Chemical and kinetic insights into the Thermal Decomposition of an Oxide Layer on Si(111) from Millisecond Photoelectron Spectroscopy.

Despite thermal silicon oxide desorption is a basic operation in semiconductor nanotechnology, its detailed chemical analysis has not been yet realized via time-resolved photoemission. Using an advanced acquisition system and synchrotron radiation, heating schedules with velocities as high as 100 K.s-1 were implemented and highly resolved Si 2p spectra in the tens of millisecond range were obtained. Starting from a Si(111)-7 × 7 surface oxidized in O2 at room temperature (1.4 monolayer of oxygen), changes in the Si 2p spectral shape enabled a detailed chemical analysis of the oxygen redistribution at the surface and of the nucleation, growth and reconstruction of the clean silicon areas. As desorption is an inhomogeneous surface process, the Avrami formalism was adapted to oxide desorption via an original mathematical analysis. The extracted kinetic parameters (the Avrami exponent equal to ~2, the activation energy of ~4.1 eV and a characteristic frequency) were found remarkably stable within a wide (~110 K) desorption temperature window, showing that the Avrami analysis is robust. Both the chemical and kinetic information collected from this experiment can find useful applications when desorption of the oxide layer is a fundamental step in nanofabrication processes on silicon surfaces.

GaAs Core/SrTiO3 Shell Nanowires Grown by Molecular Beam Epitaxy.

We have studied the growth of a SrTiO3 shell on self-catalyzed GaAs nanowires grown by vapor-liquid-solid assisted molecular beam epitaxy on Si(111) substrates. To control the growth of the SrTiO3 shell, the GaAs nanowires were protected using an arsenic capping/decapping procedure in order to prevent uncontrolled oxidation and/or contamination of the nanowire facets. Reflection high energy electron diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy were performed to determine the structural, chemical, and morphological properties of the heterostructured nanowires. Using adapted oxide growth conditions, it is shown that most of the perovskite structure SrTiO3 shell appears to be oriented with respect to the GaAs lattice. These results are promising for achieving one-dimensional epitaxial semiconductor core/functional oxide shell nanostructures.

The electronic properties of mixed valence hydrated europium chloride thin film.

We investigate the electronic properties of a model mixed-valence hydrated chloride europium salt by means of high resolution photoemission spectroscopy (HRPES) and resonant photoemission spectroscopy (RESPES) at the Eu 3d → 4f and 4d → 4f transitions. From the HRPES spectra, we have determined that the two europium oxidation states are homogeneously distributed in the bulk and that the hydrated salt film is exempt from surface mixed valence transition. From the RESPES spectra, the well separated resonant contributions characteristic of divalent and trivalent europium species (4f(6) and 4f(7) final states, respectively) are accurately extracted and quantitatively determined from the resonant features measured at the two edges. The partial absorption yield spectra, obtained by integrating the photoemission intensity in the valence-band region, can be well reproduced by atomic multiplet calculation at the M(4,5) (3d-4f) absorption edge and by an asymmetric Fano-like shape profile at the N(4,5) (4d-4f) absorption edge. The ratio of Eu(2+) and Eu(3+) species measured at the two absorption edges matches with the composition of the mixed valence europium salt as determined chemically. We have demonstrated that the observed spectroscopic features of the mixed valence salt are attributed to the mixed-valence ground state rather than surface valence transition. HRPES and RESPES spectra provide reference spectra for the study of europium salts and their derivatives.

Hysteresis and change of transition temperature in thin films of Fe{[Me2Pyrz]3BH}2, a new sublimable spin-crossover molecule.

Thin films of the spin-crossover (SCO) molecule Fe{[Me2Pyrz]3BH}2 (Fe-pyrz) were sublimed on Si/SiO2 and quartz substrates, and their properties investigated by X-ray absorption and photoemission spectroscopies, optical absorption, atomic force microscopy, and superconducting quantum interference device. Contrary to the previously studied Fe(phen)2(NCS)2, the films are not smooth but granular. The thin films qualitatively retain the typical SCO properties of the powder sample (SCO, thermal hysteresis, soft X-ray induced excited spin-state trapping, and light induced excited spin-state trapping) but present intriguing variations even in micrometer-thick films: the transition temperature decreases when the thickness is decreased, and the hysteresis is affected. We explain this behavior in the light of recent studies focusing on the role of surface energy in the thermodynamics of the spin transition in nano-structures. In the high-spin state at room temperature, the films have a large optical gap (∼5 eV), decreasing at thickness below 50 nm, possibly due to film morphology.

Flower-shaped domains and wrinkles in trilayer epitaxial graphene on silicon carbide.

Trilayer graphene is of particular interest to the 2D materials community because of its unique tunable electronic structure. However, to date, there is a lack of fundamental understanding of the properties of epitaxial trilayer graphene on silicon carbide. Here, following successful synthesis of large-area uniform trilayer graphene, atomic force microscopy (AFM) showed that the trilayer graphene on 6H-SiC(0001) was uniform over a large scale. Additionally, distinct defects, identified as flower-shaped domains and isolated wrinkle structures, were observed randomly on the surface using scanning tunneling microscopy and spectroscopy (STM/STS). These carbon nanostructures formed during growth, has different structural and electronic properties when compared with the adjacent flat regions of the graphene. Finally, using low temperature STM/STS at 4K, we found that the isolated wrinkles showed an irreversible rotational motion between two 60° configurations at different densities of states.

Direct observation of massless domain wall dynamics in nanostripes with perpendicular magnetic anisotropy.

Domain wall motion induced by nanosecond current pulses in nanostripes with perpendicular magnetic anisotropy (Pt/Co/AlO(x)) is shown to exhibit negligible inertia. Time-resolved magnetic microscopy during current pulses reveals that the domain walls start moving, with a constant speed, as soon as the current reaches a constant amplitude, and no or little motion takes place after the end of the pulse. The very low "mass" of these domain walls is attributed to the combination of their narrow width and high damping parameter α. Such a small inertia should allow accurate control of domain wall motion by tuning the duration and amplitude of the current pulses.

Hydrogen-induced surface metallization of SrTiO3(001).

Surface metallization of SrTiO3(001) by hydrogen adsorption is experimentally confirmed for the first time by photoemission spectroscopy and surface conductivity measurements. The metallic state is assigned to a quantized state in the space-charge layer induced by electron doping from hydrogen atoms. The measured two-dimensional (2D) conductivity is well above the 2D Ioffe-Regel limit indicating that the system is in a metallic conduction regime. The mean free path of the surface electron is estimated to be several nanometers at room temperature.

Current-induced domain wall motion and magnetization dynamics in CoFeB/Cu/Co nanostripes.

Current-induced domain wall motion and magnetization dynamics in the CoFeB layer of CoFeB/Cu/Co nanostripes were studied using photoemission electron microscopy combined with x-ray magnetic circular dichroism (XMCD-PEEM). Quasi-static measurements show that current-induced domain wall motion in the CoFeB layer is similar to the one observed in the NiFe layer of NiFe/Cu/Co trilayers, although the threshold current densities for domain wall depinning are lower. Time-resolved XMCD-PEEM measurements are used as an efficient probe of domain wall depinning statistics. They also reveal that, during the application of current pulses, the CoFeB magnetization rotates in the direction transverse to the nanostripe. The corresponding tilt angles have been quantified and compared to analytical and micromagnetic calculations, highlighting the influence of magnetostatic interactions between the two magnetic layers on the magnetization rotation.

Carbon contamination of soft X-ray beamlines: dramatic anti-reflection coating effects observed in the 1 keV photon energy region.

Carbon contamination is a general problem of under-vacuum optics submitted to high fluence. In soft X-ray beamlines carbon deposit on optics is known to absorb and scatter radiation close to the C K-edge (280 eV), forbidding effective measurements in this spectral region. Here the observation of strong reflectivity losses is reported related to carbon deposition at much higher energies around 1000 eV, where carbon absorptivity is small. It is shown that the observed effect can be modelled as a destructive interference from a homogeneous carbon thin film.

Time-resolved photoelectron spectroscopy using synchrotron radiation time structure.

Synchrotron radiation time structure is becoming a common tool for studying dynamic properties of materials. The main limitation is often the wide time domain the user would like to access with pump-probe experiments. In order to perform photoelectron spectroscopy experiments over time scales from milliseconds to picoseconds it is mandatory to measure the time at which each measured photoelectron was created. For this reason the usual CCD camera-based two-dimensional detection of electron energy analyzers has been replaced by a new delay-line detector adapted to the time structure of the SOLEIL synchrotron radiation source. The new two-dimensional delay-line detector has a time resolution of 5 ns and was installed on a Scienta SES 2002 electron energy analyzer. The first application has been to characterize the time of flight of the photoemitted electrons as a function of their kinetic energy and the selected pass energy. By repeating the experiment as a function of the available pass energy and of the kinetic energy, a complete characterization of the analyzer behaviour in the time domain has been obtained. Even for kinetic energies as low as 10 eV at 2 eV pass energy, the time spread of the detected electrons is lower than 140 ns. These results and the time structure of the SOLEIL filling modes assure the possibility of performing pump-probe photoelectron spectroscopy experiments with the time resolution given by the SOLEIL pulse width, the best performance of the beamline and of the experimental station.

Exchange and correlation effects in electronic excitations of Cu(2)O.

State-of-the-art theoretical methods fail in describing the optical absorption spectrum, band gap, and optical onset of Cu(2)O. We have extended a recently proposed self-consistent quasiparticle approach, based on the GW approximation, to the calculation of optical spectra, including excitonic effects. The band structure compares favorably with our present angle-resolved photoemission measurements. The excitonic effects based on these realistic band structure and screening provide a reliable optical absorption spectrum, which allows for a revised interpretation of its main structures.

SB7: the new bending-magnet double-headed dragon beamline at SuperACO.

A new beamline is now operational at LURE on bending-magnet 7 of the SuperACO storage ring in Orsay. The monochromator is of the ;dragon' type, designed to work in the energy range 150-1500 eV, and is equipped with a double vertical focusing mirror in order to allow for fast switching of light polarization. In this paper the results of photoion-yield experiments performed on N(2), Ar and Ne gases are presented. The observed resonance structures enable us to determine the available energy resolution: a resolving power higher than 8500 is obtained at the Ar 2p, N 1s and Ne K-edges when using all the optical elements at full aperture. The total flux as a function of the measured photon energy resolution and the characterization of the double-head behaviour in delivering circularly polarized light are reported.