National Institute Of Materials Physics - Romania

Radio-frequency Plasma Enhanced Chemical Vapour Deposition (in different methane dilutions) was used to synthesize adherent and haemocompatible diamond-like carbon (DLC) films on medical grade titanium substrates. The improvement of the adherence has been achieved by interposing a functional buffer layer with graded composition TixTiC1-x (x = 0-1) synthesized by magnetron co-sputtering. Bonding strength values of up to similar to 67 MPa have been measured by pull-out tests. Films with different sp(3)/sp(2) ratio have been obtained by changing the methane concentration in the deposition chamber. Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction were employed for the physical-chemical characterization of the samples. The highest concentration of sp(3)-C (similar to 87 %), corresponding to a lower DLC surface energy (28.7 mJ/m(2) ), was deposited in a pure methane atmosphere. The biological response of the DLC films was assayed by a state-of-the-art biological analysis method (surface enhanced laser desorption/ionization-time of flight mass spectroscopy), in conjunction with other dedicated testing techniques: Western blot and partial thromboplastin time. The data support a cause-effect relationship between sp(3)-C content, surface energy and coagulation time, as well as between platelet-surface adherence properties and protein adsorption profiles.

A high-performance polymeric nanostructured sensing layer for a surface acoustic wave sensor, deposited using a modified matrix assisted pulsed laser evaporation direct write technique, exhibited improved performance in terms of response time and frequency deviation. In the present work, we assessed the factors and mechanisms that account for the layer's increased sensing capabilities. The increase in the sensing performance was attributed to an increased diffusion constant, due to greater molecular mobility of polymeric chains caused by the nanoparticles embedded in the polymer matrix.

This paper analyses in detail the core levels evolution of Pb(Zr,Ti)O-3, i.e. Pb 4f, Zr 3d, Ti 2p, O 1s in various conditions: absolutely freshly prepared sample, sample stored under air, and the effects of in vacuum annealing. The aim of the study is to quantify separately the chemical reactivity at the surface and the band bending effects due to the ferroelectric polarization. It is found that freshly prepared samples present mostly inwards (down arrow) polarization. This phenomenon is mostly revealed by the Ti 2p and O 1s spectra, manifested as a distinct component with 1.8 eV lower binding energy in the O 1s binding energy and by 1.1 eV in the Ti 2p binding energy. Sample aging under air suppresses the inwards polarization, and most signal comes from surfaces not presenting ferroelectric permanent polarization perpendicular to the sample surface. This process conducts also to the formation of Pb(CO3)(2) on the surface. Annealing to temperatures up to 400 degrees C stabilizes a surface composed by a main part of surface without polarization perpendicular to the surface, and with some areas presenting outwards (up arrow) polarization. These areas have, most probably, different terminations, the polarized area being (Ti,Zr)O-2 terminated. (C) 2013 Elsevier B.V. All rights reserved.

This work presents a systematic investigation by X-ray photoelectron spectroscopy of the mechanisms of interface formation and band bending for Au/Pb(Zr,Ti)O-3 (PZT) layers grown on SrTiO3(001) with a SrRuO3 buffer layer, as function on the initial state of the PZT surface. After isolating the chemical effects, such as the formation of metal Pb at some surfaces, the evolution of the core levels with Au deposition allows one to simultaneously investigate the Schottky barrier formation and the built-in potential effects (charging induced by the static ferroelectric polarization). Areas of the sample with outwards P(+) and no polarization perpendicular to the surface P-(0) are identified for all samples. Only the freshly prepared sample exhibited inward polarization areas P(-). The built-in potential is on the order of 0.9 eV, while the Schottky band bending ranges from 0.2 to 0.6 eV towards lower absolute energies, therefore indicating that the work function of PZT exceeds that of Au deposited. We report also a chemically differentiate value of the built-in potential, manifested by a preferential distribution of the charge accumulated at the surface on Ti and O atoms. The O 1s and Ti 2p core levels manifest quite strong variations with the Au thickness for freshly prepared samples, resulting in shifts on the order of 2 eV towards lower binding energies. Au deposited on areas with an outward polarization is positively charged by the same potential as atoms from the PZT film (0.8-0.9 eV), whereas Au deposited on areas with an inward polarization forms a continuous grounded layer, which progressively pumps the accumulated charge and removes the polarization of these areas. (C) 2013 Elsevier B. V. All rights reserved.

The improvement of graphene derivates' fluorescence properties is a challenging topic and very few ways were reported up to now. In this Letter we propose an easy method to enhance the fluorescence of highly reduced graphene oxide (rGO) through non-covalent binding to a molecular fluorophore, namely the riboflavin (Rb). While the fluorescence of Rb is quenched, the Rb - decorated rGO exhibits strong blue fluorescence and significantly increased fluorescence lifetime, as compared to its pristine form. The data reported here represent a promising start towards tailoring the optical properties of rGOs, having utmost importance in optical applications. (C) 2013 Elsevier B.V. All rights reserved.

Novel complexes of type M2LCl4 center dot nH(2)O (M: Ni, n = 4; M: Cu, n = 2.5 and M: Zn, n = 1.5; L: ligand resulted from 1,3-phenylenediamine, 3,6-diazaoctane-1,8-diamine, and formaldehyde one-pot condensation) were synthesized and characterized. The ligand was also isolated and characterized. The complexes features have been assigned from microanalytical, electrospray ionization tandem mass spectrometry, IR, UV-vis, H-1 NMR, and EPR spectra as well as magnetic data at room temperature. Simultaneous thermogravimetric/dynamic scanning calorimetry/evolved gas analysis measurements were performed to evidence the nature of the gaseous products formed in each step. Processes as water elimination, fragmentation, and oxidative degradation of the organic ligand as well as chloride elimination were observed during the thermal decomposition. The final product of decomposition was metal(II) oxide except for copper complex where CuCl remained also in the oxide network. The complexes exhibited an improved antibacterial activity in comparison with the ligand concerning both planktonic as well as biofilm-embedded cells.

Self-assembled layers of 4,4'-thio-bis-benzene-thiolate spontaneously adsorbed on p-doped GaAs(1 1 1)A and GaAs(1 1 1)B electrodes were examined by EIS, XPS, and AFM investigations. XPS data provide evidence that (i) both As and Ga atoms are involved in the thiolate formation no matter which one is prevailing on the semiconducting surface and (ii) only one of the two thiol groups participates in the chemisorption bond. EIS and AFM results point to a more stable thiolate layer formed on the As-terminated surface than that formed on the Ga-terminated surface due to stronger self-assembling effects developed between the adsorbed species. (C) 2013 Elsevier Ltd. All rights reserved.

Hexagonal ferrites BaxSr1-xFe12O19 (x = 0.05, 0.15, 0.25, 0.35) were prepared by sol-gel and conventional solid state reaction techniques. Their magnetic properties, investigated by magnetometry and Mossbauer spectroscopy, were discussed in correlation to structural aspects. Whereas the hexaferrites obtained by sol-gel are almost single phase, the ones prepared by the conventional solid state reaction technique present a low amount of BaFe2O4 as secondary phase. All samples show a relative high coercive field and remanent magnetization, as specific features for permanent magnet behavior. The five Fe3+ sites of the specific elemental cell have been revealed and their relative occupancy has been derived from the Mossbauer spectra. The analyzed samples show a sensitivity of the magnetic properties (magnetic moment and anisotropy) with respect to the occupancy of the different Fe sites. (C) 2013 Elsevier B. V. All rights reserved.

The surface of a ferroelectric BaTiO3(001) single crystal was studied using synchrotron radiation induced x-ray photoelectron diffraction (XPD), x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and low-energy electron diffraction (LEED). AFM, XPS, and LEED show that the surface is BaO terminated with a (1 x 1) reconstruction. The Ba 4d, Ti 2p, and O 1s XPD results were compared with multiple scattering simulations for out-of- (P+, P) and in-plane (P-in) polarizations using a genetic algorithm to determine atomic rumpling and interlayer relaxation. Linear combinations of the XPD simulations of the surface structure of each polarization state allow determination of the domain ordering. The best agreement with experiment is found for 55% P+, 38% P-, and 7% P-in. The rumpling is smaller at the surface than in the bulk, suggesting that both domain ordering and surface structural changes contribute to screening of the polarization.

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.