S. Valeri

The oxygen effect in the growth kinetics of platinum silicides

Silicide formation is strongly affected by the presence of oxygen contained in the metal film. A study has been performed by heating at various times and temperatures samples constituted by a thin Pt film sputter deposited on a silicon substrate. Four different oxygen concentrations were implanted in the Pt film ranging from 1 to 0.1 at.%. The presence of oxygen slows down the growth rate of Pt2Si. At 315 °C in the sample with an oxygen concentration of 1 at.%, about 1000 A of Pt2Si are formed after 20 min of annealing. During the silicide formation, the oxygen originally contained in the platinum films segregates at the Pt2Si/Pt interface. This accumulation acts as a barrier for the transport of Pt and a new phase, PtSi, can form at the Pt2Si/Si interface. The dose necessary to stop the Pt2Si reaction is about (2–4)×1015 at./cm2 at 315 °C.

Structure and stability of nickel/nickel oxide core–shell nanoparticles

The results of a combined x-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HR-TEM) study of Ni nanoparticles (NP), before and after oxidation, are presented. An experimental set-up was realized for the preparation and study of pre-formed NP films, concentrating the attention on Ni NP in the diameter range between 4 and 8 nm. The XPS data were taken in situ from NPs after different stages of oxidation, including controlled dosing of O(2) gas in the experimental system and exposure to the atmosphere. The Ni 2p structure is a combination of spectra from metallic Ni in the NP core and from the oxide shell. The signal from the NP core was observed even for samples after exposure to air. From the comparison of HR-TEM experimental images with theoretical simulations, it was found that the Ni NP core has a regular multitwinned icosahedral structure, composed of single-crystal tetrahedra with (111) faces. The NiO phase is clearly observed forming islands on the NP surface.

Interlayer water and swelling properties of monoionic montmorillonites

Abstract The dehydration of two montmorillonites saturated by 10 different cations is investigated by X-ray spectroscopy, in different conditions of temperature and environmental relative humidity. We consider, in particular, the cation “solvatation” water and propose a model, on the basis of which we show that, in the case of the 15-A structure the stability of the H20-cation-silicate complex depends essentially on the electrostatic energy of the water molecule dipole in the cation field. In the 12-A case, on the other hand, sometimes the energy change associated with the redistribution of the electrical charges of the cation and of the silicate seems to prevail, depending on the interlayer spacing. We also show a correlation between cationic radius and closest interlayer spacing in the conditions of extreme dehydration.

Structural study of thin MgO layers on Ag(001) prepared by either MBE or sputter deposition

Abstract Growth, morphology and structure of thin MgO films prepared on Ag(001) substrates by different preparation procedures have been investigated by AES, LEED and modulated electron emission. Oxide layers were prepared by Mg MBE in an oxygen atmosphere or sputter deposition from bulk MgO target. In both cases stoichiometric MgO forms, which initially grows in a rocksalt tetragonally distorted structure. For 3-ML films, 3.6% expansion of the interlayer spacing along the growth axis has been measured. The misfit strain progressively reduces as the film thickness increases, and the equilibrium spacing is completely recovered at 8–10 ML thickness. In spite of the similarity in structure and strain, different deposition procedures lead to different film morphology. Sputter deposited films only partially cover the substrate. Fractional coverage (50%) has been evaluated for the 3-ML thick film, and full coverage only occurs at approximately 10 ML thickness. The MBE procedure results in almost complete layers. Fourfold broadening of spot profiles has been observed in LEED patterns of both MBE and sputter deposited films, indicating the occurrence of a similar large-scale atomic arrangement and surface morphology.

Image charge screening: A new approach to enhance magnetic ordering temperatures in ultrathin correlated oxide films

We have tested the concept of image charge screening as a new approach to enhance magnetic ordering temperatures and superexchange interactions in ultra thin films. Using a 3 monolayer NiO(100) film grown on Ag(100) and an identically thin film on MgO(100) as model systems, we observed that the Neel temperature of the NiO film on the highly polarizable metal substrate is 390 K while that of the film on the poorly polarizable insulator substrate is below 40 K. This demonstrates that screening by highly polarizable media may point to a practical way towards designing strongly correlated oxide nanostructures with greatly improved magnetic properties.

Morphology evolution and magnetic properties improvement in FePt epitaxial films by in situ annealing after growth

This paper presents a detailed study of structure, morphology, and magnetic properties in FePt thin films epitaxially grown on MgO(100) at intermediate temperatures (≅380°C). It focuses on the effects obtained by in situ annealing the FePt films after deposition. We have demonstrated that the annealing allows one to complete the ordering, thus obtaining an epitaxial L10-FePt film with large perpendicular anisotropy (up to 3×107erg∕cm3) and high perpendicular squareness and remanence ratio (both higher than 0.85). At the same time, we have found a peculiar morphology evolution by increasing the annealing time: the interconnected mazelike grains evolve towards interconnected dotlike grains of reduced size (down to 10nm). Due to the interconnection at the grains basis, the increase in the film perpendicular coercivity with the annealing process is moderate (up to 4.1kOe), leading to an increasing anisotropy/coercivity ratio with the annealing time. As a further step towards the understanding of the propertie...

AUGER AND X-RAY PHOTOEMISSION SPECTROSCOPY STUDY ON CS2TE PHOTOCATHODES

Thin films of Cs2Te have been produced and analyzed by Auger depth profiling and x‐ray photoemission spectroscopy (XPS). The formation of the photoemissive material passes through different phases, each of them has been characterized by XPS and by its total yield in the spectral region 3.5–5 eV. Copper and molybdenum substrates have been considered. While Mo behaves to all practical purposes like an ideal support for Cs2Te, strong diffusion from the substrate material into the photoemissive film has been observed on photocathodes fabricated on Cu. The ruggedness of the photocathodes has been tested by exposing them to a few hundred Langmuirs of different gases, namely O2, CO2, CO, N2, and CH4. The last three have no effect on the photocathode lifetime, while a substantial reduction of the quantum efficiency has been observed after the exposure to oxygen. The main reason for this is the formation of a thick cesium oxide layer at the surface of the photocathode. However, the oxygen pollution can be partiall...

Evidence of Catalase Mimetic Activity in Ce3+/Ce4+ Doped Bioactive Glasses

The ability of Ce-containing bioactive glasses to inhibit oxidative stress in terms of reduction of hydrogen peroxide, by mimicking the catalase enzyme activity is demonstrated here for the first time. The antioxidant properties of three bioactive glasses containing an increasing amount of CeO2 have been evaluated by following the degradation of hydrogen peroxide with time after immersion in H2O2 aqueous solutions with different concentration. XPS and UV-vis measurements allowed us to determine the Ce(3+)/Ce(4+) ratio in the bulk and on the glass surface, and to correlate it with the ability of the samples to show catalase mimetic activity. Interestingly, we have found that the bioactive glass with composition 23.2Na2O-25.7CaO-43.4SiO2-2.4P2O5-5.3CeO2 immersed in 0.1 M H2O2 aqueous solution is able to degrade 90% of it in 1 week. The reduction in bioactivity of the glasses with increasing CeO2 content is here rationalized in terms of a lower amount of phosphate groups available for the hydroxyapatite layer formation, after binding with cerium ions. In fact, classical molecular dynamics simulations revealed that the addition of CeO2 leads to the formation of cerium phosphate rich regions. The formation of an insoluble CePO4 crystalline phase is also observed by XRD analysis after thermal treatment of the glass samples.

Structure and morphology of ultrathin NiO layers on Ag(001)

Abstract The structure and morphology of thin NiO films prepared on Ag(001) by reactive growth at 460 K has been investigated as a function of the film thickness in the 3–20 monolayers range. Emphasis was on the study of the oxide layer misfit strain. Primary beam diffraction modulated electron emission and low energy electron diffraction experiments allowed the determination of the in-plane and out-of-plane strain in the oxide layer, while scanning tunneling microscopy, X-ray photoelectron spectroscopy and secondary electron imaging have been used to monitor the film morphology, stoichiometry and structure, respectively. The film strain begins to be removed at a critical thickness of 10 ML, while at 20 ML the film is fully relaxed. Strain analysis indicates that the Poisson ratio of the oxide layer is nearly equal to that of the bulk material.

MODULATED ELECTRON EMISSION BY SCATTERING-INTERFERENCE OF PRIMARY ELECTRONS

We review the effects of scattering-interference of the primary, exciting beam on the electron emission from ordered atomic arrays. The yield of elastically and inelastically backscattered electrons, Auger electrons and secondary electrons shows a marked dependence on the incidence angle of primary electrons. Both the similarity and the relative importance of processes experienced by incident and excident electrons are discussed. We also present recent studies of electron focusing and defocusing along atomic chains. The interplay between these two processes determines the in-depth profile of the primary electron intensity anisotropy. Finally, the potential for surface-structural studies and limits for quantitative analysis are discussed, in comparison with the Auger electron diffraction (AED) and photoelectron diffraction (PD) techniques.