National Institute Of Materials Physics - Romania

Electrochemical impedance spectroscopy investigations carried out in solutions with different pH brought evidence that the monolayers of L-cysteine-thiolate self-assembled on GaAs (hid) electrodes exert a complex molecular control over their electrochemical behavior. The analysis of the impedance spectra coupled with that of the XPS data and the AFM images taken before and after the EIS measurements reveled that both pH and applied potential brings significant changes at the electrified interface. The most important effect of pH is the conformational change of the L-cysteine-thiolate molecule observed at pH 11 that allows the interaction of the carboxyl group with the substrate atoms. A similar conformational change occurs at pH 5.5 but only under the applied potential control, being just a consequence of another major effect of the applied electric field. This is the H+ transfer inside the L-cysteine-thiolate film, an electric field driven process but pH dependent, which results in significant charge diminution both in the organic overlayer and in the semiconductor depletion region. (C) 2013 Elsevier Ltd. All rights reserved.

The band bending at Cu/PZT(001) interfaces is investigated by X-ray photoelectron spectroscopy (XPS) for a PZT(001) layer which exhibits initial outwards ferroelectric polarization. Two competitive processes are identified: (a) formation of the Schottky barrier between the ferroelectric and unconnected Cu islands, and (b) coalescence of the Cu islands, realisation of an electrical contact to the ground of the system, inducing the apparent loss of the component of the ferroelectric polarization perpendicular to the sample surface, at least as it manifests in band bending. Three mechanisms are proposed to explain this loss of band bending when a full metal layer connected to ground is formed on the surface: (i) over-compensation of depolarization field in the sub-surface region, (ii) formation of domains with in-plane orientation of the polarization vector and (iii) loss of polarization in the near-surface layers of the ferroelectric due to electrons provided by the metal. These result in a non-monotonous variation of binding energies with the amount of Cu deposited. High resolution transmission electron microscopy and piezoresponse force microscopy confirmed these hypotheses. The XPS data allowed also to derive the surface PZT composition, its evolution with the deposition of copper and the formation of surface compounds.

Novel complexes of M2LCl4 center dot nH(2)O type (M:Ni, n = 4; M:Cu, n = 3 and M:Zn, n = 0; L: ligand resulted from 1,4-phenylenediamine, 3,6-diazaoctane-1,8-diamine and formaldehyde one-pot condensation) were synthesized and characterised by microanalytical, ESI-MS, IR, UV-Vis, H-1 NMR and EPR spectra, magnetic data at room temperature and molar conductivities as well. The electrochemical behaviour of complexes was investigated by cyclic voltammetry. Simultaneous TG/DTA measurements were performed in order to evidence the thermal behaviour of the obtained complexes. Processes such as water elimination, fragmentation and oxidative degradation of the organic ligand as well as chloride elimination occurred during thermal decomposition. The antimicrobial assays demonstrate that the compounds exhibited good antibacterial activity, especially against S. aureus and E. coli strains, the most active being the copper(II) complex, which also exhibited the most prominent anti-biofilm effect, suggesting its potential use for the development of new antimicrobial agents. The biological activity was correlated with log P (ow) values. All complexes disrupt the membrane integrity of HCT 8 tumour cells.

Bioactive glasses are osteoproductive-type inorganic materials possessing the highest indices of bioactivity in both bulk and thin film forms. The prerequisites for reliable implant-type coatings are both their biological and mechanical performances. Whilst the bioglass films' structural, chemical and biological properties have been studied extensively, information about their mechanical performance is scarce. Here, transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, nanoindentation and pull-out measurements were employed to assess the morphological, chemical, structural and mechanical properties of the bioglass films deposited onto Ti substrates by radio-frequency magnetron sputtering (RF-MS). The biological safety of the thin bioglass films was evaluated preliminarily in vitro by investigating the adherence, proliferation and cytotoxicity of fibroblast cells cultivated on their surface. Our study emphasize the versatility of RF-MS, showing how bioglass films' features such as composition, structure, bonding strength, hardness, elastic modulus and biological response can be conveniently adapted by tuning the RF-MS working conditions, and therefore demonstrating the unexplored potential of this deposition technique for preparing quality biomimetic glass coatings. (C) 2013 Elsevier B. V. All rights reserved.

Electrode interface is a key element in controlling the macroscopic electrical properties of the ferroelectric capacitors based on thin films. In the case of epitaxial ferroelectrics, the electrode interface is essential in controlling the leakage current and the polarization switching, two important elements in the read/write processes of nonvolatile memories. However, the relation between the polarization bound charges and the electronic properties of the electrode interfaces is not yet well understood. Here we show that polarization charges are controlling the height of the potential barriers at the electrode interfaces in the case of Pb(Zr,Ti)O-3 and BaTiO3 epitaxial films. The results suggest that the height is set to a value allowing rapid compensation of the depolarization field during the polarization switching, being almost independent of the metals used for electrodes. This general behavior open a new perspective in engineering interface properties and designing new devices based on epitaxial ferroelectrics.

A single atomic Au layer is grown epitaxially on a Ge(001) surface featured by (2 x 1) reconstruction. The low energy electron diffraction pattern of the Au/Ge(001) surface indicates the formation of a square structure with the length of crystalline domains of similar to 3 nm. Ab-initio calculations show that Au growth stabilizes the Ge surface in symmetric dimers and angle-resolved photoelectron spectroscopy measurements reveal its metallic character. The modifications in the electronic properties of the Ge surface as a result of annealing are discussed and the consequences as reflected in X-ray photoelectron spectroscopy (XPS) measurements are underlined. The deformation density indicates the regions with covalent Au-Ge bonds. These bonds are identified from Au 4f and Ge 3d XPS data. (C) 2013 Elsevier B.V. All rights reserved.

Lead-free piezoelectric (Bi0.5Na0.5)(0.92)Ba0.08TiO3, doped with 5 mol %BiFeO3 (BNT-BT-BFO) nanowires was prepared from its corresponding precursor sol. A polycarbonate membrane with the thickness of 30 mu m and the pore diameter of 100 nm was used as template. Nanowires with average diameter of similar to 80 nm and different lengths of a few microns were prepared from BNT-BT-BFO precursor sol with similar to 0.03 M concentration. Ferroelectric and piezoelectric characterizations of BNT-BT-BFO nanowires were performed using AFM-PFM equipment. The HR-TEM micrograph of nanocrystals, SAED patterns, and XRD pattern indicated that BNT-BT-BFO nanowires crystallized on the lattice of rhombohedral (Na0.5Bi0.5TiO3) phase. The BNT-BT-BFO nanowires showed a significant piezoelectric response, suggesting a good piezoelectric behavior. The saturation magnetization of the nanowires, measured at room temperature and at 5 kOe magnetic field, was Ms = 0.061 emu/g. A saturated ferromagnetic hysteresis loop has been also obtained.

Gold islands forming highly controlled arrays have been fabricated by two potential step electrochemical deposition method using nanopatterned Si surface templates. In the present work, the Raman scattering studies realized using 11-mercaptoundecanoic probe molecule showed that such structures exhibit an enhanced Raman signal compared with nanostructured physical deposited thin gold film on flat silicon substrate and can be valued as surface-enhanced Raman scattering substrates. Besides the more appropriate management of nano-island arrays distribution, the high ratio of their Raman signals can be explain by the epitaxial-like growth mechanism of themetallic nano-islands, clearly showed by X-ray diffraction studies. Furthermore, the substrates enabled reproducibility and stability detection due to the chemically assembling of organothiol molecules, the X-ray photoelectron spectroscopy studies confirming formation of the thiolate species which corresponds to Au - S bonds, and also, the unwanted 'hot-spots' are missing, which make them suitable for high sensitivity biosensing applications. (C) 2013 Published by Elsevier B.V.

We report the synthesis of a room temperature ferromagnetic Mn-Ge system obtained by simple deposition of manganese on Ge(001), heated at relatively high temperature (starting with 250 degrees C). The samples were characterized by low energy electron diffraction (LEED), scanning tunneling microscopy (STM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), superconducting quantum interference device (SQUID), and magneto-optical Kerr effect (MOKE). Samples deposited at relatively elevated temperature (350 degrees C) exhibited the formation of similar to 5-8 nm diameter Mn5Ge3 and Mn11Ge8 agglomerates by HRTEM, while XPS identified at least two Mn-containing phases: the agglomerates, together with a Ge-rich MnGe similar to 2.5 phase, or manganese diluted into the Ge(001) crystal. LEED revealed the persistence of long range order after a relatively high amount of Mn (100 nm) deposited on the single crystal substrate. STM probed the existence of dimer rows on the surface, slightly elongated as compared with Ge-Ge dimers on Ge(001). The films exhibited a clear ferromagnetism at room temperature, opening the possibility of forming a magnetic phase behind a nearly ideally terminated Ge surface, which could find applications in integration of magnetic functionalities on semiconductor bases. SQUID probed the co-existence of a superparamagnetic phase, with one phase which may be attributed to a diluted magnetic semiconductor. The hypothesis that the room temperature ferromagnetic phase might be the one with manganese diluted into the Ge crystal is formulated and discussed.

A genuine GaAs surface is covered with a relatively thick layer (similar to 10 nm) of native oxide pinning the surface Fermi level within the band gap of semiconductor. The method presented in this work is related to the sulphur passivation by treating n-GaAs(100) and (110) in sulphide solutions (e.g pure ammonium sulphide and sulphur monochloride) that combines both chemical electronic passivation by reducing the surface state density. The effects of passivation were put into evidence by Photoluminescence measurements where it was observed the variation of state density. The presence of sulphur dipoles at surface was presented in a diagram of Second Harmonic Generation analysis and the general aspect of sulphur compound was identified by SEM images. The presence of the covalent bond Ga-S and the variation of surface barrier as well as the effect of crystal orientation were put into evidence by micro-Raman Spectroscopy. At the surface of n-GaAs it is developed an adherent layer of sulphur compound as a resul of chemical interaction of sulphur ions with n-GaAs surface.