of the complex mechanical strains occurring during implantation were analysed by scanning electron microscopy coupled with electron dispersive spectroscopy. Extensive biocompatibility assays (MTS, immunofluorescence, Western blot) revealed that the bioactive glass films stimulated strong cellular adhesion and proliferation of human dental pulp stem cells, without promoting their differentiation. The ability of the implant coatings to conserve a healthy stem cell pool is promising to further endorse the fabrication of new osseointegration implant designs with extended lifetime. (C) 2015 Elsevier Ltd. All rights reserved.

Electric and pyroelectric properties of AIN layers deposited on Si substrates with different resistivities were investigated. The dielectric constant was found to be around 12, while the conductance determined from dc current measurements was found to be in the 10(-9) to 10(-19) S range. The pyroelectric measurements were performed in voltage mode using two types of IR sources: a laser diode with 800 nm wavelength and a black body at 700 degrees C. A peculiar behavior was observed for the signal recorded when the laser diode was used as IR source. It was found that the Si substrate is introducing a signal component, due to the photogenerated carriers, which is adding to the pyroelectric signal generated by the AIN layer. This component is strongly dependent on the resistivity of the Si substrate. For strongly doped Si (Si++) the signal generated into the substrate represents only 10% of the recorded pyroelectric voltage. For electronic grade Si the signal generated into the substrate is about 100 times larger than the pyroelectric signal generated in the AIN layer. This effect can be used as an optical amplification of the pyroelectric signal. The frequency dependence observed for the pyroelectric signal recorded when the black body is used as IR source is typical for a pyroelectric detector. A value as large as 12.4 degrees C m(-2) K-1 was obtained for the pyroelectric coefficient using for estimation the constant signal at low modulation frequencies of the IR beam. However, the value of the pyroelectric coefficient is strongly affected by the electrical conductance of the AIN layer. As the conductance is frequency dependent it results that the value of the pyroelectric coefficient is frequency dependent, the value from above being valid only for very small frequencies of the temperature variation. It was also found that the electric and pyroelectric properties are dependent on the crystalline quality of the AIN layer. (C) 2015 Elsevier B.V. All rights reserved.

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.

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.

GeTe and GaSb thin films obtained by pulsed laser deposition were investigated by spectroscopic ellipsometry at controlled temperatures. The GeTe films were fully amorphous, while the GaSb films were partially crystalized in the as-deposited state. The Tauc-Lorentz model was employed to fit the experimental data. From the temperature study of the optical constants, it was observed the crystallization in the 150-160 degrees C range of GeTe amorphous films and between 230 and 240 degrees C of GaSb amorphous phase. A second transition in the resonance energy and the broadening parameter of the Lorentz oscillator was observed due to the crystallization of Sb after 250 degrees C. The temperatures of 85 degrees C and 130 degrees C are noticed as the start of the relaxation of the amorphous GeTe phase and as-deposited GaSb. The peaks of the imaginary part of the dielectric function red shifted after the phase change, while the variation with temperature of the crystalline phase follows the Varshni law. The electron-phonon coupling constants are 2.88 and 1.64 for c-GeTe and c-GaSb, respectively. An optical contrast up to 60% was obtained for GeTe films and a maximum value of 7.5% is revealed in the case GaSb, which is altered by the partial crystallinity of the as-deposited films. (C) 2015 AIP Publishing LLC.

The current-voltage (C-V) characteristic of epitaxial ferroelectric films is simulated assuming the presence of Schottky-type contacts at the two electrode interfaces. The model assumes that the overall capacitance of the metal-ferroelectric-metal (MFM) structure is composed of two parts: (i) one associated with the Schottky contacts, in which the ferroelectric polarization is saturated, the dielectric constant is independent on the voltage and only the linear response to the applied electric field is taken into account; (ii) one related to the ferroelectric volume, where the dielectric constant is voltage dependent through the hysteresis response of the ferroelectric polarization. Themost important result of the model is that it can simulate the experimentally observed thickness dependence of the dielectric constant without considering a so-called "dead layer" at the electrode interface. The model renders C-V characteristics in good qualitative agreement with the experimental ones in the case of an MFM structure based on epitaxial PZT films. The quantitative fit suggests that the behaviour of the ferroelectric polarization during the C-V measurement may be very different from its behaviour during the hysteresis measurement. This is explained by the fact that the two measurements have very different principles. It is also found that the dielectric constant of the ferroelectric volume has a different voltage dependence compared to the one derived from the hysteresis loop or from the experimental C-V characteristic. This is also related to the different measurement principles and to the fact that the measured capacitance of the MFM structure includes, besides the ferroelectric volume, the voltage dependent capacitance of the Schottky contacts. (C) 2015 Elsevier B.V. All rights reserved.

Powder mixtures of MgB2 and B4C with composition ((MgB2) + (B4C) x, x = 0.005, 0.01, 0.03) were consolidated by Spark Plasma Sintering at 1150 degrees C for 3 min. The average particle size of B4C raw powder was relatively high of 4 mm. Despite this, it is shown that processing processes are fast and, as in the case of the in-situ routes, for our ex-situ method carbon substitutes for the boron in the crystal lattice of MgB2. Specifics of microstructure are discussed based on electron microscopy observations. Carbon substitution and microstructure contribute to enhancement of the critical current density J(c) at high magnetic fields and of the irreversibility field H-irr. Samples are shown to be in the point pinning limit with some tendency toward the grain boundary pinning depending on B4C doping amount and temperature. An optimum composition is found for x = 0.01: for this sample, at 20 K, a J(c) of 100 A/cm(2) is obtained at 5.35 T. This value is higher than for the pristine MgB2 sample and for an optimum ex-situ nano-SiC-doped sample obtained for the same SPS processing conditions. (C) 2015 Elsevier B.V. All rights reserved.