National Institute Of Materials Physics - Romania

Bioglasses (BG) are the inorganic materials exhibiting the highest indices of bioactivity. Their appliance as films for bio-functionalization of metallic implant surfaces has been regarded as an optimal solution for surpassing their limited bulk mechanical properties. This study reports on magnetron sputtering of alkali-free BG thin films by varying the target-to-substrate working distance, which proved to play an important role in determining the films' properties. Post deposition heat-treatments at temperatures slightly above the glass transformation temperature were then applied to induce inter-diffusion processes at the BG/titanium substrate interface and strengthening the bonding as determined by pull-out adherence measurements. The morphological and structural features assessed by SEM-EDS, XRD, and FTIR revealed a good correlation between the formations of inter-metallic titanium silicide phases and the films' bonding strength. The highest mean value of pull-out adherence (60.3 +/- 4.6 MPa), which is adequate even for load-bearing biomedical applications, was recorded for films deposited at a working distance of 35 mm followed by a heat-treatment at 750 degrees C for 2 h in air. The experimental findings are explained on the basis of structural, compositional and thermodynamic considerations. (C) 2013 Elsevier B.V. All rights reserved.

We study the ternary clathrate Pr3Pd20Si6 in specific heat and ac susceptibility measurements on a high-quality single crystal, distinguishing antiferromagnetic and antiferroquadrupolar ordering, as well as a hitherto unknown magnetic low-temperature transition. The specific heat shows the direct involvement of nuclear spin degrees of freedom in the antiferromagnetic ordering, which is well supported by our calculation of the hyperfine level scheme without adjustable parameters. Pr3Pd20Si6 is, therefore, one of the rare materials where the nuclear moments are involved in the formation of the magnetic ground state.

We report on specific heat and resistivity measurements under hydrostatic pressure on the quasi-one dimensional metal TlxV6S8. We studied the interplay between the low temperature superconducting (SC) ground state and a high temperature charge density wave (CDW) instability. We observed a clear dependency of the physical properties of TlxV6S8 on the Tl concentration x. The CDW anomaly is present in all investigated samples that are strongly enhanced at half Tl filling, x = 0.47. This is also the only composition for which no signature of superconductivity is observed. The specific heat results regarding the SC phase in Tl0.63V6S8 suggest that this compound is a highly anisotropic, weak coupling superconductor. Pressure suppresses both SC and CDW transitions to lower temperatures. Nevertheless, as the CDW gap is closed at a critical pressure p(c), the increase in the density of states leads to a small enhancement of T-c suggesting that SC and CDW compete for parts of the Fermi-surface.

Epitaxial SrCuO2 thin films were grown on (0 0 1) SrTiO3 substrates by pulsed laser deposition using a stoichiometric target. X-ray diffraction indicated that the SrCuO2 films undergo a structural phase transition as a function of the substrate temperature. Films deposited at temperatures below 600 degrees C exhibit a tetragonal phase with the c-axis oriented along the growth direction while films deposited at temperatures above 700 degrees C exhibit an orthorhombic phase with the b-axis oriented along the growth direction. Atomic force microscopy indicated that the as-grown film surfaces are rather smooth and the roughness increases with increasing substrate temperature. Energy dispersive X-ray spectroscopy in agreement with X-ray diffraction intensity ratio data revealed that all films are non-stoichiometric and contain Sr vacancies (Sr/Cu similar to 0.8). The influence of film-substrate lattice matching and substrate temperature on the structural phase transition is discussed. (C) 2012 Elsevier B.V. All rights reserved.

Ba(X1/3Ta2/3)O-3 (X = Mg, Zn) thin films were grown on commercial Pt-coated Si substrates by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) method. Single phase Ba(Mg1/3Ta2/3)O-3 and Ba(Zn1/3Ta2/3)O-3 ceramic targets having an ordered hexagonal structure (with P (3) over bar m1 space group) were used for deposition. Structural, morphological and surface characterizations of the Ba(X1/3Ta2/3)O-3 (BXT) films were performed using X-ray diffraction, scanning electron microscopy and atomic force microscopy. X-ray diffraction studies evidenced a cubic (disordered) perovskite structure, with unit cell typical for Pm3m space group. Scanning electron microscopy investigations showed that BXT films have a columnar microstructure, which is oriented perpendicular to the substrate. The temperature dependence of the dielectric permittivity of the films was recorded at 100 kHz. Unlike targets, the BXT films exhibit positive values of the temperature coefficient of the dielectric permittivity. BaMg1/3Ta2/3O3 and BaZn1/3Ta2/3O3 thin films with dielectric constant of about 22.5 and 25, respectively have been obtained. (C) 2012 Elsevier B.V. All rights reserved.

The formation of an interface between Bi2O3, Fe2O3, BiFeO3, Bi0.5Na0.5TiO3, and the high work function metallic RuO2 is studied using photoelectron spectroscopy with in situ RuO2 deposition. Schottky barrier heights are derived and the valence band maximum energies of the studied materials are aligned with respect to each other as well as to other functional oxides like SrTiO3 and PbTiO3. The energy band alignment follows systematic trends compared to a large number of oxides, and can be understood in terms of the contribution of Fe 3d and Bi 6s/6p (lone pair) orbitals to electronic states near the valence band maximum. The results indicate that the valence band maxima are largely determined by the local environment of the cations, which allows to estimate valence band maximum energies of oxides with multiple cations from those of their parent binary compounds. The high valence band maximum of BiFeO3 is consistent with reported p-type conduction of acceptor doped material, while the high conduction band minimum makes n-type conduction unlikely.

Barium titanate-substituted bismuth titanate ((Bi0.5Na0.5)(0.92)Ba0.08TiO3, BNT-BT0.08) nanotubes were fabricated using sol-gel chemistry, spin casting, and a porous polycarbonate membrane template. The structure and morphology of the tubes have been investigated by scanning electron microscopy and transmission electron microscopy. The diameter and length of these tubes were about 650 nm and 20 mu m, respectively, and their wall thickness was about 50 nm. The tubes were polycrystalline with average grain size of similar to 40 nm. The BNT-BT0.08 nanotubes exhibited ferroelectric behavior as evidenced by saturated piezoresponse hysteresis loops and phase switching. BNT-BT0.08 piezoelectric nanotubes promise novel device architectures and enhanced electric properties.

The leakage current in all oxide epitaxial (La,Sr)MnO3-ferroelectric-(La,Sr)MnO3 structures, where the ferroelectric layer is either BaTiO3 or Pb(Zr0.2Ti0.8)O-3, was analyzed on a broad range of temperatures and for different thicknesses of the ferroelectric layer. It was found that, although the structures are nominally symmetric, the current-voltage (I-V) characteristics are asymmetric. The leakage current depends strongly on the thicknesses of the ferroelectric layer, on temperature and on the polarity of the applied voltage. Simple conduction mechanisms such as space charge limited currents or thermionic emission cannot explain in the same time the voltage, temperature, and thickness dependence of the experimentally measured leakage currents. A combination between interface limited charge injection and bulk controlled drift-diffusion (through hopping in the case of BTO and through band mobility in the case of PZT) is qualitatively explaining the experimental I-V characteristics. (C) 2013 AIP Publishing LLC.

Metal-ferroelectric-metal structures based on epitaxial Pb(Zr0.2Ti0.8)O-3 thin films are prepared by pulsed laser deposition on single crystal SrTiO3 substrates ((001) orientation) with buffer SrRuO3 layer as bottom electrode. Pt, Cu, and SrRuO3 are used as top contacts. The current-voltage (I-V) measurements reveal a strong influence of the top electrode interface on the magnitude of the leakage current and the shape of the I-V characteristics. The lowest current values are obtained for top Cu and the highest for top Pt. Diode-like behavior is obtained for top Cu and Pt, but the forward and reverse biases are opposite in sign. Contrary to the case of BiFeO3 layers deposited on the same type of substrates, it was found that the diode-like behavior is not switchable with the polarization reversal although the polarization values are comparable. It is also shown that the metal-ferroelectric-metal (MFM) structure based on Pb(Zr,Ti)O-3 (PZT) can be simulated and modeled as a back-to-back connection of two Schottky diodes. The diode-like behavior of the MFM structure can be induced by a slight asymmetry of the potential barriers at the electrode interfaces behaving as Schottky contacts. The study ends with a critical discussion of the MFM structures based on PZT and BiFeO3 (BFO) layers. It is shown that the switchable diode-like behavior is not uniquely determined by the polarization reversal and is not a general characteristic for MFM structures. Such behavior may be present only if the polarization induced band-bending at the interface is generating an accumulation layer at the interface. This could be possible in BiFeO3 based MFM structures due to the lower band gap compared to Pb(Zr0.2Ti0.8)O-3 thin films. (C) 2013 AIP Publishing LLC.

The growth of gold layers on Pb(Zr,Ti)O-3 (PZT) deposited on SrTiO3 is investigated by X-ray photoelectron spectroscopy in the Au thickness range 2-100 angstrom. Two phases are identified, with compositions close to nominal PZT. The 'standard' phase is represented by all binding energies (Pb 4f, Ti 2p, Zr 3d, O 1s) sensibly equal to the nominal values for PZT, whereas the 'charged' phase exhibits all core levels are shifted by similar to 1 eV toward higher binding energies. By taking into account also scanning probe microscopy images together with recent photoemission results, the 'charged' phase belongs to P(+) regions of PZT, whereas the 'normal' phase corresponds to regions with no net ferroelectric polarization perpendicular to the surface. Au deposition proceeds in a band bending of Phi(PZT) - Phi(Au) similar to 0.4-0.5 eV for both phases, identified as similar shifts toward higher binding energies of all Pb, Ti, Zr, O core levels with Au deposition. The Au 4f core level exhibits also an unusually low binding energy component 1 eV below the 'nominal' Au 4f binding energy position (metal Au). This implies the existence of negatively charged gold, or electron transfer from PZT to Au, although the 'normal' PZT phase have a higher work function, as it is derived from the band bending. Most probably this charge transfer occurs toward Au nanoparticles, which have even higher ionization energies. High resolution transmission electron microscopy evidenced the formation of such isolated nanoparticles. (C) 2013 Elsevier B.V. All rights reserved.