National Institute Of Materials Physics - Romania

Novel metal nanoporous transition metal oxides M (x) O (y) (Co3O4, CuO) have been synthesized by thermal decomposition of inorganic salts precursors (acetates, nitrates) impregnated into hexagonal mesoporous silica (OMS, ordered mesoporous silica) of SBA-15 type (prepared in-house) at different precursor loadings, the mesocomposites thus obtained being monitored after each impregnation-calcination step by small and wide angle powder XRD. The pore size for the ordered silica host range from 5.08 to 7.06 nm. Retention of the hexagonal silica framework has been observed in spite of the temperatures up to 500 A degrees C. Mesoporous Co3O4 has been obtained by leaching the silica through overnight HF dissolution, which partially preserved the small-range ordering found in the parent Co3O4@OMS composite prior to leaching. Both Co3O4 (meso) and Co3O4@SBA-15 have been tested in methane oxidation and were found to be superior to the bulk Co3O4 performance, with mesoporous Co3O4 being able to fully oxidize methane to CO2 and H2O at 350 A degrees C, while Co3O4@OMS exhibits a lower activity with 20 % conversion at 350 A degrees C. CuO@OMS shows the lowest activity, with only similar to 13 % conversion at 500 A degrees C.

A novel series of Pd(II) and Pt(II) complexes based on cyclometallated imine ligands and N-benzoylthiourea (BTU) derivatives as auxiliary ligands has been prepared and their liquid crystalline properties as well as photophysical properties have been investigated. The crystal structure of one cyclometallated Pt(II) complex with N-(p-F-phenyl)-N'-benzoylthiourea as a co-ligand has been solved. The liquid crystalline properties have been investigated by a combination of DSC, POM and variable temperature powder X-ray diffraction. These new metallomesogens display either a monotropic SmC phase or both SmA and SmC phases, depending on the number of alkoxy groups attached to the imine ligand, alkyl chain length or the use of branched alkoxy terminal groups. We found that the introduction of branched alkoxy terminal groups lead to lower transition temperatures and stabilization of the SmC phase in both the Pd(II) and Pt(II) complexes. While the Pd(II) complexes display no emission, the Pt(II) complexes show good emission properties in solution, in the solid state and as a PMMA film at room temperature, and their investigation is reported. (C) 2013 Elsevier Ltd. All rights reserved.

Magnetoresistive Fe-Co based thin film structures were produced using thermionic vacuum arc method. The purpose of this work was to obtain significant magnetic response on different granular combinatorial structures. The Giant Magnetoresistive (GMR) and combination between GMR and Tunneling Magnetoresistive (TMR) properties of the thin film structures were the aim of the work. The proposed method in order to obtain the desired granular structures is based on electron beam emitted by an externally heated cathode, accelerated by a high anodic potential. The work consisted in preparing two sets of samples, first being a combination between Fe-Co as magnetic materials embedded in a Cu matrix, with a total thickness of 200 nm. The second structure was a combination between Fe-Co (50%-50%) alloy, embedded in a matrix of Cu combined with MgO with a thickness of 200 nm. Both sets of samples were obtained by three simultaneous types of discharges. Because of the substrate positioning in respect with the three anode-cathode systems, different material concentrations were obtained, confirmed by Energy Dispersive Spectroscopy (EDS) measurement results. Structural and morphological properties were investigated using Scanning Electron Microscopy; Atomic Force Microscopy and EDS. Electrical properties of the obtained samples were studied using the 4 point measurement method. The magnetic properties were first studied using a non-destructive optical method called MOKE (Magneto-Optical Kerr Effect). Electrical resistance behavior of the granular type structures was studied for different values of the magnetic field, up to 03 T, at different values of the sample temperature. The magnetoresistive effect obtained for the two sets of samples varied from 1.5% to 81% in respect with the substrate positioning and sample temperature for a constant magnetic field. (C) 2014 The Authors. Published by Elsevier B.V. All rights reserved.

With the aim of synthesizing the mixed nanoparticle system xIn(2)O(3)-(1-x)SnO2 over all molar concentration range 0 <= x <= 1, Delta x = 0.1, we performed hydrothermal supercritical experiments on indium-tin hydrogel resulted from InCl3-SnCl4 water solution. Nanophases isostructural with InOOH and SnO2 were obtained by hydrothermal reaction at 400 degrees C, in the molar concentration range of 0.1 <= x <= 0.7; at x = 0.8 and x = 0.9 only one phase, isostructural with InOOH, was observed. Samples calcined at 500 degrees C with x in the range of 0.2 <= x <= 0.7 contain a nanoscaled phase isostructural with rhombohedral In2O3 and a second one isostructural with tetrahedral SnO2. At x = 0.8 and x = 0.9 only one phase isostructural with rhombohedral In2O3 appears: rhombohedral ITO phase. The determined band gap energies could recommend the rhombohedral ITO structure for visible light photocatalytic applications. The phase dynamics together with the concentration range for existence of the solid solutions in the InOOH-SnO2 and In2O3-SnO2 composite semiconducting nanoparticle systems have been evidenced and discussed. (C) 2013 Elsevier B.V. All rights reserved.

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.

Sol-gel route using metal alkoxides precursor and trifluoroacetic acid as in situ fluorination reagent has been used to prepare Eu3+ -doped silicate xerogel, followed by thermal annealing to obtain oxyfluoride glass ceramic containing Eu3+ -doped BaF2 nanocrystals. We have used Eu3+ as probe ion and we analyzed its characteristic features (photoluminescence, optical absorption and magnetic circular dichroism) to get information about the local environment around the ion during thermally activated evolution of the sol to xerogel and then glass ceramic. As the drying and annealing proceeds silica network is formed accompanied by precipitation of the nanofluoride crystalline phase; Eu3+ coordination changes gradually from a random and assymetric CF3COO- one (in the sol) to a symmetric one (in the BaF2 nanocrystals) given by the fluorine ions. Glass ceramization is based on a homogenous crystallization mechanism with BaF2 nucleation centres resulted from thermal decomposition of Ba-trifluoacetate at around 300 degrees C followed by subsequent growth into BaF2 nanocrystals above 600 degrees C; Eu3+-ions are incorporated during the nanocrystals growth. (C) 2013 Elsevier B.V. All rights reserved.

We report the deposition by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique of biomimetic nanocrystalline apatite coatings on titanium substrates, with potential application in tissue engineering. The targets were prepared from metastable, nanometric, poorly crystalline apatite powders, analogous to mineral bone, synthesized through a biomimetic approach by double decomposition process. For the deposition of thin films, a KrF* excimer laser source was used (lambda = 248 nm, tau(FWHM) <= 25 ns). The analyses revealed the existence, in synthesized powders, of labile non-apatitic mineral ions, associated with the formation of a hydrated layer at the surface of the nanocrystals. The thin film analyses showed that the structural and chemical nature of the nanocrystalline apatite was prevalently preserved. The perpetuation of the non-apatitic environments was also observed. The study indicated that MAPLE is a suitable technique for the congruent transfer of a delicate material, such as the biomimetic hydrated nanohydroxyapatite. (C) 2013 Elsevier B.V. All rights reserved.

In order to study specific phenomena at ferromagnetic/semiconducting interfaces, of potentially high interest in spintronics and information technology, structural aspects and magnetic properties of Fe thin films grown on Si(001) substrates by RF sputtering have been investigated using Fe-57 conversion electron Mossbauer spectroscopy (CEMS) and magneto-optic Keer effect (MOKE). Films of different thicknesses have been deposited either directly on crystalline Si substrates or on Cu buffer layers. An inherent Fe oxide layer is observed in all as prepared films, with a relative thickness decreasing drastically with the deposition time. The Cu buffer layer does not diminish either the interfacial diffusion or the oxidation process. An efficient method to prepare sharper oxygen- and silicon-free interfaces for an improved spin injection, via thermal treatment in hydrogen atmosphere, is proposed. Accordingly, the hydrogenation treatments are very efficient in the modification of the ferromagnetic film structure, phase composition, magnetic properties and interfacial mixing. (C) 2013 Elsevier B.V. All rights reserved.

KrF* excimer laser pulses of 248 nm were used for the synthesis of nanometric iron oxide films with variable thickness, stoichiometry and electrical properties. Film deposition was carried out on <1 0 0> Si and SiO2 substrates. The number of laser pulses was increased from 4000 to 6000, while ambient reactive oxygen pressure varied from 0.1 to 1.0 Pa. The film thickness depends on oxygen pressure, number of laser pulses and substrate nature. All films demonstrated semiconducting temperature behaviour with variable band gap (E-g) depending on oxygen pressure, substrate nature and temperature. Eg value was less than 1.0 eV for all deposited films. XRD analysis evidenced that films deposited on Si substrate have polycrystalline structure, while films deposited on SiO2 were amorphous. The higher oxygen pressure, the lower crystallinity of the deposited film was observed, resulting in change of thermo electromotive force coefficient (S) value. For larger substrate temperature, a better crystallization was observed in the deposited films, resulting in increased S coefficient value. The largest value of the S coefficient was about 8.7 mV/K in the range 290-295 K and it decreased to 1.0-1.6 mV/K when heating temperature changed from 240 to 330 K. The figure of merit of deposited structures was ZT = 3-6 in the range 240-330 K with a maximum of 12 at 300-304 K. We have shown that thermo-sensing characteristics of the films strongly depend on their electrical and structural properties. (C) 2013 Elsevier Ltd. All rights reserved.

Matrix-assisted pulsed laser evaporation (MAPLE) has been investigated as an alternative to the pulsed laser deposition (PLD) technique for Eu3+-doped crystalline LiYF4 thin-films deposition. MAPLE assumes laser ablation of a frozen target made of the material of interest diluted in a solvent, rather than that of a bulk target, of either pressed powder or single crystal, used in the case of PLD. Our approach stems from the assumption that laser ablation of a frozen dilute target would result in thin films with improved morphology, as compared to PLD. Indeed, we find that roughness values of samples obtained by the MAPLE technique are four times lower than in the case of PLD. A lower transmittance was noticed for PLD obtained layers with respect to those grown by MAPLE due to strong scattering of light by the morphological defects. Photoluminescence spectra are showing characteristic Eu3+-ion luminescence bands at 578, 591, 612, 650 and 698 nm (D-5(0) -> F-7(J)); crystal field splitting of the bands indicates dopant ions incorporation in the host material during transfer by either PLD or MAPLE.