National Institute Of Materials Physics - Romania

Nanostructured intrinsic and doped titania materials have long been subject to both basic and applied research, in connection with environment and energy related applications. Apart from beneficial effects. such as widening the wavelength range for surface photocatalytic activation, doping TiO2 materials with 3d ferromagnetic cations is a main route to develop ail important class of diluted semiconductors, with potential applications in spintronics. In all the previous investigations the concentration of the ferromagnetic dopant was limited to a few percents. Here, we initiate ail extended investigation of Ti1-xFexO2 within a, wider iron composition range (x = 0 - 0.55) and discuss the magnetic and optical properties of these materials in thin films in relation with their elemental composition, nano-structure and local atomic ordering.

Iron- and europium-doped (<= 1 at.%)TiO2 nanoparticles powders have been synthesized by a hydrothermal route at 200 degrees C, starting with TiCl4, FeCl3 center dot 6H(2)O and EuCl3 center dot 6H(2)O. The structure, morphology and optical peculiarities were investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS), Mossbauer spectroscopy and UV-vis measurements. The photocatalytic performance was analysed in the photodegradation reaction of phenol. Rietveld refinements of XRD patterns reveal that the as-prepared samples consist in iron- and europium-doped TiO2 in the tetragonal anatase structural shape, with particle size as low as 15 nm. By means of Mossbauer spectroscopy on both Fe-57 and Eu-151 isotopes as well as by EXAFS analyses, the presence of Fe3+ and/or Eu3+ ions in the nanosized powders has been evidenced. It was found that iron and europium ions can substitute for titanium in the anatase structure. From the UV-vis reflection spectra, by using the transformed Kubelka-Munk functions, the band gap energy (E-g) of the hydrothermal samples has been determined in comparison with that of Degussa P-25 photocatalyst. A decrease of E-g from 2.9eV found for Degussa photocatalyst to 2.8 eV for the titania doped with 1 at.% Fe has been evidenced, indicating a valuable absorption shift (similar to 20 nm) towards visible light region. However, the best photocatalytic activity in the photodegradation reaction of phenol was evidenced for the hydrothermal sample, TiO2: 1 at.% Fe, 0.5 at.% Eu, in both UV and visible light regions. The photocatalytic activities of iron-doped and iron-europium-codoped samples are high and practically the same only in visible light. The photocatalytic properties in Correlation with the structural and optical peculiarities of the hydrothermal samples are discussed. (C) 2008 Elsevier B.V. All rights reserved.

The effect of fullerene on the radical polymerization of N-vinylpyrrolidone with lauroyl peroxide in toluene was investigated kinetically. C-60 was found to act both as inhibitor and as retarder because the polymerization rate and the molecular weight of resulting poly(vinylpyrrolidone) is decreasing with the increase of the fullerene concentration (0-6.94 x 10(-4) mol l(-1)). The water-soluble poly(vinylpyrrolidone)-modified fullerene C-60 compound was characterized by differential scanning calorimetric, Infrared and Raman spectroscopy, UV absorption and photoluminescence. Based on the results obtained by optical measurements, it is argued that by the covalent attachment of the polymeric radicals to fullerene cage the extended electronic conjugation system of the C-60 is broken leading to the appearance of a polyene structure.

The Stoner instability of the paramagnetic state, yielding to the occurence of ferromagnetism, is reviewed for electron density of states reflecting changes in the dimensionality of the system. The situations treated are one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) cases and also a special case where the density of states has a parabolic shape near the Fermi level, and is half-filled at equilibrium. We recover the basic results obtained in the original work of E.C. Stoner [Proc. Roy. Soc. London A 165, 372 (1938)]; also we demonstrate that in 1D and 2D case, whenever the Stoner criterion is satisfied, the system evolves spontaneously towards maximum polarization allowed by Hund's rules. For the 3D case, the situation is that: (i) when the Stoner criterion is satisfied, but the ratio between the Hubbard repulsion energy U and the Fermi energy epsilon(F) is between 4/3 and 3/2, the system evolves towards a ferromagnetic state with incomplete polarization (the polarization parameter is between 0 and 1); (ii) when U/epsilon(F), > 3/2, the system evolves towards maximum polarization. This situation was also recognized in the original paper of Stoner, but with no further analysis of the obtained polarizations nor comparison with experimental results. We apply the result of calculation in order to predict the Hubbard interaction energy. Finally, for the case of half-filled parabolic density of states a result quite similar with the case of the free electron 3D DOS is obtained, but here the Hubbard energy has to be compared with the band half-widh 6, whereas the absolute value of the Fermi energy has no relevance in this model. The Stoner criterion is U/delta > 4/3 and for U/delta < 2 the total energy is minimized for incomplete polarization. We compare the results obtained from the present theoretical study with the newest available experimental data.

Single-walled carbon nanotubes (SWNTs) may be used in technological applications as individual entities instead of bundled tubes. The Raman signature of these two forms is still a controversial subject. The profile, peak position and relative intensity of the Raman band associated with the tangential vibration modes (G band similar to 1600cm(-1)) and radial vibration modes (RBM similar to 100-200cm(-1)) are the main parameters which can reveal the dispersion state of nanotubes. Resonant Raman scattering and absorption spectroscopy on SWNTs furnish complementary information concerning the efficiency of the nanotube dispersion in individual entities. (C) 2008 Elsevier B.V. All rights reserved.

The experimental studies on III-V semiconductor compounds surface passivation phenomena are mainly dedicated to solve some technological problems as those regarding the ways to keep the chemical stability of native oxides on surfaces. Self-assembled monolayers (SAMs) provide a simple way to produce relatively ordered structures at a molecular scale, which seems to be capable to protect the clean surface against the evolution of oxidation process. In this respect, thin films of SAMs of aliphatic thiol (dodencanthiol-CH3(CH2)(11)SH) and aromatic thiol (4, 4' tiobisbenzenthiol-S (C6H4SH)(2) have been deposited on the surface of Gap (111) samples. The electrical properties measurements of some structures based on GaP compound was performed. There were recorded current-voltage (I-V) characteristics for complex structures AuGeNi/R-SH/GaP and AuGeNi/Ar-SH/GaP in darkness and also exposed to a Xe lamp. In dark and in "reverse bias" way, the I-V characteristics present the feature of a Zenner diode for GaP/Ar-SH and a gradual increase of current for GaP/R-SH. In dark and "in forward bias" way, the current increases as for a normal diode for both GaP/Ar-SH and GaP/R-SH structures. The complex structures (e.g.: In/AuGeNi/R-SH/GaP/R-SH/AuGeNi/In) are less sensitive to light. The SEM analysis performed on a GaP/R-SH surface shows a continuous packed up layer while GaP/Ar-SH looks like an inhomogeneous deposition of layers with different thickness regions. The diodes' ideality factors determined from I-V characteristics are unusually high (n >> 2) as a possible result of inhomogeneous Schottky contacts or due to ageing effects, in the field of degradation. (C) 2009 Elsevier Ltd. All rights reserved.

The Compact Muon Solenoid (CMS) detector is described. The detector operates at the Large Hadron Collider (LHC) at CERN. It was conceived to study proton-proton (and lead-lead) collisions at a centre-of-mass energy of 14 TeV (5.5 TeV nucleon-nucleon) and at luminosities up to 10(34)cm(-2)s(-1) (10(27)cm(-2)s(-1)). At the core of the CMS detector sits a high-magnetic-field and large-bore superconducting solenoid surrounding an all-silicon pixel and strip tracker, a lead-tungstate scintillating-crystals electromagnetic calorimeter, and a brass-scintillator sampling hadron calorimeter. The iron yoke of the flux-return is instrumented with four stations of muon detectors covering most of the 4 pi solid angle. Forward sampling calorimeters extend the pseudo-rapidity coverage to high values (vertical bar eta vertical bar <= 5) assuring very good hermeticity. The overall dimensions of the CMS detector are a length of 21.6 m, a diameter of 14.6 m and a total weight of 12500 t.

Carbon Nanotubes are exotic low-dimensional systems, and due to their remarkable properties, are promising components for technological applications. The electronic and vibrational signatures raising from their existence as individual entities or associated in bundles, is still a controversed subject. A careful analysis of the G (similar to 1600 cm(-1)) and RBM (100-200 cm(-1)) band features as: profile, peak position and intensity in the Raman spectra may be a valuable indication about their dispersion state. The UV-VIS-NIR absorption spectrum comes to support this assumption. Observing the absorption spectra associated to resonant excitation of semiconducting and metallic nanotubes, may reveal complementary informations concerning the individualization procedure efficiency.

Angle-resolved X-ray Photoelectron Spectroscopy (ARXPS) has been performed on (100) Si surfaces in different conditions as regards the oxides nature - native oxides, thermally formed oxides, and also after a cleaning procedure by Ar+ ion sputtering (e.g. E= 2 keV). The most sensitive angle to surface oxidation states (Si1+, Si2+, Si3+, Si4+) was the take-off-angle (TOA): 25 degrees. Native oxides and thermally oxide phases on Si surfaces consists in a mixture of Si2O, SiO, Si2O3 and SiO2. The XPS measurements have putted into evidence a higher concentration of suboxides in high oxidation state (Si3+) on naturally oxidized Si substrates. The thermally oxidized Silicon surfaces contain suboxides in a low oxidation state (Si1+). The Ar+ ion sputtering removed rapidly the superficial silicon oxides. The analysis and computation of SiO2 film thickness on crystalline Silicon was done in the frame of modified Bethe equation for Electron inelastic mean free path (IMFP) and taking into account the intensity of SiO2 peak and Si peak together with the TOA in the XPS measurement. Native oxide thickness for SiO2 was d(oxy) similar to 24 angstrom and for thermally oxidized sample was d(oxy) similar to 27 angstrom. Due to the slightly difference in the nature oxidation states it is suggested that the silicon dioxide appeared from two different kinetics in the oxidation processes.

TiAlZrCN superhard coatings, in which Ti and Al were additions to ZrCN base compound, were prepared by the cathodic arc method. The films were deposited on Si, plain carbon steel and high-speed steel substrates in a mixture of N-2 and CH4 gases. Elemental and phase composition, chemical bondings, texture, surface roughness, hardness, adhesion, tribological characteristics and erosive-corrosive resistance were investigates as a function of gas composition and total gas flow rate, using XPS, GDOES and XRD techniques, surface profilometry, microhardness and scratch adhesion measurements, tribological and erosive tests. It was shown that the properties and performance of the coatings were strongly dependent on the CH4/(CH4+N-2) flow rate and also on the total gas flow. The tribological and anti-erosive characteristics of the TiAlZrCN coatings were found to be superior to those of reference films (ZrN, ZrC, ZrCN, and TiAlCN). Maximum hardness values (42-45 GPa) were obtained for the films prepared at CH4/(CH4+N2) ratios ranging from 0.2 to 0.4. (c) 2008 Elsevier B.V. All rights reserved.