Dr. Cristian Mihail TEODORESCU

Spin asymmetry is detected in clean Pt(001)-hex by spin-resolved photoelectron spectroscopy even in absence of external sample magnetization. Magnetization of the sample immediately after preparation yields a consistent remnant spin asymmetry in the direction of the applied magnetic field. The surfaces were also characterized by low energy electron diffraction, scanning tunneling microscopy and high resolution core level x-ray photoelectron spectroscopy, allowing one to quantify the surface component, attributed to the last surface layer enriched in electrons. The explanation of the spin asymmetry induced by electron accumulation into the last monolayer is sketched by using band ferromagnetism criteria. The orientation of the spin asymmetry in the nonmagnetized sample coincides with the direction of the rows of the hex reconstruction, while in the magnetized sample it is aligned with the direction of the external magnetizing field. A strong variation of the spin asymmetry as function of the binding energy near the Fermi level, whose amplitude depends also on the median emission angle, suggests a spin textured state in this energy range or the presence of a Stoner gap

Recently, spin asymmetry in O 2p related deep valence states was evidenced in SrTiO3(001) [Popescu et al., Phys. Scr. 99(10), 105925 (2024)]. In this work, we report the detection of a much higher (about four times) spin asymmetry in SrTiO3(011) by spin resolved photoelectron spectroscopy, with samples characterized also by core level x-ray photoelectron spectroscopy and low energy electron diffraction. The explanation of a so important spin asymmetry is related to the partial neutralization of O-2(4-) or SrTiO(4+) end layers. Missing electrons from O 2p states in the case of O-2 terminations enable robust atomic spins, according to Hund's rule. The parallel analysis of core level shifts for surface atoms and the amplitude of spin asymmetry suggests that 50% of the oxygens from the surface SrO layer of SrTiO3(001) have a 2p(5) configuration with an unpaired electron (the rest are in a 2p(6) configuration), while in the case of O-2 terminated SrTiO3(011), about 50% of surface oxygens have a 2p(5) configuration and 50% of surface oxygens are neutral (2p(4)), yielding a net charge per O-2 surface unit cell of (-1) instead of (-4). The magnetization is oriented along the rows formed by the (4 x 1) reconstruction in the 011 in-plane direction. (c) 2025 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license(https://creativecommons.org/licenses/by/4.0/).

Adsorption and desorption of ethylene on BaO-terminated (001) barium titanate are investigated by X-ray photoelectron spectroscopy. Carbon is found in an oxidized state, at a binding energy similar to that resulting from CO adsorption on BaTiO3(001). The amount of carbon adsorbed on the surface is also similar to the case of CO/BaTiO3(001). Upon heating the substrate up to the loss of its ferroelectric polarization, the C 1s signal from the oxidized spectral region vanishes. At the same time, there was no noticeable oxygen depletion of the surface after repeated C2H4 adsorption and desorption. The substrate remains stable after repeated oxidative adsorption and desorption of ethylene. Desorption occurs at different temperatures, depending on the adsorption temperature, which suggests different adsorption geometries: non-dissociated adsorption at high temperature with ethylene bond on two surface oxygen atoms, and locally dissociated adsorption at lower temperatures, in "formaldehyde-like" local configurations.

Carbon dioxide (CO2) is reversibly adsorbed and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate, as revealed in real time by high resolution and ultrafast photoelectron spectroscopy and certified by low energy electron diffraction. Desorption proceeds when the substrate is heated above its Curie temperature. The amount of CO2 adsorbed is derived to be between one molecule for a surface BaO unit cell (adsorption below room temperature) and one molecule for two unit cells (adsorption above room temperature). The molecule is bound with its carbon to surface oxygen, forming a CO3 structure. The BaTiO3(001) surface is unaffected by repeated cycles of adsorption-desorption. The relatively high amount of CO2 adsorbed and the stability of the substrate after repeated adsorption and desorption processes promotes barium titanate as a promising candidate for decarbonization technologies.

Carbon monoxide (CO) is reversibly adsorbed on and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate. All processes are characterized in real time via photoelectron spectroscopy. Adsorption proceeds on different sites/geometries as a function of substrate temperature. Below room temperature, CO is adsorbed on surface Ba. At room temperature, adsorption proceeds on surface oxygen, whereas at high temperatures, "hollow" site adsorption occurs with carbon coordinated with three oxygens, one oxygen initially belonging to CO and two oxygens from the substrate. The amount of CO adsorbed is about one molecule for 10 surface unit cells, which is slightly increased at low temperatures. CO is desorbed if the substrate is heated above the Curie temperature, which is a sign of the definitory role of ferroelectric polarization. The BaTiO3(001) surface is unaffected by repeated cycles of adsorption-desorption.

Atomically clean SrTiO3(001) is characterized by low energy electron diffraction, core level and valence band photoelectron spectroscopy, the latter also with spin resolution. Samples prepared by a sputtering-annealing procedure exhibited in-gap states in the valence band spectra, Ti3+ components in Ti 2p core level spectra and a noticeable spin asymmetry in the 3-9 eV binding energy range, which corresponds to valence states of mainly O 2p character. Upon annealing in oxygen, the spin asymmetry vanishes, accompanied by the intensity decrease of the contribution of titanium low ionization states and of in-gap states, indicating that these three phenomena are mutually connected. The observed spin asymmetry may be generated by indirect exchange mediated by the in-gap states between O 2p orbitals, or by the partial Ti 3d character of these states, which acquire non-zero spin in case of incomplete oxygen coordination.

Pb(Zr,Ti)O-3 (PZT) is the most common ferroelectric (FE) material widely used in solid-state technology. Despite intense studies of PZT over decades, its intrinsic band structure, electron energy depending on 3D momentum k, is still unknown. Here, Pb(Zr0.2Ti0.8)O-3 using soft-X-ray angle-resolved photoelectron spectroscopy (ARPES) is explored. The enhanced photoelectron escape depth in this photon energy range allows sharp intrinsic definition of the out-of-plane momentum k and thereby of the full 3D band structure. Furthermore, the problem of sample charging due to the inherently insulating nature of PZT is solved by using thin-film PZT samples, where a thickness-induced self-doping results in their heavy doping. For the first time, the soft-X-ray ARPES experiments deliver the intrinsic 3D band structure of PZT as well as the FE-polarization dependent electrostatic potential profile across the PZT film deposited on SrTiO3 and LaxSrMn1-xO3 substrates. The negative charges near the surface, required to stabilize the FE state pointing away from the sample (P+), are identified as oxygen vacancies creating localized in-gap states below the Fermi energy. For the opposite polarization state (P-), the positive charges near the surface are identified as cation vacancies resulting from non-ideal stoichiometry of the PZT film as deduced from quantitative XPS measurements.

Recently, Kittel's theory of ferromagnetic domains in thin films in one dimension, i. e. with the domains extended infinitely over one in-plane direction and with the anisotropy axis oriented perpendicular to the film was revisited by considering the film thickness and unbalanced domains with up and down magnetization, yielding to the computation of magnetic hysteresis [C. M. Teodorescu, Res. Phys. 46 (2023) 106287]. In this work, the above study is extended to samples featuring two-dimensional domain landscapes, for materials with strong magnetic anisotropy, typically characterized by a superunitary ratio between the anisotropy energy and the stray field energy densities. This allows one to compute the most stable structures for vanishing average magnetization together with hysteresis curves for thin films with perpendicular magnetic anisotropy and two-dimensional rectangular domains and also for thin films with in-plane magnetic anisotropy. For two-dimensional films with perpendicular magnetic anisotropy, the most stable structure for = 0 is found to be that with domains infinitely elongated along one in-plane direction, i. e. the one-dimensional case treated in the preceding work. For thin stripes with in-plane magnetization, the domain size l is approximately linear with the stripe lateral size d for low film thickness, while for large film thicknesses it follows a Kittel-like law, but as function of the stripe size l similar to d(1/2). For in-plane magnetized thin films of infinite lateral extent, the most stable structure is the single domain. As for hysteresis curves, the two-dimensional case with perpendicular magnetic anisotropy is shown to evolve from a 2D landscape derived from the checkerboard structure, but with unbalanced domains for magnetization near saturation, towards one-dimensional domain structures for lower magnetization. In some cases and depending also on the demagnetization factor, the one-dimensional case is not reached, and the film exhibit 2D structures on the whole range of the magnetization curve. The hysteresis obtained for thin magnetic stripes with in-plane magnetization also can exhibit a rich structure, with minor cycles on the wings of the magnetization curves evolving towards ,,normal" hysteresis (again, depending on the film thickness, stripe lateral size and demagnetization factor). An infinite thin film with in-plane anisotropy features a steplike magnetization dependence on the applied field.

In 1946 and 1949, Charles Kittel proposed a simple model for the size of ferromagnetic domains that is still widely used nowadays [C. Kittel, Phys. Rev. 70 (1946) 965-971 and Rev. Mod. Phys. 21 (1949) 541-583], including for other ferroic systems, such as ferroelectrics and multiferroics. Kittel's theory is revisited in this work, with a more detailed demonstration and emphasizing the main assumptions utilized, by using SI units instead of CGS units, as in the original Kittel's works. The validity limits of the Kittel's scaling law where the domain width varies with the square root of the sample thickness towards low thicknesses is derived, with the possibility of evolution towards large domains for ultralow thicknesses. Further, Kittel's model is extended to the case where the sample has a non-vanishing net magnetization and it is shown how magnetization curves at zero temperature can be obtained. This is discussed by supposing constant width of a pair of neighboring domains with opposed magnetization, or by allowing this width to vary as function on the net magnetization of the sample. Though this latter assumption seems to be more reasonable from the point of view of the evolution towards a single domain state at saturation, it seems that the model able to yield most accurate vales of the coercive field is the domain with fixed width of the pair of domains, which justifies the assumption of domain wall pinning". The introduction of the demagnetization factor associated with the finite size of the film yields a maximum thickness up to which the films present hysteresis curves. The validity of this theory for ferrelectric domains is also briefly discussed.

Probing of the free surface ferroelectric properties of thin polar films can be achieved either by estimating the band bending variance under the top-most layer or by studying the extent of the extrinsic charge accumulated outside the surface. Photoemitted or incoming low-energy electrons can be used to characterize locally both properties in a spectromicroscopic approach. Thin ferroelectric lead zirco-titanate (PZT) is investigated by combining low energy/mirror electron microscopy (LEEM/MEM) with photoemission electron microscopy (PEEM) and high-resolution photoelectron spectroscopy (XPS). Significant extrinsic negative compensation charge is proven to accumulate on the surface of the outward polarized thin film, indicated by high MEM-LEEM transition values, up to 15.3 eV, and is correlated with the surface electrostatic potential, which can be partially screened either by electrons interacting with the sample or by soft X-rays through the ejection of secondary electrons and generation of positive charge under the surface. A radiation-induced surface charge compensation effect is observed. The study indicates that air-exposed high quality ferroelectric thin films show large negative surface potentials, determined locally on the surface, which are nevertheless sensitive to beam damage and molecular desorption. These values represent a confirmation of previously estimated surface potential energy values determined from the LEED data on clean surfaces.

Recently, a simple model was proposed for the microscopic energy associated to the ferroelectric phase, to be used in a statistical approach in order to derive the equations of state for a ferroelectric thin film [C. M. Teodorescu, Phys. Chem. Chem. Phys., 2021, 23, 4085-4093]. The stabilization energy for an elemental dipole in a polar thin film is the result of the interaction of this dipole with the field generated by charges accumulated at surfaces or interfaces of the thin film. An essential parameter of this interaction is the permittivity of the film, assumed to be a material constant, together with the maximum value of an elemental dipole and the density of the elemental dipoles. These can be connected to three experimental parameters which are the saturation polarization P-s, the coercive field at zero temperature E-c((0)) and the Curie temperature T-C. However, for a ferroelectric material both the global and the differential permittivity depend on the temperature and on the polarization. This raises the question whether such a non-constant permittivity should be used in the stabilization energy of the ferroelectric phase, and whether it can be identified self-consistently with the function resulting after applying the statistics based on the microscopic model. In such case, a mutual interdependence should exist between P-s, E-c((0)) and T-C. A model is built up, able to predict coercitivity, however E-c((0)) and T-C yield values several orders of magnitude higher than the experimental ones. Therefore, one has to introduce a background dielectric constant of several hundreds to accommodate the result of the model with the experimental data. The poling history of the film has to be taken into account, together with the presence of a small bias field. The model is able to predict self-consistently the equation of state of a ferroelectric, and in particular the linear decrease of the coercive field with temperature. The microscopic parameters, in particular the background dielectric constant and the density of elemental dipoles may be expressed directly from experimental quantities.

A recent theory of band ferromagnetism in 3d metals predicts 're-entrant' ferromagnetism at temperatures far above the boiling point of these metals in normal conditions (Teodorescu, C.M., 2021. Spin asymmetry originating from densities of states: Criterion for ferromagnetism, structures and magnetic properties of 3d metals from crystal field based DOSs. Results in Physics 25, 104,241). Metals, and in particular iron rich alloys, are still solid at such extremal temperatures in the Earth's inner solid core. It follows that this piece of the Earth may become ferromagnetic. This hypothesis is investigated in this work in more details, by using densities of states derived by ab initio density functional theory calculations for hexagonal close-packed iron and applying the basic theory of band ferromagnetism derived in the above Reference. The temperature for 're-entrant' ferromagnetism increases with the pressure, ranging between about 6530 and 6640 K for pressures between 330 and 360 GPa; these temperatures are in the range of most estimates for the temperature of the inner solid core of our planet. The dimension of the ferromagnetic "innermost inner core" (IMIC) derived from the estimated Fe magnetic moment are within the dimensions of a IMIC with different anisotropy in the propagation of seismic waves. For body centered cubic Fe no 're-entrant' ferromagnetism is predicted based on the actual model. It follows that the Earth's inner solid core with hexagonal close-packed structure is the main responsible for the geomagnetic field, and also most probably the reversal of this field proceeds by simple rotation of the magnetization of this core, while keeping a non-vanishing magnetic field during the reversal. This might prevent the Earth's surface bombardment with energetic charged particles during the reversals, with beneficial effects for complex lifeforms and for mankind civilization.

The catalytic hydrotreatment of humins, the solid byproduct produced from the conversion of C6 sugars (glucose, fructose) to 5-hydroxymethylfurfural (HMF), using supported Pd@zeolite (Beta, Y, and USY) catalysts with different amounts of Pd (i.e., 0.5, 1.0 and 1.5 wt%) was investigated under molecular hydrogen pressure. The highest conversion of humins (52.0%) was obtained on 1.5Pd@USY catalyst while the highest amount of humins oil (27.3%) was obtained in the presence of the 1Pd@Beta zeolite sample, at P-H2 = 30 bars and T = 250 degrees C. The major compounds in the humins oil evidenced by GC-MS are alcohols, organic acids, ethers, and alkyl-phenolics. However, although all these classes of compounds are obtained regardless of the nature of the catalyst used, the composition of the mixture differs from one catalyst to another. Furanic compounds were not identified in the reaction products. A possible explanation may be related to their high reactivity under the reaction conditions, in the presence of the Pd-based catalysts these compounds lead to alkyl phenolics, important intermediates in the petrochemical industry.

A deeper understanding of the coupling at the interface of multiferroics heterostructures is being achieved by the use of synchrotron radiation techniques. Here, the authors use k-resolved soft X-ray photoemission spectroscopy and first principles calculations to investigate the band structure of several multiferroic heterostructures, isolating the distinct signature of the interface. Physics of the multiferroic interfaces is currently understood mostly within a phenomenological framework based on screening of the polarization field and depolarizing charges. Additional effects still unexplored are the band dependence of the interfacial charge modulation and the associated changes of the electron-phonon interaction, coupling the charge and lattice degrees of freedom. Here, multiferroic heterostructures of the colossal-magnetoresistance manganite La1-xSrxMnO3 buried under ferroelectric BaTiO3 and PbZrxTi1-xO3 are investigated using soft-X-ray angle-resolved photoemission. The experimental band dispersions from the buried La1-xSrxMnO3 identify coexisting two-dimensional hole and three-dimensional electron charge carriers. The ferroelectric polarization modulates their charge density, affecting the coupling of the 2D holes and 3D electrons with the lattice which forms large Frohlich polarons inherently reducing mobility of the charge carriers. Our k-resolved results on the orbital occupancy, band filling and electron-lattice interaction in multiferroic oxide heterostructures modulated by the ferroelectric polarization disclose most fundamental physics of these systems needed for further progress of beyond-CMOS ferro-functional electronics.

Photoelectron spectromicroscopy data cubes with sub-micrometer spatial resolution from a lead zirconate titanate thin film are fitted in each spatial point for several areas investigated, and correlations between the results of the fitting parameters are established, enabling one to suggest that surface band bending manifests also in the case of samples with multiple polarization states. These surface band bendings may be used for preliminary assessment of polarization states by using the contrast in binding energy. However, the individual curve fitting of each spectrum and the analysis of correlations between the derived parameters (binding energies and amplitudes) yields results of deeper significance in deriving the distribution of band bending. This allows in some cases discriminating between the origin of the individual components, assessing charging effects and compensation mechanisms, also enabling one to establish correlations between areas with different polarization. It is found that the major part of the investigated areas consist in regions with outwards polarization and without out-of-plane polarization, with the presence of some isolated metal Pb clusters. On a single area, components attributed to inwards polarization are detected, and their formation occurs at the expense of areas without out-of-plane polarization, mostly for a given proportion of the outwards polarization.

A simple view of ferroelectricity is proposed for a thin film with uniform polarization oriented perpendicular to its surface, starting from the assumption that this situation is always accompanied by charge accumulation in the outer metal electrodes, in the contamination layers or near the surface, in the ferroelectric film itself. Starting with the formula derived for an "elemental" dipole moment in the film, simple statistical mechanics allows one to derive hysteresis cycles, and their dependence on temperature starting with only two parameters: the dielectric constant of the material and the maximum value of the dipole moment of a unit cell. Values obtained for Curie temperatures and coercive fields agree well with experiments. "Exact" energy dependencies on the asymmetry parameter are derived, and their connection with the Landau-Ginsburg-Devonshire is proven. By considering also the dipolar interaction in a continuous model, in addition to the ordering energy in the presence of surface charge accumulation, one may estimate the distribution of the polarization inside the film and the validity of the hypothesis of uniform polarization.

Ferromagnetism in 3d metals is re-examined in a simple band model. It is shown that the molecular field model cannot account for the low values of coercive field in ferromagnetic pure metals, and that the standard Stoner theory of band ferromagnetism incorrectly evaluates the total electronic energy and cannot predict reasonable Curie temperatures. A simple band model for magnetism is formulated, yielding a criterion for ferromagnetism even in absence of a Hubbard term, involving only the density of states (DOS) at the Fermi level, its derivative and the filling of the 3d band. By introducing a double-peaked DOS, one may explain the occurrence of ferromagnetism in bcc Fe, hcp-fcc Co and fcc Ni, the stabilization of fcc-hcp or bcc structures across all 3d elements, the occurrence of antiferromagnetism in chromium, and derive reasonable Curie temperatures. 'Re-entrant' ferromagnetism is predicted at ultrahigh temperatures, suggesting an alternate origin for the geomagnetic field.

Carbon monoxide is adsorbed at room temperature on graphene formed on atomically clean Pt(001)-hex by chemical vapor deposition, starting with ethylene, in ultrahigh vacuum. The graphene formation is characterized in situ by high resolution photoelectron spectroscopy (HRPES), by low energy electron diffraction (LEED) and by near-edge X-ray absorption fine structure (NEXAFS). The formation of graphene destroys the hex reconstruction of Pt(001) and graphene exhibits totally in-plane sp(2) bonding. CO adsorption is characterized by HRPES and a rigid shift towards higher binding energies by about 96 meV is experienced by Pt 4f core levels, together with a shift towards lower binding energy by 36 meV of the C 1s level corresponding to graphene, while the amplitude analysis of carbon and platinum peaks suggests the intercalation of carbon oxide between graphene and the metal substrate. The presence of oxidized carbon is evidenced by a separate component in the C 1s spectrum (attributed to carbon bond to oxygen) and by the occurrence of the O 1s signal. The coverage expressed in terms of the ratio of the integral amplitudes of the carbon bond to oxygen to the amplitude of the carbon from graphene approaches 3 %, yielding a CO coverage of Pt(001) of about 0.12 monolayer. The derived atomic ratio (O 1s):(C 1s bond to O) is initially close to 1, then evolves in time towards values close to 2, which means that CO is progressively oxidized upon adsorption and irradiation with soft X-rays. The relative amount of oxygen and oxidized carbon decreases in time under irradiation with soft X-rays. Weakly bound graphene on incommensurate metal surfaces may be used as atomic scale nanoreactors for trapping and immediate oxidation of carbon monoxide.

Gold is deposited on atomically clean, inwards polarized, ferroelectric lead zirco-titanate deposited by pulsed laser deposition on strontium titanate (001) single crystal, then carbon monoxide adsorption and desorption experiments are investigated by in situ fast photoelectron spectroscopy using synchrotron radiation. Atomic force microscopy and high resolution photoelectron spectroscopy are consistent with the formation of 50?100 nm nanoparticles, and their Au 4f core levels point to a negative charge state of gold. As compared with a similar experiment performed on ferroelectric lead zirco-titanate with similar polarization state and without gold, the saturation coverage after exposure to carbon monoxide increases by about 68 %, and also most of the additional carbon is found in oxidized state. Desorption experiments with in situ follow-up by photoelectron spectroscopy are performed as function of temperature, and the neutral carbon intensity decreases when the ferroelectric polarization decreases, while the components corresponding to oxidized carbon remain unchanged. It looks that neutral carbon adsorption is strictly related to the polarization of the ferroelectric film, while carbon still found in molecular form is related to its carbonyl bonding on metal nanoparticles, independent of the polarization state of the substrate. Desorbed carbon at higher temperature uptakes oxygen from the substrate.

The emerging field of electronics based on ferro-functional materials relies on driving effectively and predictably a ferroelectric system between different polarization states through bias applied to metallic contacts. This requires detailed understanding of the growth mechanisms and electronic properties of the interface, including ferroelectric and material - dependent band alignment and Schottky barrier heights. Whether the major contribution at the interface band alignment comes from the work function difference or from the ferroelectric state is still under debate. Here, using X-ray photoemsion and ab-initio calculations, we derive the complex microscopic picture of metal/ferroelectric interface formation, including growth mechanism, valence alteration, ferroelectric-dependent electrostatic potential and thickness - dependent compensation mechanisms of ferroelectricity, starting from the ultrathin growth of Cu up to 100 angstrom on BaTiO3. One establishes the evolution of the band bending and of the build-in potential from the initial probed thickness of the ferroelectric in the range of 3 lambda (lambda - the inelastic mean free path) while gradually approaching the contact region with the metal at higher thickness of the top layer. We find that the well-defined orientation of the ferroelectric polarization lead to a band bending at the interface, which add at the bending expected from the work function difference of the two joining materials.

The development of robust, safe, cost-effective and efficient photocatalytic systems for water splitting should take into account the presence of a proper and powerful photon absorber and an efficient, low-cost and earth-abundant electrocatalyst to perform the reaction at high conversions. In this study, Ni-Zn/TiO(2)ternary composites with high photocatalytic activity for water splitting under UV irradiation were successfully prepared via a simple and low-cost deposition-precipitation route. Thus, different Ni : Zn molar ratios (1 : 0, 1 : 1, 3 : 1, 6 : 1, 9 : 1, and 0 : 1) were deposited on TiO(2)in order to reach a total metal loading of 50 wt. %. The obtained composites were characterized using several techniques, such as: X-ray diffraction, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The most active synthesized composite, namely Ni-Zn/TiO2(9 : 1), exhibits H(2)generation rate above 17 mmols g(-1) h(-1), which is nearly one thousand times higher than that obtained with TiO(2)Evonik P25. Our study demonstrates that TiO(2)becomes a degenerated semiconductor in the presence of Ni and ZnO, with remarkable photocatalytic properties. Thus, the obtained results can open new opportunities in the preparation of very active materials for hydrogen production based on the optimization of three-component structures.

Carbon layers are deposited on 100 nm thick atomically clean (001) lead zirconate titanate (PZT) in ultrahigh vacuum, ruling out the presence of any contaminants. X-ray photoelectron spectroscopy is used to assess the substrate surface or interface composition, substrate polarization and the thickness of carbon layers, which ranges from less than one monolayer (1 ML) of graphene to several monolayers. Atomically clean PZT(001) exhibit inwards polarization, and this polarization reverses the sign upon carbon deposition. Cationic vacancies are detected near the PZT surface, consistent with heavy p doping of these films near the surface. The carbon layers exhibited a consistent proportion of atoms forming in-plane sp(2) bonds, as detected by near-edge absorption fine structure (NEXAFS) analysis and confirmed partially by scanning tunneling microscopy (STM). In situ poling with simultaneous in-plane transport measurements revealed the presence of resistance anti-hysteresis versus the polarization orientation for films with less than 1 ML carbon amount, evolving towards 'normal' hysteresis for thicker carbon films. The anti-hysteresis is explained in terms of a mixed screening mechanism, involving charge carriers from the sp(2) carbon layers together with holes or ionized acceptors in PZT(001) near the interface. For thicker films, the compensation mechanism becomes extrinsic, involving mostly electrons and holes from carbon, yielding the expected hysteresis.

Manganese is deposited at high temperature on (001) oriented ferroelectric lead zirco-titanate prepared in two different ways: sputter-annealed or just simply annealed in ultrahigh vacuum. Room temperature ferromagnetism (FM) is obtained for Mn deposited on sputter-annealed substrates, while for the other sample preparation a paramagnetic behaviour is obtained. Also, for the first case a clear inwards component of the polarization P( - ) is observed by X-ray photoelectron spectroscopy and piezoresponse force microscopy. Composition analysis evidenced formation of Pb vacancies in the case of FM - P(( - ) )sample, consistent with hole formation near the surface, needed both to stabilize the inwards polarization state and to intermediate ferromagnetism between Mn2+ ions. The indirect exchange ferromagnetism mediated by holes is stronger, most probably because the interaction energy is proportional with the carrier effective mass. Also, whereas in the case of unsputtered substrate a stable surface Mn oxide is formed, defect formation by sputtering seems to favor Mn migration inside the sample. This also induces the formation of a thin film where ferromagnetism and the orientation of ferroelectric polarization might have the same origin, i. e. holes accumulated near the outer surface.

The competition between interface barrier in the Schottky-Mott limit and polarization driven mechanism is established during gradual formation of metal (Au) - ferroelectric (BaTiO3) interface. X-ray photoelectron spectroscopy provides core level energies and valence band positions in the contact region, to monitor the band alignment from the very first stages of metal deposition on BaTiO3. The band bending at metal/ferroelectric (FE) interface is extracted from the shift of core levels (Ba 3d, Ti 2p) as a function of the metal thickness. It is shown that the interface band alignment mechanism involves a well-defined polarization orientation washing out the bending expected from the work function difference. The sudden modification of the binding energies within ferroelectric at the first 2 angstrom Au indicates that the ferroelectric compensation mechanism triggered by the metal overlayer initiates already at ultrathin top layer, while subsequent growth contributes only at a gradual correction of the potential in the FE. The emerging picture is confirmed in first-principle calculation indicating the preferences of Au to grow preferentially to different terminated regions and to stabilize distinct ferroelectric polarization.

Spirobifluorene-based porous organic polymers (POP) were synthesized following two different protocols; the acetylenic coupling reaction conditions and the Sonogashira cross-coupling reaction. These were utilized as support for the hydrogenation of a series of species containing unsaturated C=C and C=O bonds (4-nitrostyrene, 4-bromobenzophenone, acetophenone, 7-nitro-1-tetralone and 1,2-naphtoquinone confirmed their efficiency). POP1 prepared via a copper-catalysis protocol was completely inactive, while POP2-4 containing residual Pd exhibited different activities in accordance to the accessibility of the substrates to the metal. Further deposition of 0.5wt% Pd led to active and stable catalysts. They were easily separated by filtration, and after re-dispersion, afforded the same performances for ten successive cycles. This study also evidenced the specific role of the support in these reactions by comparing the behavior of Pd/POP with that of a Pd/C catalyst with the same loading of palladium. The deposition of Pt on these supports led to sub-nanometric particles and, in accordance, to a different catalytic behavior reflected merely by differences in the selectivity.

Growth of Ag films of up to 30 nm thickness on Si(1 1 1) 7 x 7 at room temperature is investigated by low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). LEED revealed the coexistence of Ag and Si spots starting with 1 monolayer (ML) of Ag deposited. The Ag lattice constant, starting with 25 ML, is slightly higher than for bulk Ag and increase linearly with Ag thickness, reaching about 4.2 nm for the thickest films. The average terrace widths detected from LEED spot profile analysis are about 30 nm for clean Si(1 1 1) 7 x 7 and about 5.5 nm for the thickest Ag(1 1 1) film, in agreement with STM observations. The intensity variation of core levels analyzed by XPS is taken into account by a model assuming the initial formation of Ag islands with linear variation of coverage vs. the amount of Ag deposited, followed by growth in a quasi layer-by-layer mode. The interface barrier is in the range of 0.4 eV, lower than all values reported previously. Ag deposited on Si(1 1 1) 7 x 7 at room temperature provides flat Ag(1 1 1) for synthesis of 2D materials, and may be used for low barrier Schottky diodes.

By platinum deposition on a 150 nm thick film of lead zirco-titanate oriented PZT(001), grown on strontium titanate (001) single crystals with a strontium ruthenate buffer layer, which did not show initial preferential out-of-plane orientation of its ferroelectric polarization, a band bending near the interface towards lower energies is observed using photoelectron spectroscopy, by following all core levels from the substrate (Pb 4f, Zr 3d, Ti 2p, O 1s). This is unexpected given the fact that platinum has a larger work function than PZT and a rectifying contact for electrons is expected to be built at the interface. This observation may have two explanations: (i) platinum forms an alloy with elements from PZT yielding a metal with considerable lower work function; (ii) platinum provides electrons to the substrate which are able to compensate the depolarization field generated by the outwards polarization state. Several arguments are brought in favor of the second hypothesis, especially the attenuation of core levels from the substrate which is well described by exponential functions with reasonable values of the photoelectron inelastic mean free path, suggesting the formation of a sharp interface. High resolution transmission electron microscopy confirmed the sharpness of the interface. (C) 2017 Elsevier B.V. All rights reserved.

We investigate the effect of the nature of the substrate and the bottom interface on the out-of-plane polarization orientation of ultrathin (10-nm) lead zirconate titanate (PZT) thin films of (001) orientation by photoelectron spectroscopy of samples without surface contamination. The substrate nature is varied between insulator (strontium titanate, STO) and semiconductor (Nb-doped STO, STON) and finally to a metal with a work function lower than that of PZT (strontium ruthenate, SRO). Outward polarization is obtained for PZT/STON(001) and inward polarization is obtained for PZT/STO(001) and PZT/SRO(001). Explanations are given for all these typical cases, the main elements being charge accumulation for compensation of the depolarization field, self-doping of PZT films, and the interface electric field driving the orientation of the polarization of the ferroelectric films. We find p-type self-doping is correlated with the inward polarization, and the driving field is formed between a negatively charged region with negatively ionized acceptors near the interface with the substrate and the p-type degenerate region with holes accumulated inside, toward the surface. This mechanism may be reversed under the assumption of n-type self-doping, positively ionized donors near the interface, and accumulated electrons toward the surface in the case of an interface with a substrate with a higher work function, being in line with recent data (PZT/Pt or BaTiO3/SRO).

Ni films of 20 nm nominal thickness were grown on Ge(001) substrates by molecular beam epitaxy at several different temperatures from room temperature up to 400 C. X-ray diffraction and X-ray photoelectron spectroscopy reveal the nucleation of Ni-Ge compounds (NiGe, Ni2Ge, Ni5Ge2) as well as a departure from the fcc Ni structure exhibited by the films at and beyond a temperature of 100 C. The binding energy of the Ni 2p peak increases from the RT value (852.7 eV) by 0.51.1 eV for the Ni/Ge(001) samples, while the Ge 2p binding energy changes by 0.60.7 eV after Ni growth compared to a clean Ge(001) substrate (there is only a +/- 0.15 eV shift among the samples grown on substrates at higher temperatures). By increasing substrate temperature, we obtained higher intermixing of Ni and Ge, but rather than both Ni and Ge interdiffusing, we find that Ni diffuses further into the germanium with higher substrate temperature, forming increasingly Ni-rich Ni-Ge compounds diluted into the Ge matrix. Based on Magneto-optic Kerr Effect measurements, Ni/Ge(001) grown on substrates at 100 and 200 C does not exhibit a hysteresis loop, while the samples on 300 and 400 C substrates show magnetic behavior, which we attribute to the magnetic character of hexagonal Ni5Ge2 (which is determined here for the first time to be a ferromagnetic phase). (c) 2017 Elsevier B.V. All rights reserved.

The positions of the low energy electron diffraction (LEED) spots from ferroelectric single crystal films depend on its polarization state, due to electric fields generated outside of the sample. Onemay derive the surface potential energy, yielding the depth where the mobile charge carriers compensating the depolarization field are located (delta). On ferroelectric Pb(Zr, Ti)O-3(001) samples, surface potential energies are between 6.7 and 10.6 eV, and d values are unusually low, in the range of 1.8 +/- 0.4 angstrom. When delta is introduced in the values of the band bending inside the ferroelectric, a considerably lower value of the dielectric constant and/or of the polarization near the surface than their bulk values is obtained, evidencing either that the intrinsic 'dielectric constant' of the material has this lower value or the existence of a 'dead layer' at the free surface of clean ferroelectric films. The inwards polarization of these films is explained in the framework of the present considerations by the formation of an electron sheet on the surface. Possible explanations are suggested for discrepancies between the values found for surface potential energies from LEED experiments and those derived from the transition between mirror electron microscopy and low energy electron microscopy.

We report the structural, electronic and magnetic investigation using extended X-ray absorption fine structure spectroscopy (EXAFS), photoelectron microscopy, spin-resolved photoemission and magneto-optical Kerr effect on the properties of MnGe systems obtained by molecular beam epitaxy deposition of manganese on Ge(001) wafers annealed on temperatures between 50 and 450 C. Magnetic ordering can be achieved when the substrate temperature is higher than 250 C, when the manganese tends to diffuse into the Ge matrix and segregate in MnGe-like compounds, as proved by EXAFS. High spatial resolution photoelectron spectroscopy reveals Mn inhomogeneities in the 5-10 m range, even though Mn is found mostly in the same chemical state all over the surface.

This contribution is a review of recent aspects connected with photoelectron spectroscopy of free ferroelectric surfaces, metals interfaced with these surfaces, graphene-like layers together with some exemplifications concerning molecular adsorption, dissociations and desorptions occurring from ferroelectrics. Standard photoelectron spectroscopy is used nowadays in correlation with other characterization techniques, such as piezoresponse force microscopy, high resolution transmission electron spectroscopy, and ferroelectric hysteresis cycles. In this work we will concentrate mainly on photoelectron spectroscopy and spectro-microscopy characterization of ferroelectric thin films, starting from atomically clean ferroelectric surfaces of lead zirco-titanate, then going towards heterostructures using this material in combination with graphene-like carbon layers or with metals. Concepts involving charge accumulation and depolarization near surface will be revisited by taking into account the newest findings in this area.

The stability of thin films of lead zirco-titanate (PZT) under intense soft X-ray beams is investigated by time-resolved photoelectron spectromicroscopy with a lateral resolution below 1 micrometer. Surface dissociation is observed when samples are irradiated with intense (5 x 10(23) photons per s per m(2)) soft X-rays, with promotion of reduced lead on the surface. On areas exhibiting outwards polarization (P(+)), the reduced lead is formed at the expense of P(+)-PZT. On areas presenting co-existing P(+) states with areas without out-of-plane polarization (P-(0)), the reduced lead is formed at the expense of the P-(0)-PZT component, while the P(+)-PZT remains constant. The main dissociation mechanism was found to be triggered by 'hot' electrons in the conduction band, with energies exceeding the surface dissociation energies. Dissociation occurs basically when the electron affinity is larger than the dissociation energy of PbO (for P(+) areas) or PbO- (for P-(0) areas). Such mechanisms may be adapted for dissociation of other molecules on surfaces of ferroelectric thin films or for quantifying the stability of ferroelectric surfaces interacting with other radiation, with applications in the fields of photocatalysis or photovoltaic devices.

We propose a novel idea to improve the surface properties of carbon-based Pt-free electrocatalysts in Polymer Electrolyte Membranes (PEMs) and Alkaline Fuel Cells (AFCs). Our concept is based on the addition of oxygenophilic and hydrophobic ionic liquids (ILs) to form a thin passivating layer at the triple point between the electrocatalyst-electrolyte-gas interface where the Oxygen Reduction Reaction (ORR) takes place.

This paper reports on the aging of carbon nanowalls (CNW) and modification of their wettability by the storage time, growth conditions, and post-fabrication plasma treatments. The as-deposited CNW initially exhibit marked hydrophilic behavior (fresh CNW), but within a few days they become highly hydrophobic (aged CNW). Their final hydrophobicity is closely related to their topography which is controlled by the deposition parameters. In addition, subsequent fluorinated plasma treatments result in super-hydrophobic CNW layers, irrespective of the hydrophilic or hydrophobic character of the pre-treated samples. To explain this, we show that the CNW edges contain many defects initially, but such defects become passivated in time. As a result, the surfaces become highly hydrophobic after aging or fluorination, having inert stable terminations.

Tuneable nitrogen doped carbogels have been synthesised by a simple one-pot hydrothermal carbonisation, followed by pyrolysis at 1000 degrees C, using highly available and low cost precursors such as glucose and ovalbumin. Different physical activation ratios of nitrogen/oxygen were used to demonstrate a sustainable and easy method for changing surface area, pore size and elemental composition in order to investigate their effect on the oxygen reduction reaction when used as electrocatalysts. A ratio of nitrogen mixed with 2% of oxygen was found to be most beneficial for enhancing the catalytic activity by creating a high surface area of 874 m(2) g(-1) as well as a favourable ratio of pyridinic to graphitic nitrogen. The influence of sulphur doping and/or boron on the carbogel structure was investigated. Incorporation of sulphur does not interfere with the structure formation, but decreases the surface area and nitrogen content resulting in diminished ORR performance. However, boron doping with boric acid results in a different carbogel structure by acting as a catalyst, creating an altered morphology, surface area, pore properties and higher nitrogen content by fully utilising ovalbumin as a nitrogen source instead of as a structure directing/surface stabilising agent. Nitrogen content is found to determine the limiting current, while the oxygen content has a small influence on the onset potential. An assumed synergistic effect between nitrogen and boron generates higher electron transfer numbers and lower hydrogen peroxide yields in boron nitrogen co-doped carbogels than those observed in purely nitrogen doped systems.

We report the molecular beam epitaxy growth of Ni on a clean Ge(001) surface with an intermediate NiGe layer forming at the interface at room temperature. The crystallinity of the substrate is lost after the deposition of more than 2 Ni monolayers. The Schottky barrier formation is investigated by X-ray photoelectron spectroscopy. The method allows us to infer a 0.39-0.45 eV band bending at the interface between the compound and Ge(001). Magneto-optical Kerr effect measurements were conclusive in detecting the ferromagnetic ordering of Ni outermost layers. (C) 2017 Elsevier B.V. All rights reserved.

Reducing the recombination rate of photo-generated electron-hole pairs in the surface of pristine TiO2 materials can be done, among others, via local spatial charge separation in the photocatalytically active surface region. A local electric field acting for this purpose can be ensured, for instance, in hetero-junction regions formed at the interface between a TiO2 film and a WO3 ultra-thin layer. The option for the WO3-TiO2 semiconductor pair is related to the suitable fit of their band structures. To model the interface, a more in-depth knowledge of local atomic environment is required. Here, we discuss the local atomic ordering and the related effects in the interface region of TiO2/WO3 and WO3/TiO2 structures grown on Si (100) substrates. Materials characterization was done by using XRD, XPS and XAS techniques. We demonstrate that tungsten atoms enter as W6+ or W4+ cations into the rutile-type TiO2 lattice, by substituting the Ti4+ cations. While W6+-Ti4+ substitution leaves the surrounding rutile matrix unchanged, the W4+-Ti4+ substitution induces a local rutile-to-anatase transition. The current results are relevant in designing new applications structures with enhanced photocatalytic performances.

Atomically clean lead zirco-titanate PbZr0.2Ti0.8O3 (001) layers exhibit a polarization oriented inwards P(-), visible by a band bending of all core levels towards lower binding energies, whereas as introduced layers exhibit P(+) polarization under air or in ultrahigh vacuum. The magnitude of the inwards polarization decreases when the temperature is increased at 700 K. CO adsorption on P(-) polarized surfaces saturates at about one quarter of a monolayer of carbon, and occurs in both molecular (oxidized) and dissociated (reduced) states of carbon, with a large majority of reduced state. The sticking of CO on the surface in ultrahigh vacuum is found to be directly related to the P(-) polarization state of the surface. A simple electrostatic mechanism is proposed to explain these dissociation processes and the sticking of carbon on P(-) polarized areas. Carbon desorbs also when the surface is irradiated with soft X-rays. Carbon desorption when the polarization is lost proceeds most probably in form of CO2. Upon carbon desorption cycles, the ferroelectric surface is depleted in oxygen and at some point reverses its polarization, owing to electrons provided by oxygen vacancies which are able to screen the depolarization field produced by positive fixed charges at the surface.

Hepatocellular carcinoma (HCC) is the most common primary tumor of the liver, ranking as the second most common cause of death from cancer worldwide. Magnetic nanoparticles (MNPs) have been used so far in tumor diagnosis and treatment, demonstrating great potential and promising results. In principle, three different approaches can be used in the treatment of tumors with superparamagnetic iron oxide nanoparticles: magnetically induced hyperthermia, drug targeting and selective suppression of tumor growth. This review focuses on the use of iron oxide nanoparticles for the diagnosis and treatment of liver cancer and offers a walkthrough from the MNPs imaging applicability to further therapeutic options, including their potential flaws. The MNP unique physical and biochemical properties will be mentioned in close relationship to their subsequent effects on the human body, and, also, their toxic potential will be noted. A presentation of what barriers the MNPs should overcome to be more successful will conclude this review.

We investigate band bending effects occurring at the interface between atomically clean Ge(001) and molecular beam epitaxy (MBE) deposited copper and platinum. Low energy electron diffraction(LEED) confirmed the crystallinity of the surface, evidenced the formation of (2 x 1) and (1 x 2) reconstructions, and revealed that it is strongly affected with metal deposition. X-ray photoelectron spectroscopy (XPS) data let us assume a Stranski-Krastanov growth mechanism and confirmed that the observed band bending is associated to an ohmic contact in both cases. For the platinum contact, the high values of the apparent inelastic mean free path (IMFP) derived from the evolution of the XPS intensities indicate a prevalence of mixture of Pt with Ge nearby the interface. Pt deposited on Ge(001) does not behave like a Schottky contact, as one may have expected due to the higher work function of platinum. The observed effect is similar to the ease where interfacial Pt had a lower work function by 2.25/1.96 eV than that of metallic Pt. We propose a model to explain this fact by the effective mass variation or to the conduction band broadening due to the strong intermixing of platinum with germanium under the surface. (C) 2016 Elsevier B.V. All rights reserved.

Carbon layers grown on lead zirco-titanate (PZT) weakly interact with the substrate and exhibit a nearly two dimensional character, up to a carbon surface density approaching that of graphene. The first feature is evidenced by X-ray photoelectron spectroscopy, and the second by angle resolved near-edge-absorption spectroscopy (NEXAFS). The binding energies and lineshape parameters of C 1s are similar to that of graphene. The dichroism of C K-edge NEXAFS shows the prevalence of in-plane sp(2) bonds for layers whose effective coverage is below the graphene surface density. The polarization state of the substrate, oriented outwards, is preserved upon carbon deposition. The surface Pb content is strongly affected by the carbon ad-layers.

A bimodal (micro/mesoporous) COF was synthesized by coupling tetrakis-1,3,5,7-(4'-iodophenyl) adamantane with 4,4'-diethynylbiphenyl following a Sonogashira protocol. The COF preparation strategy led, however, to the incomplete recovery of the palladium catalyst and ICP-OES analysis indicated that around 0.1 wt% palladium remained inside the pores. Noteworthily, the remnant palladium catalyst is still accessible and can be valorised in additional catalytic reactions like the hydrogenation of nitrostyrene. Further deposition of 0.5 wt% active metals (like palladium or gold) enhanced the catalytic activity and tuned the catalyst selectivity with respect to analogous metal catalysts prepared using active carbon as a support. The resulting COF-supported metal NPs are stable and recyclable catalysts. Under normal conditions, this COF is also able to adsorb large amounts of weak electrophilic gases like carbon dioxide.

We report the applicability of a hybrid system comprising a La3+-based catalyst and an Au/TiO2 photocatalyst in the decomposition of chemical weapons. This system is able to perform complete degradation of soman, sarin and VX in less than 1 minute under low basic conditions and visible light irradiation.

Photoelectron spectroscopy studies of (001) oriented PbTi0.8Zr0.2O3 (PZT) single crystal layers with submicron resolution revealed areas with different Pb 5d binding energies, attributed to the different charge and polarization states of the film surface. Two novel effects are evidenced by using intense synchrotron radiation beam experiments: (i) the progressive increase of a low binding energy component for the Pb core levels (evidenced for both 5d and 4f, on two different measurement setups), which can be attributed to a partial decomposition of the PZT film at its surface and promoting the growth of metallic Pb during the photoemission process, with the eventuality of the progressive formation of areas with downwards ferroelectric polarization; (ii) for films annealed in oxygen under clean conditions (in an ultrahigh vacuum installation) a huge shift of the Pb 5d core levels (by 8-9 eV) towards higher binding energies is attributed to the formation of areas with depleted mobile charge carriers, whose surface density is insufficient to screen the depolarization field. This shift is attenuated progressively with time, as the sample is irradiated with high flux soft X-rays. The formation of these areas with strong internal electric field promotes these films as good candidates for photocatalysis and solar cells, since in the operation of these devices the ability to perform charge separation and to avoid electron-hole recombination is crucial.

The surface enhanced Raman scattering (SERS) effect is explained using the interaction of a polarized molecule with its instantaneous image dipole in a metal surface. This model explains why SERS is obtained mostly on noble metals (Au, Ag), since these metals usually have lower inherent contamination as compared with other more reactive metals; thus, molecules may be found closer to the metal surface. It is shown how stronger SERS amplifications may be obtained using nanostructured surfaces, once the excited molecules are localized in concave sites. The dependence on the fourth power of the incoming radiation electric field is obtained by taking into account the dynamics of adsorption-desorption processes of molecules. The SERS effect is maximal when the excitation frequency is red-shifted with respect to the bulk plasmon resonance. Also, the SERS amplification factor may be dictated by the polarizability of the investigated molecule, alpha, in a much more critical way than just a power law alpha(2) or even alpha(4). By comparing the dipole induced charge density with the amplitudes of plasma waves, the domain of validity of the present theory is derived to be in the low separation regime, where the distance between molecules and metal substrates is below a few nanometres. Some data from the literature are analyzed in the framework of this model, namely the distance, frequency and temperature dependence of the SERS signal, all confirming the validity of the model.

Interfaces formed by gold and copper on single crystal layers of (0 0 1) PbZr0.2Ti0.8O3 (PZT) produced by pulsed laser deposition and exhibiting outwards polarization are analyzed by X-ray photoelectron spectroscopy. The stoichiometry of the layers reproduces reasonably that of the PZT target. The band bending occurring at the interface between PZT and the metals is investigated by analyzing the core level shifts as function on the metal deposition. It is found that for Au/PZT(0 0 1) the gold layer is not continuous and the observed band bendings can be attributed to a Schottky mechanism, whereas for Cu/PZT(0 0 1) the copper layer is continuous; in this latter case, the observed band bendings towards higher energies (lower binding energies) can be attributed to a concomitant bending due to the Schottky effect together with the disappearance of the initial bending due to the outwards polarization of the samples. Metal Pb is observed to segregate only in the case of Cu/PZT(0 0 1), therefore the surface self-reduction might also be connected to the presence of a metal with lower work function, which for larger coverage forms a continuous metal layer, able to provide electrons to the surface. High resolution transmission electron spectroscopy yielded the disappearance of the tetragonal distortion in the case of Cu/PZT(0 0 1), in line with the assumption of disappearance of the polarization-induced band bending. (C) 2015 Elsevier B.V. All rights reserved.

The compensation of the depolarization field in ferroelectric layers requires the presence of a suitable amount of charges able to follow any variation of the ferroelectric polarization. These can be free carriers or charged defects located in the ferroelectric material or free carriers coming from the electrodes. Here we show that a self-doping phenomenon occurs in epitaxial, tetragonal ferroelectric films of Pb(Zr0.2Ti0.8)O-3, consisting in generation of point defects (vacancies) acting as donors/acceptors. These are introducing free carriers that partly compensate the depolarization field occurring in the film. It is found that the concentration of the free carriers introduced by selfdoping increases with decreasing the thickness of the ferroelectric layer, reaching values of the order of 10(26) m(-3) for 10 nm thick films. One the other hand, microscopic investigations show that, for thicknesses higher than 50 nm, the 2O/(Ti+Zr+Pb) atomic ratio increases with the thickness of the layers. These results suggest that the ratio between the oxygen and cation vacancies varies with the thickness of the layer in such a way that the net free carrier density is sufficient to efficiently compensate the depolarization field and to preserve the outward direction of the polarization.

The ability of photoelectron spectro-microscopy with sub-micrometer lateral resolution to identify ferroelectric domains by analysis of surface band bendings is demonstrated on lead zirco-titanate PZT(1 1 1) thin films grown by pulsed laser deposition. Conventional synchrotron radiation X-ray photoelectron spectroscopy allowed one to derive the surface composition of the sample and evidenced shifts toward higher binding energy when the sample is subject to intense soft X-ray beam. A basic model is developed which supposes that photogenerated carriers reduce the depolarization field, yielding a lower torque applied to the ferroelectric polarization. As a consequence, the out-of-plane component of the polarization increases. Domain migration during irradiation with soft X-ray is inferred from the relative amplitude of the components with different binding energy. When the flux density of soft X-ray is on the order of 1011 photons/(s mu m(2)), metal Pb clusters are formed at the surface on areas with the out-of-plane component of the polarization pointing outwards only. (C) 2015 Elsevier B.V. All rights reserved.

Monte-Carlo estimations of the integrals of Bose-Einstein distribution function for magnons are performed, by avoiding number of approximations involved in the usual derivation of the Bloch T-3/2 law, describing the dependence of magnetization with temperature in the low temperature regime, where the main mechanism of magnetization decrease is due to spin waves. More precisely: (i) the magnon dispersion law is considered the exact one (depending on the crystal structure) and not the quadratic approximation epsilon(k) alpha k(2); (ii) the integrals are performed over the first Brillouin zone and the limit of the integral is not extended to infinity; (iii) the dimensionality of the system is taken into account: 1D, 2D and 3D systems are considered; (iv) finite size magnetic systems are treated by rigorous summation of the Bose-Einstein distribution function, without using the continuous limit. The results can be summarized as follows: (a) Infinite three-dimensional (3D) systems exhibit deviations from the Bloch T-3/2 law, namely the deviation from zero Kelvin magnetization vertical bar Delta M vertical bar/M(0) behaves as T-gamma, where gamma is sensibly (by some 10 %) larger than 3/2 and, also, depends on the crystal structure considered. (b) Finite 3D systems exhibit more drastic deviation from the Bloch law, in that the gamma exponent deviates seriously from 3/2, going up to 2.5 for small systems of about 1,000 atoms. (d) Finite 2D systems also show serious deviations from the Bloch-like T law. As described a few years ago [C.M. Teodorescu, Surf. Sci. 601, 4292 (2007)], finite temperature magnetization may be considered only in finite size 2D systems. Several recent examples from literature are analyzed in the framework of the actual theoretical results. It is shown that M(T) analysis in the low temperature regime allows one to extract the average nanoparticle size of the magnetic moieties, and as well the exchange interaction and average spin quantum number.

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.

X-ray photoelectron spectroscopy (XPS) analyses of lead zirco-titanate Pb(Zr,Ti)O-3(001) single crystal thin layers as a function of the time spent between sample preparation by pulsed laser deposition and introduction in to a ultrahigh vacuum revealed the fact that freshly prepared samples showed a shift of the C 1s towards a higher binding energy, together with shifts of core levels originating from the substrate (particularly Ti 2p and O 1s) towards a lower binding energy. This behaviour is explained by considering that the molecules of contaminants (fatty acids, alcohols, esters) are adsorbed preferentially on areas exhibiting outwards polarization P(+). Thus, photoelectrons originating from contaminants will have larger binding energies because of the charge state of the P(+) areas, whereas the substrate XPS signals from these P(+) areas are attenuated by the contaminants, with the consequence of a prevalence of XPS substrate signals originating from the P(-) areas, shifted towards lower binding energies. Piezoresponse force microscopy confirmed the assumptions derived from XPS results and suggests the existence of an interplay between the adsorption of contaminants and the surface polarization state.

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.

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.

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.

The interplay between magnetic properties and structure and interdifussion at interfaces is analyzed mainly by surface science methods and by core level spectroscopies (based on X-ray absorption XAS and X-ray photoelectron spectroscopy XPS) on model systems implying deposition of magnetic metals (Fe, Co, Sm) on usual semiconductors (Si, GaAs, InAs). The Chapters begins with a review of the core level spectroscopies and of derived techniques, such as X-ray photoelectron diffraction (XPD) from XPS and X-ray magnetic circular dichroism (XMCD) from XAS, together with a brief description of other surface science techniques employed, such as low energy electron diffraction (LEED), reflection high energy electron diffraction (RHEED), magneto-optical Kerr effect (MOKE), and with some basics of the molecular beam epitaxy (MBE) method. The examples are organized in pairs, namely one analyzes comparatively (i) interfaces formed by Fe or by Sm on Si(001), (ii) by Fe on GaAs(001) and on InAs(001), (iii) and by Co on bare GaAs(011) and on GaAs(011) passivated with Sb, in order to outline how small changes of the nature of the metal deposited, of the substrate (though identical from the chemical point of view) and of its initial state may result in strong deviations concerning both the quality of structures obtained and their magnetic properties. For instance, it is shown that Sb/Si(001) yields better properties than Fe/Si(001), Fe/InAs(001) exhibits lower reactivity and enhanced Fe magnetic moments than Fe/GaAs(001), and that passivation with antimony of GaAs(011) substrates yields to a reduced As out-diffusion into the metal layer, yielding lower tetragonal distortion and enhanced Co magnetic moments.

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.

Surface- and bulk-phosphated ceria catalysts were prepared and studied in propane oxidative dehydrogenation (ODH) at 823 and 873K. The catalysts were characterized by N2 adsorption at 77K, XRD, TEM, and diffuse reflectance IR Fourier transform (DRIFT), Raman, X-ray photoelectron (XPS), and energy dispersive X-ray (EDX) spectroscopies. Both series of catalysts presented an increase in the ODH selectivity with respect to pure ceria mainly at the expense of total oxidation selectivity. Thus, the selectivity to propene was approximately 74% with surface-phosphated catalysts and 62% with bulk-phosphated catalysts. For the surface-phosphated samples, P is confined to the surface and subsurface regions of the ceria particles, whereas P is also dispersed in the bulk of the oxide in the bulk-phosphated samples. Finally, all the characterization techniques led us to the conclusion that Ce4+ cations that interact with P are responsible for the observed increase in the ODH.

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 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.

The surface structure, interface reactivity, electron configuration and magnetic properties of Sm layers deposited on Si(0 0 1) at various temperatures are investigated by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS) and magneto-optical Kerr effect (MOKE). It is found that metal Sm is present on samples prepared at low temperature, with an interface layer containing SmSi2 and Sm4Si3. When samples are prepared at high temperature, much less metal Sm is found, with an increasing amount of SmSi2. Room temperature ferromagnetism is observed for all prepared layers, with a decrease of the saturation magnetization when samples are prepared at high temperature. It is found that ferromagnetism implies mostly a compound with approximate stoichiometry Sm4Si3. Also, the decrease in the intensity of the XAS 2p(3/2) -> 3d white lines with the corresponding increasing amount of SmSi2 may be explained by assuming a higher occupancy of Sm 5d orbitals (5d(2) configuration), most probably due to hybridation effects. (C) 2012 Elsevier B. V. All rights reserved.

Ferromagnetic FexGe1-x with x = 2%-9% are obtained by Fe deposition onto Ge(001) at high temperatures (500 degrees C). Low energy electron diffraction (LEED) investigation evidenced the preservation of the (1 x 1) surface structure of Ge(001) with Fe deposition. X-ray photoelectron spectroscopy (XPS) at Ge 3d and Fe 2p core levels evidenced strong Fe diffusion into the Ge substrate and formation of Ge-rich compounds, from FeGe3 to approximately FeGe2, depending on the amount of Fe deposited. Room temperature magneto-optical Kerr effect (MOKE) evidenced ferromagnetic ordering at room temperature, with about 0.1 Bohr magnetons per Fe atom, and also a clear uniaxial magnetic anisotropy with the in-plane [110] easy magnetization axis. This compound is a good candidate for promising applications in the field of semiconductor spintronics.

Iron layers are grown on GaAs(001) single crystal wavers by magnetron sputtering and characterized by magneto-optical Kerr effect (MOKE) and X-ray photoelectron spectroscopy (XPS). It is found that all deposited layers, starting with 2 nm thickness, are ferromagnetic at room temperature with a relatively high coercitive field (500 to 750 Oe). The average Fe magnetic moment is larger for the thinnest Fe film deposited, of about 0.52 Bohr magnetons per Fe atom. The average Fe magnetic moment decreases to 0.26 Bohr magnetons, then to 0.17 Bohr magnetons for 4 and 8 nm, resepctively. XPS evidenced that the outermost Fe layers are oxidized; however, the thinnest Fe film presented the lower oxidation state. We may connect this reaction with Fe-As bonds, resulting in a nonferromagnetic interface compound. Indeed, XPS depth profiling of the 8 nm sample evidenced the formation of a very thin (about 1.4 nm) Fe metal layer immediately at the interface with GaAs. In this layer, Fe may reach an atomic magnetic moment as high as 1 Bohr magneton.

Phenylboronic-acid-modified nanoparticles (NPs) are attracting considerable attention for biological and biomedical applications. We describe here a convenient and general protocol for attaching multiple copies of para-substituted phenylboronic acid moieties onto either iron-oxide-, silica-or diamond-derived NPs. The boronic acid fiinctionalized NPs are all fabricated by first modifying the surface of each particle type with 4-azidobenzoic ester functions. These azide-terminated nanostructures were then reacted with 4-[1-ozo-4-pentyn-1-yl) amino]phenylboronic acid units via a Cu(I) catalyzed Huisgen cycloaddition to furnish, conveniently, the corresponding boronic-acid modified NPs (or "borono-lectins") targeted in this work. The potential of these novel "borono-lectins" as antiviral inhibitors was investigated against the Hepatitis C virus (HCV) exploiting a bioassay that measures the potential of drugs to interfere with the ability of cell-culture-derived JFH1 virus particles to infect healthy hepatocytes. As far as we are aware, this is the first report that describes NP-derived viral entry inhibitors and thus serves as a "proof-of-concept" study. The novel viral entry activity demonstrated, and the fact that the described boronic-acid-functionalized NPs all display much reduced cellular toxicities compared with alternate NPs, sets the stage for their further investigation. The data supports that NP-derived borono-lectins should be pursued as a potential therapeutic strategy for blocking viral entry of HCV.

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.

Ce 3d X-ray photoelectron spectroscopy (XPS) spectra is characterized by the presence of "shake-up" and "shake-down" satellites, which complicate the analysis of the XPS data and especially the identification of different ionization states. The present paper proposes a new model for interpreting the 3d XPS lines of cerium oxide (CeO2). This model supposes 6 pairs of doublets with spin-orbit splitting, three corresponding of trivalent cerium and three corresponding of tetravalent cerium. The three components used for each ionization state correspond to the "shake-down" process, to the "parent" (Koopman) line, and to the "shake-up" line, in order of increasing binding energy. From the time dependence of Ce 3d and C 1s XPS spectra, a model for the contamination process is derived and also the length of the alkyl chains of the hydrocarbons may be estimated. The present analysis allowed a more accurate computation of the Ce 3d atomic sensitivity factor (ASF), in accord with the values found for other rare earths elements.

A new green method for the synthesis of reduced graphene oxide-gold nanoparticle (rGO-AuNP) hybrids in aqueous solution that exploits the ability of ascorbic acid (AA) to operate as an effective dual agent for both graphene oxide (GO) and gold ion reduction is reported. Through careful investigation of the production of rGO-AuNP hybrids stabilized with polyvinylpyrrolidone (PVP), several versatile routes were devised with the aim of controlling the size, shape and distribution of AuNPs anchored onto the graphene sheets as well as the GO reduction. Particularly, when rGO is used as a platform for Au ion nucleation, a relative sparse distribution of AuNPs of size ranging from 20 nm to 50 nm is noticed. In contrast, when gold ions are added to the solution prior to any GO reduction, the density of large AuNPs is rather low relative to the uniformly packed small sized AuNPs (3-12 nm). The progress of GO reduction is explained by considering the contribution of the catalytic activity of AuNPs, besides the reducing activity of AA. Finally, a plausible mechanism for the nucleation and distribution of AuNPs onto the graphenic surface is assumed, highlighting the significance of oxygen moieties. The green method developed here is promising for the fabrication of gold-graphene nanocomposites with tunable surface "decoration", suitable for surface-enhanced Raman spectroscopy (SERS).

Manganese is deposited onto GaAs(001) substrates in high vacuum conditions (10(-7) hPa), with substrates held at 300 degrees C. It is shown that this procedure yields to the diffusion of magnanese into gallium arsenide and the formation of a layer which exhibits room temperature ferromagnetism, with highly diluted Mn (below 1 atomic percent). X-ray absorption fine structure determinations at the Mn and Ga K-edges evidenced that Mn is not placed into substitutional Ga sites in GaAs. Most probably, Mn forms MnO clusters with rocksalt local structure. These clusters are the origin of the detected ferromagnetism.

Samarium is deposited on Si(001) at various temperatures (room temperature to 400 A degrees C), and the surface structure, interface reactivity, electron configuration, and magnetic properties are investigated by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and magneto-optical Kerr effect (MOKE), respectively. It is found that metal Sm is present on samples prepared at room temperature with an interface layer containing mostly Sm2+ and a lower amount of Sm3+. When samples are prepared at high temperature, much less Sm-0 is found with an increasing amount of Sm2+. Freshly prepared Sm-0 and SmSi2 layers react strongly with oxygen from the residual gas, promoting formation of Sm2O3 at the expense of both metal Sm and SmSi2. Room temperature ferromagnetism is observed for all prepared layers with a decrease of the saturation magnetisation when samples are prepared at high temperature. It is found that ferromagnetism implies mostly Sm3+ and Sm metal. In addition to these findings, this work proposes a new assignment of the Sm 3d chemically shifted components. Also, a noticeable variation of the XPS Sm 3d spin-orbit splitting is found as a function of the Sm ionization state.

The band (or Stoner) ferromagnetism in systems exhibiting a linear density of states, such as a graphene sheet, where the density of states g(e) is proportional to e, is investigated as function of temperature. The calculations are performed by neglecting spin-wave excitations and some arguments are presented for this approximation. It is found that the occurrence of ferromagnetism becomes easier at finite temperature than in the low temperature limit, especially for systems with low values of carrier density. An almost linear dependence of the magnetization on temperature is predicted; the temperature of vanishing magnetization is linear with the value of the equilibrium Fermi energy, irrespective of the value of the interaction (Hubbard) parameter. Also, for low values of the Hubbard energy an increase in the average value of the polarization with the temperature is predicted in the range of low temperatures. The most important application of such systems consists of control over the onset of magnetization by the charge density (the value of the Fermi energy).

High quality pulsed laser deposited lead zirconate titanate (PZT) films are obtained by pulsed laser deposition on SrRuO3(111) single crystal layers and characterized by X-ray photoelectron spectroscopy (XPS), to determine the surface composition. It is found that a minor amount of Pb forms PbO2 at the surface and also some Pb is included into the contamination layer, in form of a Pb(CO3)2 layer of about 1?nm thickness, occupying about one quarter of the PZT surface. The stoichiometry of the outermost 45?nm layers yielded as PbZr0.25Ti0.80O2.5, which suggest the formation of an oxygen depleted, Brownmillerite-like layer at the surface, of at least 5?nm thickness.

This study presents a correlated study of structural, reactivity, and magnetic properties of ultrathin Fe layers grown on Si(001) by molecular beam epitaxy in ultrahigh vacuum. The interface reactivity is characterized by Auger electron spectroscopy. The surface structure is characterized by low electron energy diffraction with spot profile analysis. The magnetism of the synthesized layers is investigated by magneto-optical Kerr effect. At room temperature, metal Fe layers with poor long-range order are synthesized; these layers are ferromagnetic with an extremely low coercitive field (below 1 Oe). The reactivity with Si is low in this case, with formation of an interface layer of about 8 angstrom Fe equivalent thickness with about 7 at.% Si diffused. Samples synthesized at higher temperatures (500 degrees C) exhibit better long-range order, though the Fe reactivity with Si is higher and leads to the formation of an interface compound whose approximate stoichiometry is very close to Fe(3)Si. Once this compound is formed (for an equivalent Fe thickness of about 14 monolayers), disordered metal Fe islands are developing with subsequent Fe deposition, which contain also about 8 at.% Si diffused. These structures exhibit a much lower ferrimagnetism, with saturation magnetization about one order of magnitude lower than in the case of the room temperature synthesis. In this case of high temperature synthesis, two phases are observed, a ferrimagnetic one and a superparamagnetic one.

Structural aspects and atomic intermixing processes in Be/W bilayers deposited on Si(0 0 1) substrates with Fe buffer layers enriched in the (57)Fe Mossbauer isotope have been studied via atomic force microscopy, grazing incidence X-ray diffractometry, X-ray reflectometry, X-ray photoelectron spectroscopy and conversion electron Mossbauer spectroscopy. The mentioned investigations allowed a full sequential characterization of the involved interfaces. Various ionic configurations appeared for Fe or W, while an amorphous state was observed in the case of Be. It has been proven that the Be layer has a negative influence on the roughness of the whole structure, which however presents an oxidation gradient from more oxidized elements at the surface towards more reduced elements in deeper layers. A strong diffusion of the W atoms inside the Be layer, induced by the deposition method, as well as of the Fe atoms inside the Be layer, induced by thermal annealing, has been evidenced. (C) 2011 Elsevier B.V. All rights reserved.

TiO2:Fe thin films prepared by pulsed laser deposition exhibit in some case light dependent saturation magnetization, as determined from Kerr magnetometry measurements performed in dark or by illuminating the sample. This phenomenon is studied in correlation with local atomic structure investigated by extended X-ray absorption fine structure, composition and chemical state analyzed by X-ray photoelectron spectroscopy and by X-ray absorption near-edge structure. It is found that light-controllable magnetism is a property of a mixture of Fe and oxidized Fe clusters embedded in the anatase TiO2 matrix.

This work presents recent studies concerning the synthesis of ultrathin ferromagnetic Fe layers on Si(001) and the correlated follow-up measurement of their structural properties, interface reactivity, and magnetism. This study is undertaken as function of the amount of Fe deposited and of substrate temperature. The interface reactivity is characterized by Auger electron spectroscopy. The surface structure is characterized by low electron energy diffraction (LEED). The local order of Fe atoms is investigated by X-ray absorption fine structure (XAFS) and the magnetism by magneto-optical Kerr effect (MOKE). A general trend established is that a higher deposition temperature stabilizes a better surface ordering, but also enhances Fe and Si interdiffusion and therefore decreases the magnetism. A surprising effect obtained by Fe deposition at room temperature is that, despite the rapid disappearance of the long range order with Fe deposition (no LEED pattern is observed for Fe coverage exceeding one monolayer), the material exhibits a significant uniaxial in-plane magnetic anisotropy. When the deposition is performed at high temperature (500 degrees C), a weak ferromagnetism is still observed, with saturation magnetization of about 10 % of the value obtained for room temperature deposition. The combined MOKE and EXAFS studies allowed inferring consistent values for the range of Fe thicknesses where the reaction takes place and the main properties of the distinct formed layers.

Amorphous titania thin films with increasing Fe content have been prepared by RF magnetron sputtering. X-ray absorption spectroscopy revealed modifications of both local structures/environment of the Ti and Fe atoms, with formation of phases containing amorphous material and a magnetite-like phase. The temperature dependence of the electrical conductivity of the films was investigated for temperatures higher than half of the Debye temperature (T > 391 K). It was found that the electrical conductivity in the amorphous Fe/TiO2 films obeys the Meyer-Neldel rule. The origin of this behavior is explained on the basis of the multiphonon-assisted hopping model.

Single molecule magnets are of great interest due to a multitude of potential applications for some of which thin films are required. Traditional physical vapor deposition techniques are not suitable for the deposition of these fragile materials with low decomposition temperatures. Matrix Assisted Pulsed Laser Evaporation technique has been employed for the growth of thin films of the single molecule magnet Mn-12(Propionate) on Si and glass substrates. In this paper we report on the appropriate growth conditions and also the morphology, chemical composition and magnetic behavior of the films. Continuous Mn-12(Propionate) films with properties similar to bulk materials have been obtained. (c) 2011 Elsevier B.V. All rights reserved.

Different hybrid structures were obtained by coating magnetic nanoparticles of perovskite type manganite at optimal doping (La0.67Sr0.33MnO3, LSMO) with different quantities of polypyrrole (PPy). The amorphous layer of polypyrrole surrounding the crystalline magnetic core was observed by high resolution transmission electron microscopy (HRTEM) and analyzed by using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements in near edge structure (XANES) techniques. By analyzing the magnetic behavior of the samples one can observe that the surface modification of magnetic nanoparticles by PPy results in an increase in the saturation magnetization of the composites. The process is ascribed to paired electrons transferred from the delocalized p states of the PPy into the outer disordered layers of the manganite. The analysis of pre-edge peak of the Mn K-edge XANES spectra in the case of PPy coated LSMO nanoparticles indicates that the charge transfer between polymer and nanoparticles is (directed) going to missing or distorted oxygen positions, hence increasing the 3d electrons' mobility and orbital hybridization between the neighboring manganese ion. As a consequence, within the surface layers of LSMO nanoparticles, both energy bands disrupted the structure, and the double exchange process between Mn ions was reestablished determining the saturation magnetizations and pre-edge features increase, respectively. (C) 2012 American Institute of Physics. [doi:10.1063/1.3686662]

Transmission electron microscopy and X-ray photoelectron spectroscopy analyses are performed to investigate Ge nanoparticles embedded in an amorphous SiO2 matrix. GeSiO thin films are prepared by two methods, sol-gel and radio frequency magnetron sputtering. After the deposition, the sol-gel films are annealed in either N-2 (at 1 atm and 800 A degrees C) or H-2 (at 2 atm and 500 A degrees C), and the sputtered films in H-2 (at 2 atm and 500 A degrees C), to allow Ge segregation. Amorphous Ge-rich nanoparticles (3-7 nm size) are observed in sol-gel films. Crystalline Ge nanoparticles in the high pressure tetragonal phase (10-50 nm size) are identified in the sputtered films. The size of the nanoparticles increases with Ge concentration in the volume of the film. At the film surface, the Ge concentration is much larger that in the volume for both sol-gel and sputtered films. At the same time, at the film surface, only oxidized Ge is observed.

Clean Si(001) single crystal surfaces provided different surface reconstructions: p(1 x 2) and c(n x 2) (n = 4, 6) at room temperature. The in situ oxidation of these surfaces was followed by Auger electron spectroscopy and by X-ray photoelectron spectroscopy. It is found that, in similar ultrahigh vacuum conditions, much faster contamination (about 500 times) occurs when the samples are investigated by AES than by XPS, owing to the interaction of the electron beam with the sample surface. With the sample subject to the AES investigation, the contamination occurs by forming >Si2C=O complexes based on the Si dimers. During XPS, reaction with water molecules from the residual gas should also be taken into account.

Clean Si(001) single crystal surfaces are obtained by cycles of long (30 mins.) annealings in ultrahigh vacuum (fairly below 1 x 10(-9) mbar). The surface reconstruction is investigated by low energy electron diffraction (LEED). This paper reports, in addition to the well-known p(2 x 1) reconstruction, the first observation of c(4 x 2) at room temperature and also the completely new c(6 x 2) reconstruction. The in situ oxidation of these surfaces was investigated by Auger electron spectroscopy (AES) and by X-ray photoelectron spectroscopy (XPS). It is found that, in similar ultrahigh vacuum conditions (6 x 10(-10) mbar), much faster contamination (about 500 times) occurs when the samples are investigated by AES than by XPS, owing mainly to the interaction of the electron beam with the sample surface. Also, much gentler surface bombardment with electrons, such as in LEED, still enhances sample oxidation. Therefore, XPS proves to be a much more convenient technique for non-destructive assessment of the surface composition. When the surface is subjected to the AES investigation, we found that the contamination occurs by forming >Si2C=O complexes based on the Si dimers.

Pure and europium (Eu3+) doped cerium dioxide (CeO2) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of similar to 250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce4+ sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 degrees C, a remarkable high surface area of similar to 120 m(2) g (-1) is preserved whereas an enrichment of the surface Ce4+ relative to Ce3+ ions and relative strong europium emission with a lifetime of similar to 1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.

Chromium-doped titanium oxide thin films were investigated in the as-deposited state and after thermal treatment (723 K for 3 h in air). X-ray diffraction data revealed an improvement in film crystallinity induced by the thermal treatment. Extended X-ray absorption fine structure data revealed similar atomic neighboring around Cr atoms in both as-deposited and annealed samples. A lattice contraction of similar to 2% is observed in the annealed samples. The 67% enhancement of the amplitude of the Cr 1 s X-ray absorption fine structure pre-edge peak after thermal treatment, which is a sign of "dipole-forbidden" 1 s -> 3 d transitions, suggests strong alteration in the number of Cr 3 d vacancies, in spite of similar Cr local environment in the two kinds of investigated samples. We discuss here the Cr+ -> Cr4+ and Cr2+ -> Cr6+ changes induced by thermal treatment, and/or the evolution in local structures without inversion center. Refractive index dispersion spectra in the visible wavelength domain allowed us to compute the values of the dispersion energy, the single-oscillator energy and the coordination number of Ti atoms in both as-deposited and annealed samples. (C) 2011 Elsevier B. V. All rights reserved.

The etherification of biomass-based alcohols with various linear alpha-olefins under solvent-free conditions was followed in a space- and time-resolved manner on 9 mu m large H-Beta zeolite crystals by confocal fluorescence microscopy. This allowed us to visualize the interaction with the substrate and distribution of the coke products into the catalyst at the level of an individual zeolite crystal during the etherification process. The spectroscopic information obtained on the micrometer-scale zeolite was in line with the results obtained with bulk characterization techniques and further confirmed by the catalytic results obtained both for micrometer-scale and nanoscale zeolites. This allowed us to explain the influence of the substrate type (glycerol, glycols, and alkenes) and zeolite properties (Si/Al ratio and particle size) on the etherification activity. The etherification of the biomass-based alcohols takes place mainly on the external surface of the zeolite particles. The gradual blockage of the external surface of the zeolite results in a partial or total loss of etherification activity. The deactivation could be attributed to olefin oligomerization. The high conversions obtained in the etherification of 1,2-propylene glycol with long linear alkenes (up to 80%) and the pronounced deactivation of the zeolite observed in the etherification of glycerol with long linear alkenes (max. 20% conversion) were explained by the spectroscopic measurements and is due to differences in the adsorption, i.e., in the center of the zeolite particle for glycerol and on the external surface in the case of glycols.

Nanoparticles of iron oxide embedded in C(60) matrices are synthesized by co-evaporation of iron and C(60)-fullerene, and analyzed using X-ray photoelectron spectroscopy, X-ray absorption near-edge structure spectroscopy and MOKE magnetometry. C(60) molecules in the neighborhood of the iron oxide nanoclusters transfer charge to the oxide, and the charge deficit fully delocalizes onto the fullerene molecules. The composition of the nanoclusters of iron oxide is similar to both hematite and magnetite, in comparable proportions. One analyzes the amplitude of the pre-edge XANES peak, yielding the average ionization state of absorbing Fe atoms, which is confirmed by the simulations of XANES spectra.

Cobalt-doped vanadium oxide thin layers prepared by pulsed laser ablation are investigated from the following points of view: (1) the chemical states by X-ray photoelectron spectroscopy (XPS), (2) the local atomic order by X-ray absorption fine structure at both vanadium and cobalt K-edges, (3) the morphology of the films by atomic force microscopy (AFM) and (4) the magnetic properties by magneto-optical Kerr effect (MOKE). The chemical composition of the host matrix was found to be close to VO2 at the sample surface, with V2O3 in the bulk. Co ions are found near the surface in high ionisation states Co4+ (for the samples synthesised in a high vacuum condition, denoted by VO1), or with Co(4-)+ (for the samples synthesised in an oxygen atmosphere, denoted by VO2), whereas in the bulk, Co1.5+ is obtained for VO1 and Co2+ is obtained for VO2. The AFM revealed nanoparticles with sizes 10-25 nm for VO1 samples, whereas a few bigger nanoparticles are observed for VO2 samples. The VO1 samples presented high coercitive fields with a relatively low saturation magnetisation at room temperature, superposed with a superparamagnetic component attributed to the observed nanoparticles, whereas the VO2 samples presented double-loop hysteresis curves, indicating the co-existence of two kinds of magnetic moieties with antiparallel coupling at zero applied field. The proposed two magnetic phases are Co-doped V2O3 and VO2.

Unimodal porous system (denoted as SnTf-MCM-41) and bimodal porosity (denoted as SnTf-UVM-7) were prepared in a two-step synthesis. The triflic acid was incorporated into previously synthesized Sn-containing porous silicas. Chemical analysis was carried out by electron probe microanalysis (EPMA), textural properties were determined by transmission electron microscopy (TEM) and from nitrogen adsorption-desorption isotherms (77 K), while structural characterization by X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) measurements. The structural characterization provided evidences on the direct interaction of triflate with incorporated tin species. The acidity of these catalysts was determined from the ammonia chemisorption measurements. The catalysts have been tested for transesterification of sunflower oil under both microwave and ultrasound activation. These experiments showed a direct reaction between the acidity of the catalysts and catalytic performances. No leaching of the triflate species or catalyst deactivation have been detected over several runs.

The Pd-TPPTS complex (TPPTS - trisodium salt of 3,3',3 ''-phosphanetriyl benzenesulfonic acid) and PdCl42- salt heterogenised onto Zn2AlNO3 layered double hydroxide (LDH) using an ion-exchange procedure, have been shown to be efficient green catalysts in the cycloisomerisation reaction of acetylenic carboxylic acids to the corresponding 5-membered heterocycles.

Electron states at the SiO2/4H-SiC interface have been investigated using capacitor structures and especially, the influence of excess nitrogen, introduced by ion implantation, at the interface is studied in detail. Implanted and nonimplanted n-type samples with an interfacial concentration of nitrogen of similar to 10(19) cm(-3) and 10(16) cm(-3), respectively, were analyzed by capacitance-voltage (C-V) measurements, performed at different temperatures and probe frequencies, and thermal dielectric relaxation current (TDRC) measurements performed in the temperature range of 35-295 K. Three main categories of electron states are disclosed, true interface states (D-it), fast near interface states (NIToxfast) and slow near interface states (NIToxslow). The density versus energy distributions of D-it and NIToxfast have been deduced from the TDRC data and they are shown to give a close quantitative agreement with the shape and frequency dependence of the C-V curves. Further, the amount of NIToxslow extracted from TDRC is demonstrated to be responsible for the parallel shifts and hysterezis effects occurring in the C-V characteristics. All three categories of electron states are reduced in concentration in the implanted samples. This holds particularly for NIToxfast with a peak at similar to 0.1 eV below the conduction band edge of 4H-SiC that is suppressed by at least two orders of magnitude relative to the nonimplanted samples. The decrease for D-it is also substantial (a factor of similar to 10) while the loss for NIToxslow is considerably smaller (only similar to 30%). The results provide firm evidence that NIToxfast and NIToxslow do not originate from the same kind of defect center. (C) 2010 American Institute of Physics. [doi:10.1063/1.3457906]

The ability of a sol-gel route for the synthesis of cobalt doped ZnO (Zn 1-xCoxO, x = 0.04-0.11) films grown on Si (100) and glass substrates is investigated. A homogeneous and stable Zn (1-x) CoxO sol was prepared by dissolving zinc nitrate hexahydrate and cobalt acetate tetrahydrate in a PVP (polyvinylpyrrolidone) solution, followed by annealing at 800 degrees C. Local structure studies of the Zn1-xCoxO thin films by XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure) proved the co-existence of a few amount of small metal cobalt aggregates with Co in non-stoichiometric ConOm aggregates, with n > m, and m similar to 4. Low temperature magneto-optical Kerr effect (Faraday rotation) measurements of the magnetization versus field give a direct proof of a superparamagnetic behavior of the magnetic aggregates and allowed an estimate of the number of magnetically active atoms in Co aggregates, which is close to the number of Co excess atoms inferred from XANES and EXAFS considerations: n - m similar to 3 atoms per aggregate. To this main superparamagnetic phase, a weak ferromagnetic phase with coercitive field of similar to 50 Oe is superimposed, most probably due to metal cobalt nanoclusters.

ZnO:Co thin films are prepared by electrochemical deposition at different overpotentials and investigated by scanning electron microscopy, optical spectroscopy, and cathodoluminescence, X-ray photoelectron spectroscopy and Kerr magnetometry (MOKE). An increase of structural disorder and crystallite reorientation are observed for cobalt-doped samples. MOKE magnetometry revealed room-temperature ferromagnetic behavior only for ZnO: Co deposited at -850 mV. These are the samples with the lower cobalt content and lowest structural perturbation of the ZnO matrix by cobalt. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

A new analytical approximation of the diffraction peak size profile due to the lognormal distribution of spherical crystallites is derived. In comparison with the existing approximation constructed with the condition of conserving the volume-averaged column length of the exact profile [Popa & Balzar (2002). J. Appl. Cryst. 35, 338-346], the new approximation conserves both volume- and area-averaged column lengths. Moreover, it is a better approximation for large distribution dispersions. Like the old approximation, the present one is appropriate for implementation in the whole powder pattern fitting codes, Rietveld included.

Spectral emission of a Xenon discharge in the presence of NaCl powder is strongly modified and dominated by the XeCl excimer band at 308 nm. Materials introduced in gas electrical discharges interact with the reactive species produced in the plasma: electrons, ions and metastable atoms. In this paper, the influence of ions and metastable atoms of a capacitive RF Xenon discharge plasma (20W, 30MHz) 5 Torr on the structure of a NaCl powder introduced in the discharge has been investigated.

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.

In a previous paper [C.M. Teodorescu and G.A. Lungu, J. Optoelectron. Adv, Mater. 10, 3058 (2008)] we studied the zero temperature problem of the occurence of band ferromagnetism and of the derivation of the Stoner criterion for systems of variable dimensionality: 1D, 2D, 3D. The dimensionality of the system is reflected by a different shape of the density of states. For ideal 2D systems, the density of states is a constant and this seems to be the simplest case to be modelled. In this paper we integrate to this simplest model of constant density of states the influence of temperature, in order to analyse temperature-dependent ferromagnetism in two-dimensional systems, such as magnetic surfaces. Some surprising results are obtained, namely: (i) in contrast to the common belief, in this case the influence of the temperature is to favour, not to inhibit ferromagnetism, i.e. in some conditions ferromagnetism may be obtained at finite temperature. even for systems where the zero temperature Stoner criterion is not satisfied; (ii) for a careful choice of the ratio between the Hubbard energy parameter U and the equilibrium zero-temperature Fermi level value epsilon(mu) (0), systems nonmagnetic at low temperature which become magnetic at higher temperature may be possible. A short review of the experimental data which may be interpreted within the present formalism is also given.

Iron local environment was investigated by EXAFS in Fe- and (Fe, Eu)-doped TiO(2) photocatalysts, prepared by hydrothermal and high-energy ball milling (HEBM) routes. In the case of the hydrothermal samples, the substitution of Ti(4+) by Fe(3+) ions was evidenced. For the samples prepared by HEBM, the iron environment corresponds to mixed metallic and oxidized (FeO, alpha-Fe(2)O(3)) configurations, without a clear evidence of iron incorporation into the TiO(2) lattice. This could be related to the catalyst contamination by iron microparticles detached from the balls during milling process.

ZnO:Co thin Films are prepared by electrochemical deposition at different overpotentials and investigated by scanning electron microscopy, X-ray photoelectron spectroscopy and Kerr magnetometry (MOKE). Increse of structural disorder and crystallite re-orientation are observed for cobalt doped samples (especially for those obtained at - 750 and at - 800 mV overpotentials). MOKE magnetometry revealed room temperature ferromagnetic behaviour only for ZnO:Co deposited at - 850 mV. These are the samples with the less cobalt content and lowest structural perturbation of the ZnO matrix by cobalt.

Various approaches have been reported during the last decade to enhance the photo-catalytic and super-hydrophilic characteristics of the intrinsic TiO2 materials. Results on the photo-degradation activity of RF-sputtered nitrogen-doped titania thin films are presented here with respect to two environmental pollutants in gas- and liquid phases, as a function of dopant concentration. This study was accomplished by monitoring the time dependence of pollutant concentration in contact with the films, both under UV and solar light illumination. The synergic effects of surface morphology, crystalline and electronic structure of the materials are discussed in relation with the observed experimental facts. The results presented here show a close correlation between the oxidative power of the films and their previously reported wettability features. (C) 2009 Elsevier B.V. All rights reserved.

TiO2:Fe thin films prepared by pulsed laser deposition exhibit in some case light dependent saturation magnetization, as determined from Kerr magnetometry measurements performed in dark or by illuminating the sample. This phenomenon is Studied in correlation with local atomic Structure investigated by extended X-ray absorption fine structure, composition and chemical state analyzed by X-ray photoelectron spectroscopy and by Xray absorption near-edge structure. It is found that light-controllable magnetism is a property of a mixture of Fe and oxidized Fe clusters embedded in the anatase TiO2 matrix.

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.

Fe(III)-doped TiO2 aerogels are prepared by acid catalyzed sol-gel method followed by supercritical drying, and then heat treatment. Raman spectra together with X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns of the iron-doped TiO2 aerogel samples revealed the existence of both anatase and brookite crystalline phases. It was found that the brookite phase formation is favored by the increase of the iron content in the dried samples. XRD measurements show that the lattice constant c of anatase phase decreases with the dopant addition, while the value of a remains essentially unchanged. The microstructure of the investigated samples is relatively compact with small mesopores as revealed from transmission electron microscopy (TEM). The most enhanced photocatalytic activity was exhibited by the TiO2 aerogel sample with 1.8 at.% Fe(III) whose apparent rate constant of the salicylic acid photodegradation was found to be of almost six times higher than that of Degussa P25.

Recent experiments evidenced room temperature ferromagnetism in ZnO:Co diluted magnetic semiconductors, however the diluted semiconductor nature and the ferromagnetism strongly depends on the preparation method employed. We have investigated the ability of the sol-gel route for the synthesis of cobalt doped ZnO films grown on Si (100) and glass substrates. A homogeneous and stable Zn (1-x) CoxO sol was prepared by dissolving zinc nitrate hexahydrate and cobalt acetate tetrahydrate in a PVP (polyvinylpyrrolidone) solution, followed by annealing at 800 degrees C. Local structure studies of the Zn1-xCoxO thin films by XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure) proved the co-existence of a few amount of small metal cobalt aggregates with Co in non-stoichiometric ConOm aggregates, with n > m, and m similar to 4. Low temperature (1.5 K) Kerr magnetometry give a direct proof of a superparamagnetic behavior of the magnetic aggregates and allowed an estimate of the number of magnetically active atoms in Co aggregates, which is close to the number of Co excess atoms inferred from XANES and EXAFS considerations: n - m similar to 3 atoms per aggregate. To this main superparamagnetic phase, a weak ferromagnetic phase with coercitive field of similar to 200 Oe is superimposed, most probably due to metal cobalt nanoclusters.

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.

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.

A series of TiO2-ZrO2 aerogels with different ZrO2 contents (3-10 %) were prepared by an acid catalyzed sol-gel method followed by low-temperature supercritical drying and heat treatment. The structure and morphology of mixed aerogels were studied by means of Raman spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), xenon sorption and elemental analysis. XRD spectra refinements show that the calcined TiO2-ZrO2 aerogels consist mainly in anatase phase accompanied by a small fraction of tetragonal ZrO2. The Raman spectra proof that the network of the calcined mixed aerogels mainly preserves an anatase structure similar to that of the calcined TiO2 aerogel. The TEM images reveal that the anatase particles present round shapes with a highly homogeneous size (about 3-8 nm). Areas containing chains of amorphous tetragonal zirconia were also identified by the TEM investigations. The addition of zirconia to titania significantly increased the surface area and stabilized the anatase phase of titania. The best catalytic efficiency for the salicylic acid photodecomposition was obtained for the aerogel with 9.39% zirconia that exhibited an apparent rate constant of about three times higher than that of the pure titania aerogel.

Cobalt-doped vanadium oxide thin layers prepared by pulsed laser ablation are investigated by (i) X-ray photoelectron spectroscopy, (ii) the local atomic order by X-ray absorption near-edge structure (XANES), (iii) the morphology of the films was investigated by atomic force microscopy (AFM), and (iv) magnetic properties were quantified by magneto-optical Kerr effect (MOKE). In most cases, the chemical composition of the host matrix was found to be the vanadium (5+) oxide V2O5 at the sample surface and lower ionization states (+2 and +3) in the bulk. Co ions are found either in high ionization state Co5+ (for samples synthesized in high vacuum condition, denoted by VO1), or with Co in lower ionization states Co4+ (for samples synthesized in a mixture of argon and oxygen atmosphere, denoted by VO2). Consistent information was obtained from chemical shifts from individual core level scans in XPS, compared with existent data in litterature, and the amplitude of the pre-edge peak in XANES, which is a sign of quadrupole 1s -> 3d dipole-forbidden transition and whose amplitude is proportional to the number of 3d vacancies per atom. AFM revealed big particles with sizes > 100 mu m for VO1 samples, whereas smaller nanoparticles with sizes ranging between 20 and 30 mu m were observed for VO2 samples. VO1 samples presented very high coercitive fields with a relatively low saturation magnetisation at room temperature, whereas VO2 samples presented double-loop hysteresis curves, indicating the coexistence of exchange bias between two kinds of magnetic moieties with strong anisotropy.

The Bloch T-3/2 law is obtained for three-dimensional magnons at low temperatures. When decreasing the dimensionality of the magnetic system, the 3/2 exponent is expected to be equal to one for two-dimensional (2D) systems. I present a theoretical sketch of 2D spin wave theory, in which a long magnon wavelength cutoff is introduced, connected to the lateral size of the 2D system investigated. I report a study by X-ray magnetic circular dichroism at the Ni L-edges on the onset of ferromagnetic, order on 1.5 atomic Ni layers deposited on Cu(1 0 0), with spin and orbital moments' dependence with temperature. A linear dependence is found for both spin and orbital moments with the same initial slope. This temperature dependence can be used to probe the size of the 2D magnetic islands, which is particularly useful for embedded 2D objects. (C) 2007 Elsevier B.V. All rights reserved.

Nitrogen doping was proposed recently as a low-cost means to shift the absorption edge of titania towards 450-500 run. Results are reported here on the preparation of nitrogen-doped 250 nm thick TiO2 films on glass substrates by RF magnetron sputtering. The nitrogen content in the films was modified by changing the N-2 partial pressure in the discharge from 0.00 to 0.27 Pa. An additional amount of oxygen was added in the deposition chamber (Po-2 = 0.11 Pa) to compensate for oxygen depletion in the films. Surface composition and structure were derived from XPS and XRD data, respectively. XRD data revealed a mixture of amorphous phase and rutile polymorph in the as-deposited films, while an anatase-rich phase occurs in the samples deposited under N2 pressure of 0.05 and 0.16 Pa. Above 0.16 Pa, a rutile-rich phase is present. Surface wettability was investigated from contact angle data of de-ionized water with solid surface. The films deposited under mid-range N2 pressure in the discharge are super-hydrophilic. The photo-induced super-hydrophilicity decays after 36 h. Film wettability is discussed in terms of the synergic effects of surface roughness (measured by AFM) and rutile-anatase TiO2 phase transition, induced by doping. The TiO2 surface super-hydrophilicity (and catalytic efficiency) are related to beneficial properties of anatase phase (E-g = 3.2 eV), associated with a low recombination rate of charge carriers in the surface. (C) 2007 Elsevier B.V. All rights reserved.

We report here on the characteristics of RF-sputtered 300 nm thick films of TiO2-2xNx prepared on glass substrates at 350 degrees C, by adjusting the N-2:Ar partial pressure ratio in the deposition chamber between 0.00 and 0.33. XRD, XPS, AFM and contact angle data were used to derive film structure, elemental composition and oxidation state of Ti, surface morphology and hydrophilicity, respectively. The band gap was derived from spectral data in the 350-450 nm range. Film structure and composition were changed by adjusting the partial pressure of the reactive gases during sputtering and by post-deposition annealing at 400 degrees C in air, for 90 min. The values of the contact angle of films' surface with de-ionized water and of surface free energy per unit area show that films are super-hydrophilic for high-nitrogen content. Correlations are made between film structure, elemental composition, electronic and wettability properties. (c) 2007 Elsevier B.V. All rights reserved.

The reactive sputtering technique was used to obtain undoped and Fe-doped TiO2 thin films deposited on glass substrates. At 250 degrees C substrate temperature, undoped TiO2 films crystallize in a mixed rutile/anatase phase, while Fe-doped films exhibit the rutile phase only. Presence of Fe3+ ions into the TiO2 lattice is suggested by the intensity variation of forbidden 1s -> 3d transitions between the Ti and Fe K-edges. Ti K-edge EXAFS data are assessed to a mixture of the two kinds of surroundings, a rutile-like crystalline phase, identified also by X-ray diffraction, and a nanosized or amorphous anatase-like surrounding. The local atomic order about Fe atoms is quite different and could be related also to an amorphous phase. The Swanepoel method is used to obtain the dispersion of the refractive index below the interband absorption edge. The dispersion energy, the single-oscillator energy and the coordination number of the Ti atoms are evaluated using the single-oscillator model (Wemple-DiDomenico). (C) 2007 Elsevier B.V. All rights reserved.

The aim of the present work is the investigation of the core-shell Fe@Au nanoparticles obtained by the inverse micelles method. Also hybrid structures between Fe@Au nanoparticles and the well-known conducting polymer polypyrrole (PPY) were obtained and investigated. The properties of the composites were investigated by TEM, HRTEM, X-ray diffraction (XRD), X-ray Photoelectron spectroscopy (XPS) and magnetization measurements. The TEM, HRTEM measurements show that two categories of core-shell nanoparticles with mean diameters of 5 nm and 25 nm, respectively, are formed. The XPS investigations of the core-shell Fe@Au nanoparticles indicate that besides Fe-0 inside the cores, small amounts of Fen,111, located onto the gold surface were also formed during the samples preparation. The magnetization of the investigated nanocomposites measured versus increasing and decreasing magnetic field shows no hysteresis loop, this behavior being consistent with a superparamagnetic behavior. The behavior of the SQUID magnetization vs. temperature under field cooled (FC) and zero field cooled (ZFC) at 0.1 T magnetic field for Fe@Au nanoparticles confirmed the existence of superparamagnetism. The superparamagnetic model was used to fit the experimental magnetization vs. applied magnetic field as it was measured by SQUID up to 5 T. (C) 2007 Elsevier B.V. All rights reserved.

Results are reported on the characterization of 200-250 nm thick TiO(x) transparent films grown at temperatures of 150 degrees C and 500 degrees C by reactive pulsed-laser ablation of a metallic Ti target under 0.13-13.3 Pa oxygen atmosphere. Film structure and composition were investigated by X-ray diffraction and X-ray photoelectron spectroscopy. The samples deposited at 150 degrees C reveal a mixture of amorphous TiO(2) and Ti(2)O(3), irrespective of oxygen pressure. The O:Ti atomic ratio fluctuates in their surface around 1.83 for oxygen pressure ranging between 0.13 Pa and 2.66 Pa. The samples deposited at 500 degrees C feature different characteristics, as a function of oxygen pressure: (a) below 2.66 Pa of O(2) the films contain a mixture of significant amount of anatase and rutile TiO(2) phases, along with titanium suboxides; (b) above this threshold, the rutile phase vanishes, the anatase TiO(2) phase remaining dominant along with small amounts of nanocrystalline suboxides. The size of the anatase nanocrystallites decreases with the increase of oxygen pressures. The samples deposited at 500 degrees C feature a slight improvement of surface stoichiometry, from roughly TiO(1.8) to TiO(1.9). The films deposited at high substrate temperature and oxygen pressure are highly hydrophilic. (c) 2006 Elsevier B.V. All rights reserved.

Thin layers of Fe are deposited at 100 degrees C on GaAs(1 0 0) and InAs(1 0 0) substrates by molecular beam epitaxy. These structures are characterized by photoelectron spectroscopy (PES), in order to derive their chemical composition and interface reactivity, and by X-ray magnetic circular dichroism (XMCD) recorded at room temperature in remanence mode, in order to derive the atomic magnetic moment of Fe. As previously reported, Fe/GaAs(1 0 0) exhibits a strong and complicated interface reactivity, with considerable intermixing of Fe with Ga and As. Unlike the above structure, Fe/InAs(1 0 0) exhibits a much lower interface reactivity, whereas the Fe magnetic moment increase is much more pronounced as function of Fe thickness. The total atomic ferromagnetic moment reaches at room temperature 2.0 Bohr magnetons by about I nm Fe effective thickness, which is almost the Fe bcc bulk value (2.2 Bohr magnetons). The novelty of the present study is a direct comparison of the two interfaces prepared and measured in the same experimental arrangements. (c) 2006 Elsevier B.V. All rights reserved.

CdMnS ternary alloys have attracted much attention because they permit to tune the energy gap, the effective mass and the lattice constant by varying the concentration of the magnetic material. Growth and physical characterization of Cd1-xMnxS thin films, prepared in different conditions on glass and silicon substrates by thermal evaporation technique is presented. The starting powders, CdS and Mn, were mixed in a crucible in various molar ratios. The samples were characterized by XRD, AFM and XPS. The blue shift of band gap of thin films might be ascribed to the size effect of the small grains and to the fact that Cd was substituted by Mn in the CdS structure.

The hydrophilicity of RF sputtered thin films of: (a) pure TiO2 and (b) TiO2 doped with 0.3% Ce, 0.4% Nb, and 0.4% N (atomic percents) was investigated macroscopically by measurements of the contact angle between water and film surface. The results are discussed in terms of the connection of the hydrophilic and photocatalytic properties of the materials with their structure, morphology and optical characteristics. The 280 nm thick films were deposited on optical glass substrates at 250 degrees C. Film structure and surface morphology were investigated by X-ray diffraction and atomic force microscopy. The surface roughness was derived from atomic force microscopy and ellipsometric data. The contact angle of de-ionized water with film surface was monitored during photo-activation and after irradiating with near-UV light. The surface super-hidrophilicity of all the investigated samples decays, when samples are kept in darkness for 48 h after irradiation. The hydrophilic behavior of the doped TiO2 thin films is discussed in terms of the effects of surface roughness, phase transformations enhanced by doping and charge carrier recombination. (c) 2006 Elsevier B.V All rights reserved.

Epitaxial Pb(Zr,Ti)O-3 (PZT) thin films with thicknesses in the range of 50-200 nin and with 0.2 Zr/(Zr + Ti) ratio, were grown by pulsed laser deposition (PLD). The substrates used for PLD deposition are single crystalline 0.5% Nb-doped (1 0 0)SrTiO3 (STON). SrRuO3 (SRO) thin films were deposited as bottom and top electrodes in order to have minimum structural misfit, to insure on one side high quality growth, and on the other side to minimize the influence of the ext,ended structural defects. Structural and electrical characterization was performed. The epitaxial PZT films are c-axis oriented and have an average roughness of 0.4 nm. The ferroelectric behavior was proved in all investigated films by the presence of the hysteresis loops and by the butterfly shape of the capacitance-voltage (C-V) characteristics. The ferroelectricity was present even in the samples with relative high leakage currents, down to a thickness of 50 nm. These results are essential when small thickness is needed for miniaturization of ferroelectric devices using PZT. (c) 2005 Elsevier B.V. All rights reserved.

Nanostructured Ni/C-60 thin films, produced by co-evaporation of Ni and fullerene, have been investigated by both X-ray diffraction (XRD) and X-ray magnetic circular dichroism (XMCD). X-ray diffraction has shown the co-existence of diffraction specific peaks for the fullerene face-centered cubic crystal structure and diffraction peaks of Ni nanoparticles in the face-centered cubic structure, which are broadened by nanoparticule finite dimensions. Analysis of peak widths shows that the Ni nanocrystallite size ranges from 4.7 to 19.2 nm. The XMCD signals for a sample series, preparated on relatively low-temperature substrates during the co-evaporation, can be interpreted as having distinct contributions due to both bulk and surface Ni atoms. These two kind of atoms are antiferromagnetic coupled. The Ni atoms which are at the interface with the fullerite matrix show ail enhanced orbital magnetic moment, while the orbital magnetic moment of Ni atoms in the bulk has very low values, as it can be expected for a crystalline field with a cubic symmetry.

Interface reaction and magnetism of epitaxially-grown Fe on InAs(100) are studied by core-level photoemission (As 3d and In 4d) and Fe 2p X-ray magnetic circular dichroism using synchrotron radiation. The reactivity of Fe/InAs(100) is relatively low compared to that of other interfaces involving deposition of 3d metals on III-V semiconductors. As a consequence, we observe a magnetic signal at Fe L-2,L-3 edges for the lowest thicknesses studied (1 ML). The atomic magnetic moment reaches a value close to that of the bulk alpha-Fe (2.2 mu(B)) for Fe coverages exceeding 5 ML. A ferromagnetic compound with approximate stoichiometry of FeAs is formed at the interface. The orbital magnetism represents between 12 and 20% of the total momentum, due to 3d density of states depletion and to crystal-field modification of the electronic levels. These properties make the Fe/InAs(100) interface very promising for spin-tunneling devices.

Ru-zeolites prepared via deposition of aqueous solution of ruthenium chloride on X, L, ZSM-5 and APO-54 were investigated. The impregnated solids were characterized by the following techniques: N-2 sorption, H-2 chemisorption, TPR, XRD, XPS, EXAFS and Mossbauer spectroscopy. It was found that deposition of Ru is influenced by the pore structure and the chemical composition of the supports, in particular the concentration and strength of the protonic sites, with the formation of the different species. The packing of Ru as well as the degree of the reduction and the metal particle size are different according to the penetration depth of the metal and the nature of the zeolite. The amount of chlorine possibly remaining as adatoms of Ru is very low or inexistent. In calcined and reduced catalysts no chloride peak could be evidenced by XPS. The experiments confirmed that the use of large amounts of Ru chloride precursor leads to rather large metal particles. (C) 1999 Elsevier Science B.V. All rights reserved.

Two Pd-Dy/gamma-Al2O3 catalysts, with 1 wt.% Dy and various Pd loadings (0.1 and 0.5 wt.%) have been investigated by EXAFS at the Dy L(III)-edge, and compared with 1 % Dy/gamma-Al2O3. The Dy-carrier interaction was found to change with the Pd dispersity.