Dr. Aurel-Mihai VLAICU

We explored the possibility to guide the forming process in a Ta/TiO2/Pt memristive device using an X-ray nanopatterning procedure, which enables the manipulation of the oxygen content at the nanoscale. The irradiation of selected areas of the sample by a 65 x 58 nm2 synchrotron X-ray nanobeam locally generated oxygen vacancies which resulted in the formation of a conductive filament in the desired position in the material. The subsequent application of an electric field between the electrodes was exploited to achieve reversible bipolar resistive switching. A multitechnique characterization was then performed, highlighting a local increase in the height of the crystal and the formation of a dislocation network, associated with the presence of Wadsley defects. Our results show that X-ray nanopatterning could open new avenues for a more deterministic implementation of electroforming in oxide-based memristive devices. We tuned the oxygen content in a Ta/TiO2/Pt memristive device at the nanoscale by a synchrotron X-ray nanobeam. We obtained a conductive filament of oxygen vacancies in the desired position in the material to achieve a controlled resistive switching.

Special attention has recently been paid to surface-defective titanium dioxide and black TiO2 with advanced optical, electrical, and photocatalytic properties. Synthesis of these materials for photodegradation and mineralization of persistent organic pollutants in water, especially under visible radiation, presents interest from scientific and application points of view. Chemical reduction by heating a TiO2 and NaBH4 mixture at 350 degrees C successfully introduced Ti3+ defects and oxygen vacancies at the surface of TiO2, with an increase in the photocatalytic degradation of amoxicillin-an antibiotic that is present in wastewater due to its intense use in human and animal medicine. Three TiO2 samples were prepared at different annealing temperatures to control the ratio between anatase and rutile and were subjected to chemical reduction. Electron paramagnetic resonance investigations showed that the formation of surface Ti3+ defects in a high concentration occurred mainly in the anatase sample annealed at 400 degrees C, contributing to the bandgap reduction from 3.32 eV to 2.92 eV. The reduced band gap enhances visible light absorption and the efficiency of photocatalysis. The nanoparticles of similar to 90 m(2)/g specific surface area and 12 nm average size exhibit similar to 100% efficiency in the degradation of amoxicillin under simulated solar irradiation compared with pristine TiO2. Mineralization of amoxicillin and by-products was over 75% after 48 h irradiation for the anatase sample, where the Ti3+ defects were present in a higher concentration at the catalyst's surface.

The discovery of multifunctional properties related to electro-activity of organic systems of biomolecules is important for a variety of applications, especially for devices in the realm of biocompatible sensors and/or bioactuators. A further step towards such applications is to prepare thin films with the required properties. Here, the investigation is focused on the characterization of films of guanine and cytosine nucleobases, prepared by thermal evaporation-an industrial accessible deposition technique. The cytosine films have an orthorhombic non-centrosymmetric structure and grow in two interconnected nanostructured fractal patterns, of nearly equal proportion. Piezoresponse force microscopy images acquired at room temperature on the cytosine films display large zones with antiparallel alignment of the vertical components of the polarization vector. Guanine films have a dense nano-grained morphology. Our studies reveal electrical polarization switching effects which can be related to ferroelectricity in the films of guanine molecules. Characteristic ferroelectric polarization-electric-field hysteresis loops showing large electrical polarization are observed at low temperatures up to 200 K. Above this temperature, the guanine films have a preponderant paraelectric phase containing residual or locally induced nano-scopic ferroelectric domains, as observed by piezoresponse force microscopy at room temperature.

We explore the cross coupling between the ferroelectric and ferromagnetic phases in Ni/BaTiO3(001) heterostructures and demonstrate the modulation of the magnetism and incidence of exchange bias in the ultrathin metallic Ni overlayer, depending on the ferroelectric state of the bottom layer. We establish that 5-nm-thick monocrystalline Ni film deposited on BaTiO3 with ferroelectric polarization pointing towards the surface (P+) favors the organization of Ni into uniform ferromagnetic domains. Ni grown on BaTiO3 with opposite ferroelectric polarization is featured by emerging exchange-bias coupling between the ferromagnetic Ni top layers and the antiferromagnetic reacted interface, as theoretically explained by first-principles calculations. We explicitly obtain the morphology of the magnetic domains of the crystalline Ni layer in atomic and magnetic force microscopy measurements (AFM/MFM). The resemblance of AFM and MFM images indicate that, although with radically different morphologies, in both cases all spins orient in the Ni plane. Consequently, the distinct signature of the ferroelectric-ferromagnetic coupling extracted from the magneto-optical Kerr effect measurements encodes all the information of sample magnetism. The peculiar magnetic coupling depending on the ferroelectric state indicates new ways of engineering the functionality of metal/ferroelectric interfaces.

A one-step method assisted by hydrothermal treatment was approached to obtain nanocrystalline 1 and 10 mol. % In doped 2 mol.% Pd-SnO2 powders using a non-ionic surfactant Brij52 and Polyethylene glycol 6000 (PEG) as templates. Depending on In content, the samples were labeled as Pd1InSn and Pd10InSn. The obtained materials consist of nanosized crystallites packed into micrometric grains with a high porosity, as revealed by the morphological and structural investigations (SEM, TEM). A dependence of the grain size with respect to the In content has been revealed i.e. the sample Pd1InSn was showing an average grain size of around 10 nm, whilst for the sample Pd10InSn the average grain size was found to be around 5 nm. The XPS investigations highlighted the differences occurred in the surface chemistry in terms of surface hydroxylation as well as the chemical states of Pd. The sensing properties towards different CO concentrations have been examined under infield background conditions, at low operating temperature of 50 degrees C. The sensing mechanism model for CO was discussed in detail according to the possible interplay between oxygen and water related species based on the experimentally results acquired through simultaneous electrical resistance and work function measurements.

The K alpha and K beta x-ray spectra of Se, Y, and Zr were studied experimentally and theoretically in order to obtain information on the K alpha(1) line asymmetry and the spin doublet in K beta(1,3) diagram lines. Using a high-resolution antiparallel double-crystal x-ray spectrometer, we obtained the line shapes, that is, asymmetry index and natural linewidths. We found that the corrected full width at half maximum of the K alpha(1) and K alpha(2) lines as a function of Z is in good agreement with the data in the literature. Furthermore, satellite lines arising from shake-off appear in the low-energy side of the K alpha(1) and K alpha(2) lines in Se but, in Y and Zr, it was very difficult to identify the contribution of the shake process to the overall lines. The K beta(1,3) natural linewidth of these elements was also corrected using the appropriate instrumental function for this type of x-ray spectrometer, and the spin doublet energies were obtained from the peak positions. The corrected full width at half maximum (FWHM) of the K alpha(1) x-ray lines increases linearly with Z, but this tendency was found to be, in general, not linear for K alpha(3) x-ray lines. This behavior may be due to the existence of satellite lines originated from shake processes. Simulated line profiles, obtained using the multiconfiguration Dirac-Fock formalism, accounting for radiative and radiationless transitions and shake-off processes, show a very good agreement with the high-resolution experimental spectra.

(1) Background: The high-voltage anodic-plasma (HVAP) coating technique has a series of specificities that are not simultaneously met in other deposition methods. This paper aimed at assessing the potential of HVAP to synthesize quality multilayers for X-ray optics. (2) Methods: Nanolayers of W, Ta, B, and Si were deposited as mono-, bi-, and multilayers onto very smooth glass substrates by HVAP, and their thickness and density were analyzed by X-ray reflectometry. The minimal film thickness needed to obtain continuous nanolayers was also investigated. (3) Results: Nanolayer roughness did not increase with layer thickness, and could be lowered via deposition rate, with values as low as 0.6 for the W nanolayer. Minimal film thickness for continuous films for the studied metals was 4 nm (W), 6 nm (Ta), 2.5 nm (B), and 6 nm (Si). (4) Conclusions: The investigation revealed the range of parameters to be used for obtaining quality nanolayers and multilayers by HVAP. Advantages and possible improvements are discussed. This deposition technique can be tailored for demanding applications such as X-ray mirrors.

Nanoclustered Pd (2 mol%) was used to decorate Zn doped SnO2 (10 mol% Zn) in order to increase its sensing performances. Zn doped SnO2 built from nanoparticles was prepared by a hydrothermal method using a nonionic surfactant -Brij52 and Tripropylamine (TPA) as co-templates. The presence of well-dispersed Zn2+ ions in the SnO2 matrix leads to a nonstoichiometric surface. Pd was deposited by subsequent wet impregnation using hydrazine as reducing agent. The as obtained powders were deposited as thick layers onto commercial substrates, in order to obtain the sensitive structures. The coexistence of a mixture of valence states (Pd-0, Pd2+ and Pd4+) was highlighted on the surface of the as prepared layers. Several aspects have been followed regarding the Zn and Pd dispersion into the SnO2 matrix: the large scale and low scale morphology (SEM and TEM/HRTEM) in relation with the synthesis route, the obtained crystallographic phases (XRD, SAED) and the way in which the Zn2+ ions are inserted into the SnO2 structure (XRD, XPS, EPR), the spatial distribution of the added chemical elements, Zn and Pd (SEM, STEM, EDS). All these morphological and structural aspects, as well as the Pd surface chemistry, have been correlated with the sensing properties of the nanostructured materials under controlled gas atmosphere. Through this study, we could harvest the specific role of the aforementioned loadings towards selective detection of low NO2 concentrations, between 350 ppb to 5 ppm, at low operating temperature of 100 degrees C, for infield conditions.

Previous electron spin resonance investigations correlated with data from cathodoluminscence and photoluminescence measurements have shown that impurity ions consisting mainly of isotopes with zero nuclear moments are involved in the structure of the observed paramagnetic point defects. In the present microstructural and compositional investigation we demonstrate that oxygen, carbon and silicon impurity atoms exhibiting low natural content of isotopes with non-zero nuclear spin are indeed present in cBN crystallites selected from amber coloured BORAZON CBN400 and CBN 500 super abrasive powders, as well as in the black coloured BORAZON CBN1000 and CBN Type 1. It is also shown that aggregates of impurity atoms are present next to the extended cBN lattice defects, which could explain the non-uniform distribution of the electro- and opto-active impurities reported in a spectroscopy investigation.

The work demonstrates growth by the Verneuil method of SrTiO3 single crystals of 30 mm in diameter. Experiments are performed under an industrial environment. Growth was for 4.75 h, i.e., within one production shift. The optimum growth conditions for which the length of the region with bubbles D is zero and the effective length EL (i.e., the crystal length of commercial value) is maximized are for the amount of SrCO3 additive of similar to 3 wt % and for H-2 outer flow rate of similar to 35 L/min. These two parameters show the strongest influence on the bubble-free growth, but other growth parameters (H-2 inner flow rate, O-2 flow rate increase, rotation speed) were also optimized. Selected crystals are characterized from the structural, microstructural, optical, and THz spectroscopy viewpoints, and they are compared with a commercial substrate and with crystals reported in the literature. This work opens the possibility for the industrial growth of large SrTiO3 single crystals and commercialization of large area substrates.

The results of the present Q-band electron spin resonance (ESR) investigation on amber colored cubic boron nitride (cBN) crystalline superabrasive powder (BORAZON CBN400) offer further support to the hypothesis that impurity ions with high natural abundant zero nuclear spin isotopes, distributed non-uniformly, are involved in the structure of the observed paramagnetic centers. One could thus explain the absence of any hyperfine structure in the multifrequency electron spin resonance spectra of both presently and previously investigated cBN crystalline powders and single crystals. The scanning electron microscopy, cathodoluminescence and photoluminescence studies performed on single crystallites selected from the same cBN400 batch further confirm the presence of electro- and photo-luminescent active impurity related centers, non-uniformly distributed in the cBN crystallite host lattice. The observation of an intense and reproducible thermoluminescence spectrum, up to high radiation doses, attributed to several trapping centers involving impurities, is also reported here.

We report a study related to the influence of heat treatment (up to 300 degrees C) on the structure of GaSb \GeTe, SnSe\GeTe and GaSb\SnSe stacked phase change memory films and of their counterparts with Hf thin film barrier between the layers. Samples were prepared by pulsed laser deposition and investigated by X-ray reflectometry and X-ray diffraction in order to evaluate the inter-films diffusion and the temperature threshold where this process is initiated. The thickness and mass density variations of films after each heat treatment, as well as the efficiency of hafnium barrier film, to eliminate potential atomic diffusion issues, were investigated.

The K beta x-ray spectra of the elements from Ca to Ge have been systematically investigated using a high resolution antiparallel double-crystal x-ray spectrometer. Each K beta(1,3) natural linewidth has been corrected using the instrumental function of this type of x-ray spectrometer, and the spin doublet energies have been obtained from the peak position values in K beta(1,3) x-ray spectra. For all studied elements the corrected K beta(1) x-ray lines FWHM increase linearly as a function of Z. However, for K beta(3) x-ray lines this dependence is generally not linear in the case of 3d elements but increases from Sc to Co elements. It has been found that the contributions of satellite lines are considered to be [KM] shake processes. Our theoretically predicted synthetic spectra of Ca, Mn, Cu, and Zn are in very good agreement with our high-resolution measurements, except in the case of Mn, due to the open-shell valence configuration effect (more than 7000 transitions for diagram lines and more than 100 000 transitions for satellite lines) and the influence of the complicated structure of the metallic Mn.

Sm3+, Pr3+ and Dy3+-doped Ca3Nb1.6875Ga3.1875O12 - CNGG and Ca3Li0.275Nb1.775Ga2.95O12 - CLNGG crystals are of interest as solid-state laser materials emitting in the yellow-orange spectral range, especially for diode pumping due to their partially disordered nature. In this work, for the first time to our knowledge, single crystals of Sm, Pr and Dy-doped CNGG and CLNGG crystals were grown by the Czochralski method. For the doping of CNGG and CLNGG crystals, five new stoichiometric garnets were synthesised by solid-state reaction method: praseodymium-gallium-garnet (PrGG), dysprosium-gallium-garnet (DyGG) and praseodymium-lithium-niobium gallium-garnet (PrLNGG), samarium-lithium-niobium-gallium-garnet (SmLNGG), and dysprosium-lithium-niobium-gallium-garnet (DyLNGG). Samarium-gallium-garnet (SmGG) was also sintered and used for the doping of Sm:CNGG crystal. Structural properties of sintered materials and grown crystals were investigated by X-ray diffraction and the chemical compositions of the grown crystals were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) method. The spectroscopic investigations of the grown crystals have shown that they are promising laser materials in the yellow-orange spectral range.

Because of the unique properties of the ferroelectric perovskite particles with a well-defined anisotropic form like shape-and size dependent at low dimensions they have all the attention of the scientific world. Extensive morphostructural techniques will be used to characterize the piezoelectric material.

Green compacts of B4C or B4C added with 1 vol% graphite were infiltrated with molten Si and subsequently were subject of processing by floating zone partial re-melting (FZPR). In FZPR only the low temperature fusible component, in this case Si, is melted. A fully dense B4C-based ceramic is obtained. It contains free-Si, SiC and B4C. In the center of the FZPR ceramic without graphite addition, the amount of Si is decreased when compared to the infiltrated material. Some impurity elements such as Al, Fe, or Ti detected in the raw B4C powder are preferentially gathered at the edges of the sample. In the sample added with graphite, formation of a high amount of SiC in the infiltrated material hinders Si shift from the center to the edges. The pulling rate and the particle size of the B4C raw powders are also important. It is recognized that sintering of powders larger than 10-20 gm is usually difficult: our approach is demonstrated to be suitable for processing of B4C powders with a very different particle size, from 10 to 250 gm. The FZPR ceramic had a Vickers hardness of 9-38 GPa depending on location of the indentation imprint and on the sample. A tensile strength of 114-188 MPa that is up to about 2-3 times higher than for the infiltrated material was recorded. Work indicates that the proposed processing approach offers extended control possibilities towards fabrication of new composite materials not available by traditional technologies.

Thermal behavior of repa-germanium (C6H10Ge2O7, Ge-132) during heating in air or in argon is investigated using DSC-TGA, XRD, SEM,TEM, and FT-IR measurements. Nine domains of thermal transformations were identified from room temperature to 1200 degrees C, in air or argon. The first reversible transformation is below 220 degrees C and it was assigned to an isomerization process, based on DSC, XRD and IR measurements. The next five transformation domains (220-910 degrees C) are decompositions accompanied by weight loss. The main product of thermal decomposition is Ge. The next transformation domain (910-970 degrees C) corresponds to melting of Ge, both in argon and air. In the air, this step is followed by oxidation of Ge (970-1100 degrees C) and, finally, by melting of GeO2. Amorphous phases formed between 220 and 720 degrees C. Observed processes are discussed based on crystal chemistry and bonds dynamics considerations. (C) 2016 Elsevier B.V. All rights reserved.

Disordered Sm3+ doped Y3ScxAl5-xO12 (Sm:YS(x)AG) polycrystalline ceramics with compositional parameter x = (0.05, 0.5, 1, 2) and different Sm3+ ions concentrations were obtained by solid state reaction method. XRD investigations show the linear increase of the lattice constant with compositional parameters x. New spectroscopic data obtained from high resolution optical absorption and emission spectra of Sm3+ doped YS(x)AG ceramics reveal composition effects on Sm3+ optical spectra: modification of the shapes and shifts of the lines, presence of the additional satellites and unresolved multicenter structure, etc. The analysis of these data allowed us to establish a partial structure of Sm3+ energy levels in Sm:YS(x)AG (x = 2) ceramics. The emission kinetics of the (4)G(5/2) level for different Sm3+ concentrations and Sc content in Sm:YS(x)AG were measured and analyzed. (C) 2016 Elsevier B.V. All rights reserved.

Spark Plasma Sintering (SPS) and High Pressure-High Temperature (HPHT) methods were chosen in order to study the behaviour of metastable cubic boron nitride (cBN) during sintering of Al2O3 + 30 vol.% cBN composites at low and high pressure. Relatively low sintering temperatures were used to avoid the undesired reverse transformation of cBN to hexagonal, graphite-like form. The microstructure, and phase composition as well as physical and mechanical properties of the resulting Al2O3-cBN composites were investigated. In the ball-on-disc tests, the coefficient of friction and the specific wear rate of the sintered samples were determined by rotating the sample against a stationary alumina ball. The best composites obtained by SPS (at 1300 degrees C/75 MPa) had slightly lower density, Young's modulus and hardness than those obtained by HPHT but their wear resistance was much better. Formation of hBN was suppressed up to 1300 degrees C during SPS consolidation at the pressure of 75 MPa. (C) 2016 Elsevier Ltd. All rights reserved.

The present study reveals the synthesis of metallic particles at atmospheric pressure using a radiofrequency low-temperature argon plasma jet. Copper bulk material of the powered electrode acted as solid precursor in the process and the metallic particles were obtained directly in gaseous environment. The particles were collected onto Si (100)-oriented substrates downstream of the atmospheric plasma jet and were ex situ characterized via optical microscopy, scanning electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. We obtained copper particles, reddish brown in color, either of nano-or micro-metric sizes. Additionally, the plasma species and gas temperature were determined by OES. In conclusion, it was demonstrated that conversion of bulk metals into particles is possible at atmospheric pressure using a radiofrequency plasma jet and the development of several applications is recommended.

Epitaxial TiC films were deposited on MgO (001) by DC magnetron sputtering in a reactive atmosphere of Ar and CH4 at 800 degrees C. The films elemental composition and chemical bonding was investigated by Auger electron spectroscopy (AE5), X-ray photoelectron spectroscopy (XPS) and micro-Raman spectroscopy. The crystallographic structure, investigated by X-ray diffraction, exhibited an increased degree of (001) orientation with the film thickness, with a cube-on-cube epitaxial relationship with the substrate. The films morphology and electrical properties were determined by atomic force microscopy (AFM) and Hall measurements in Van der Pauw geometry. The influences of the film thickness (57-545 nm) on the morphological and electrical properties were investigated. The thinnest film presented the lowest resistivity, 160 [152, cm, showing an atomically flat surface, while higher values were obtained for the thicker films, explained by their different morphology dominated by low aspect ratio nanoislands/ nanocolumns. (C) 2013 Elsevier B.V. All rights reserved

We report results regarding the in vitro toxicology of gamma-Bi2O3 represented by its isomorphous phase Bi12TiO20 (gamma-BTO). The gamma-BTO microparticles were synthesized by two methods: coprecipitation from a bismuth nitrate tetrabutyl titanate solution and solid state reaction of Bi2O3 and TiO2 oxides. The structural and morphological characteristics of the obtained materials were determined using X-ray diffraction (XRD), selected area electron diffraction (SAED), transmission (TEM) and scanning (SEM) electron microscopy. The elemental composition was investigated using energy dispersive spectrometry (EDS). The cytotoxicity and oxidative/nitrosative stress (intracellular reactive oxygen species (ROS) and nitric oxide (NO) release) induced by the studied microparticles in HepG2, SH-SY5Y and 3T3-L1 cell cultures were determined using the MIT, DCF-DA (2 ',7 '-dichlorfluorescein-diacetate) and Griess methods respectively. Depending on the cell type and gamma-BTO concentration, results showed only weak cytotoxic effects after 24 h of gamma-BTO exposure and cell proliferation effects for longer treatment times. Only reduced NO release increases (corresponding to high gamma-BTO concentrations) were detected in case of SH-SY5Y and 3T3-L1 cells. The intracellular ROS production (higher for HepG2 cells) appeared inversely proportional to the gamma-BTO concentration. The obtained results indicated a promising in vitro biocompatibility of gamma-BTO and encourage further studies regarding its potential for biomedical applications. (C) 2014 Elsevier Ltd. All rights reserved.

Electroless deposition was successfully applied in developing crystalline particles of zinc oxide onto polyester textile materials; this deposition is here presented in comparison with other materials made from poly(lactic acid), polyamide or hemp. Structural and spectroscopic characterization of the raw and deposited samples has been performed. The structure of zinc oxide particles was that of wurtzite type as indicated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Crystallites were 20-500 nm in diameter and up to 1 mu m in length. The grown particles cover the fibers not only on the fabric surface but in the textile depth. Contact angle measurement by the sessile drop method was used to study the wettability behavior of the investigated composite systems. The hierarchical roughness structure generates superhydrophobic properties onto polyester fabrics, for which water contact angles exceed 150 degrees. The other functionalized samples also become more hydrophobic after deposition. Cassie-Baxter model was found suitable to describe the behavior, though the fraction of surface occupied by the water-solid interface is high enough. The electroless deposition technique applied previously for cotton fabrics was once more proven to be highly reproducible, easy scalable, and cheap, allowing a wide range of applications. (c) 2013 Wiley Periodicals, Inc.

A sandwich structure of four double layers of Ag (5 nm)/As2S3 (82.7 nm) has been prepared by Pulsed Laser Deposition (PLD) method. The effect of broadband light on the multilayer structure has been investigated. The X-ray reflectivity (XRR) patterns after different irradiation times have been measured. Although the fully intermixing of Ag and As2S3 layers should be expected during irradiation with visible light, however even after 5 h of irradiation the intermixing is not completed. The characteristic features of XRR diagrams for long irradiation times have been interpreted by scattering of X-ray radiation on clusters of Ag or Ag-As2S3. (c) 2013 Elsevier B.V. All rights reserved.

Nanocomposites based on TiO2 aerogel and Ag nanoparticles have been successfully obtained through different synthesis methods and their specific surface areas have been determined by N-2 sorption (BET method). The photocatalytic potential for salicylic acid degradation has been evaluated. It was found that under visible light irradiation, all synthesized nanocomposites exhibit higher photocatalytic activity than the commercially available Aeroxide P25. By correlating the structural parameters with the photocatalytic performances, it has been found that the Ag nanoparticles and brookite phase presence alongside the anatase play important roles on the visible photocatalysts behavior. For the Ag containing samples with mixed anatase brookite phases, it has been observed that the visible photocatalytic performance decreases with the increase in brookite crystalline phase content. On the other hand, the addition of Ag nanoparticles results, as expected, in a clear enhancement of the visible photocatalytic activity. (C) 2013 Elsevier B.V. All rights reserved.

The Griess assay has been used to determine the possible changes in the measured NO2- concentrations induced by TiO2 nanoparticles in three types of nitrite-containing samples: aqueous NaNO2 solutions with known concentrations, and two types of cell culture media-Roswell Park Memorial Institute medium (RPMI-1640) and Dulbecco's Modified Eagle Medium (DMEM-F12) used either as delivered or enriched in NO2- by NaNO2 addition. We have used three types of titania with average particle sizes between 10 and 30 nm: Degussa P25 and two other samples (undoped and Fe3+-doped anatase TiO2) synthesised by a hydrothermal route in our laboratory. The structural, morphological, optical and physicochemical characteristics of the used materials have been studied by X-ray diffraction, transmission electron microscopy (EDX), Mossbauer spectroscopy, Brunauer-Emmett-Teller nitrogen adsorption, UV-Vis reflectance spectroscopy, dynamic light scattering and diffuse reflectance infrared Fourier transform spectroscopy. The opacity and sedimentation behaviour of the studied TiO2 suspensions have been investigated by photometric attenuance measurements at 540 nm. To account for the photocatalytic properties of titania in a biologically relevant context, multiple Griess tests have been performed under controlled exposure to laboratory natural daylight illumination. The results show significant variations of light attenuance (associated with NO2- concentrations in the Griess test) depending on the opacity, sedimentation behaviour, NO2- adsorption and photocatalytic properties of the tested TiO2 nanomaterials. These findings identify material characteristics recommended to be considered when analysing the results of Griess tests performed in biological studies involving TiO2 nanoparticles.

Ba(Zn1/3Ta2/3)O-3 (BZT) thin films were grown on Pt-coated Si substrates at 500 degrees C substrate temperatures by pulsed electron beam deposition method and post-annealed at 600 and 650 degrees C for 1 h. The X-ray diffraction patterns indicate that the as-grown films are partially crystallized but single-phase cubic perovskite structure was formed in annealed films. The temperature dependence of the dielectric constant of the BZT films was recorded in the -100 to + 100 degrees C range. The annealing treatment induces a decrease of the temperature coefficient of the dielectric permittivity with an order of magnitude, from 2000 to 100 ppm/degrees C. The influence of the annealing treatments on the temperature behavior of the BZT films was evidenced; a dielectric constant of about 21 at room temperature was obtained for the films annealed at 650 degrees C. (C) 2012 Elsevier B. V. All rights reserved.

The synthesis of a new garnet, Er3Li0.275Nb0.275Ga4.45O12 (ErLNGG), by solid-state reaction, is reported. A comparison of the fluorescence spectra of Er3+ in ErLNGG, Er-doped (0.1 at.%) calcium lithium niobium gallium garnet (CLNGG), and Er(50 at.%):CLNGG is presented. The narrowing of luminescence lines suggests an ordering of the partially disordered CLNGG with the increase of erbium concentration.

The electronic structure of metallofullerene Ce@C-82 is probed by resonant x-ray emission spectroscopy at the Ce L-3 absorption edge. We observed a satellite structure in x-ray absorption and resonant emission spectra for Ce@C-82, which, we show, corresponds to the charge transfer induced by the core-hole potential in the final state, similarly to Pr@C-82. This charge-transfer satellite may be a common feature in metallofullerenes. The temperature dependence of the electronic structure is also investigated.

The attractive properties of ceria, particularly the conductivity and chemical stability, have led to vast research efforts to investigate, characterize and develop such materials. One of the main applications of this ceramic is in the solid oxides fuel cells for intermediate temperatures IT-SOFC. The aim of this work is the preparation and characterization of cubic ceria nanopowders doped with 10 mol % yttria or Scandia. A thermal treatment (calcinations) was applied on the obtained nanopowders, which were consequently investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected aria electron diffraction (SAED).

Yttria doped ceria reinforced with yttria doped alumina compound for IT-SOFC applications has been prepared by sol-gel method and sintered at 1300 degrees C, 1400 degrees C, 1500 degrees C. XRD, and SEM show the presence of a needle-like cerium-magnetoplumbite (CeAl11O17) phase in the compound; the oxygen deficient phase grows from the alumina phase by using ceria from the surrounding matrix and releasing oxygen ions As the sintering temperature is increased, the alumina phase is gradually transformed into CeAl11O17. Compared to the yttria doped ceria without reinforcement, the obtained compounds with ceria-magnetoplumbite show only a slight decrease of the Young elasticity modulus. However, the samples become brittle after backing in oxygen atmosphere (1000 degrees C, and 1500 degrees C).

The synthesis of a new garnet, Er3Li0.275Nb0.275Ga4.45O12 (ErLNGG), by solid-state reaction, is reported. A comparison of the fluorescence spectra of Er3+ in ErLNGG and in Er-doped (5 at. %) Calcium Lithium Niobium Gallium Garnet (CLNGG) suggests an ordering of the partially disordered CLNGG when Ca2+ ions are completely substituted by Er3+ ions.

CuIn1-xGaxS2 (CIGS2) thin-films for solar cells were prepared by rf-magnetron sputtering and were deposited on glass substrate. These films were prepared using a stepwise process consisting of succesive deposition of CuInGa (d = 1500 nm) and ZnS (d = 200 nm) layers. Each layer was structurally characterized by X-ray diffraction and atomic force microscopy. The microstructural and optical properties of CIGS2 component films of the solar cell in comparison with those of ZnS and CuInGa films separately deposited onto glass substrates under the same conditions, were studied. Transmission spectra of our thin films are strongly influenced by deposition conditions and nature of the support material and they were recorded for each component film and CIGS2 solar cell.

Gold layers were deposited at oblique incidence onto glass plates. A B30.2 Hochvakuum Bedampfungsanlage equipment was used in this aim. The deposition conditions were chosen in order to obtain nanostructured layers. Correlations were found among these conditions and the corresponding nomograms were then obtained. Examples of such depositions were given and the layers structure was characterized and additionally supported by observing the molecular alignment given in the liquid crystal cells obtained with these gold layers.

TiO2 nanopowders, doped with Fe3+ and Eu3+ were obtained by high-energy ball milling and their physical properties were investigated as a function of the doping content and ball milling time. A noticeable red shift and high photoactivity in the degradation and catalytic oxidation reactions of styrene and phenol were found for all doped specimens.

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.

An x-ray spectroscopy study was performed for YbCU5-xAlx (x = 0.0-2.0) using high-resolution partial-fluorescence yield (PFY) and resonant inelastic x-ray scattering (RlXS) at the Yb L-3 absorption edge. From a careful analysis of the PFY and RlXS spectra, the mean-valence of Yb was estimated and is found to increase quite rapidly for compositions between 0 <= x <= 1.0, indicating strong intermediate-valence behavior. The mean valence continues to increase gradually with x and becomes nearly trivalent for x = 2.0. Our results, however, reveal that valence fluctuation occurs even at x = 1.5, for which non-Fermi liquid quantum critical behavior is known. The valence evolution cannot be explained solely in terms of chemical pressure effects. The study suggests the role of valence-coupled spin fluctuations for the quantum critical behavior.

The L alpha and L beta spectra of tungsten were measured using a high-resolution single-crystal x-ray spectrometer. The observed spectra were fitted into Lorentzians. The fit residuals of the L alpha and L beta spectra indicate the presence of satellites in the vicinity of each spectrum, which are originated from Coster-Kronig transitions. Linewidths, energies, and intensities were estimated for each diagram line and compared with previous data. The L beta(2) satellite line observed by Salgueiro er al. [J. Phys. (Paris), Colloq 48, C9-609 (1987)] was confirmed on the high energy side of the L beta(2) line. The origin of this satellite is discussed experimentally and theoretically. [S1050-2947(98)02011-3].

The crystal structure of (Bi1.82Pb0.18) (ST1.84Pb0.16) CuO6 was determined from single-crystal intensity data measured on a four-circle diffractometer. The structure is orthorhombic, space group Cccm (No. 66); the lattice parameters: a=5.392(3) Angstrom, b=24.603(5) Angstrom, c=5.300(3) Angstrom, V=703.2 (5) Angstrom(3) (the space group can be denoted as Amaa by a cyclic transformation of the cell constants). The R value was 0.048 for 418 unique reflections with I>3.00 sigma(I). One of the O atoms bonded to Bi ions is disordered at two sites with a half occupancy and B-eq=3.6(6) Angstrom(2); although the thermal parameter is not so large as that reported by Torardi et al. [Phys. Rev. B 38, 225 (1988)], the disorder suggests that the crystal has a lower symmetry. The valence state of the Cu ion in the present compound was evaluated to be trivalent based on the Cu-O distances [Asbrink and Norrby, Acta Crystallogr. B 26, 8 (1970)] and the valence of Bi was estimated in comparison with that in other compounds. The O(3) sublattice dynamics in these types of superconductors is discussed based on the structural investigations.

The x-ray-absorption cross section above the L edges in xenon gas has been measured using synchrotron radiation. Multielectron excitation effects are investigated over a few hundred eV region from the Xe L-I, L-II, and L-III edges and the contributions from the effects of shake-up and shake-off to the photoabsorption spectrum are elucidated. Several multielectron excitation features were detected and analyzed by the theoretical energy of the shake-up process. Previous observations of the [2(s,p)5(s,p)] and [2(s,p)4d] transitions have been confirmed. [2(s,p)4p] transitions are clearly identified in the present study. It is very difficult to detect the [2s3s] multielectron transition with the sensitivity of similar to 2.0 x 10(-4) at the L edge jump. The [2s3d] edge was distinguished using the first derivative of the absorption curve. A new transition is found between [2(s,p)4p] and [2(s,p)4d] transitions and identified as a three-electron transition [2(s,p)4d5p]. Moreover, the difference in the behavior of the multielectron excitation as a function of x-ray energy among the L-I and L-II, or L-III edges is confirmed and investigated. [S1050-2947(98)01802-2].