Electronic tuneability of a structurally rigid surface intermetallic and Kondo lattice: CePt5_5 / Pt(111)

We present an extensive study of structure, composition, electronic and magnetic properties of Ce--Pt surface intermetallic phases on Pt(111) as a function of their thickness. The sequence of structural phases appearing in low energy electron diffraction (LEED) may invariably be attributed to a single underlying intermetallic atomic lattice. Findings from both microscopic and spectroscopic methods, respectively, prove compatible with CePt$_5$ formation when their characteristic probing depth is adequately taken into account. The intermetallic film thickness serves as an effective tuning parameter which brings about characteristic variations of the Cerium valence and related properties. Soft x-ray absorption (XAS) and magnetic circular dichroism (XMCD) prove well suited to trace the changing Ce valence and to assess relevant aspects of Kondo physics in the CePt$_5$ surface intermetallic. We find characteristic Kondo scales of the order of 10$^2$ K and evidence for considerable magnetic Kondo screening of the local Ce $4f$ moments. CePt$_5$/Pt(111) and related systems therefore appear to be promising candidates for further studies of low-dimensional Kondo lattices at surfaces.Comment: 14 pages, 11 figure

Observation of an atomic exchange bias effect in DyCo4 film

The fundamental important and technologically widely employed exchange bias effect occurs in general in bilayers of magnetic thin films consisting of antiferromagnetic and ferromagnetic layers where the hard magnetization behavior of an antiferromagnetic thin film causes a shift in the magnetization curve of a soft ferromagnetic film. The minimization of the single magnetic grain size to increase the storage density and the subsequent demand for magnetic materials with very high magnetic anisotropy requires a system with high HEB. Here we report an extremely high HEB of 4 Tesla observed in a single amorphous DyCo4 film close to room temperature. The origin of the exchange bias can be associated with the variation of the magnetic behavior from the surface towards the bulk part of the film revealed by X ray absorption spectroscopy and X ray magnetic circular dichroism techniques utilizing the bulk sensitive transmission and the surface sensitive total electron yield modes. The competition between the atomic exchange coupling in the single film and the Zeeman interaction lead to an intrinsic exchanged coupled system and the so far highest exchange bias effect HEB amp; 8201; amp; 8201;4 Tesla reported in a single film, which is accommodated by a partial domain wall formatio

A detailed investigation of the onion structure of exchanged coupled magnetic Fe3-dO4@CoFe2O4@Fe3-dO4 nanoparticles

Nanoparticles that combine several magnetic phases offer wide perspectives for cutting edge applications because of the high modularity of their magnetic properties. Besides the addition of the magnetic characteristics intrinsic to each phase, the interface that results from core-shell and, further, from onion structures leads to synergistic properties such as magnetic exchange coupling. Such a phenomenon is of high interest to overcome the superparamagnetic limit of iron oxide nanoparticles which hampers potential applications such as data storage or sensors. In this manuscript, we report on the design of nanoparticles with an onion-like structure which has been scarcely reported yet. These nanoparticles consist of a Fe3-dO4 core covered by a first shell of CoFe2O4 and a second shell of Fe3-dO4, e.g., a Fe3-dO4@CoFe2O4@Fe3-dO4 onion-like structure. They were synthesized through a multistep seed-mediated growth approach which consists consists in performing three successive thermal decomposition of metal complexes in a high-boiling-point solvent (about 300 °C). Although TEM micrographs clearly show the growth of each shell from the iron oxide core, core sizes and shell thicknesses markedly differ from what is suggested by the size increasing. We investigated very precisely the structure of nanoparticles in performing high resolution (scanning) TEM imaging and geometrical phase analysis (GPA). The chemical composition and spatial distribution of atoms were studied by electron energy loss spectroscopy (EELS) mapping and spectroscopy. The chemical environment and oxidation state of cations were investigated by 57Fe Mössbauer spectrometry, soft X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). The combination of these techniques allowed us to estimate the increase of Fe2+ content in the iron oxide core of the core@shell structure and the increase of the cobalt ferrite shell thickness in the core@shell@shell one, whereas the iron oxide shell appears to be much thinner than expected. Thus, the modification of the chemical composition as well as the size of the Fe3-dO4 core and the thickness of the cobalt ferrite shell have a high impact on the magnetic properties. Furthermore, the growth of the iron oxide shell also markedly modifies the magnetic properties of the core-shell nanoparticles, thus demonstrating the high potential of onion-like nanoparticles to accurately tune the magnetic properties of nanoparticles according to the desired applications. © 2021 American Chemical Society

Magnetic Coupling and Single-Ion Anisotropy in Surface-Supported Mn-based Metal-Organic Networks

The electronic and magnetic properties of Mn coordinated to 1,2,4,5-tetracyanobenzene (TCNB) in the Mn-TCNB 2D metal-ligand networks have been investigated by combining scanning tunneling microscopy and X-ray magnetic circular dichroism (XMCD) performed at low temperature (3 K). When formed on Au(111) and Ag(111) substrates the Mn-TCNB networks display similar geometric structures. Magnetization curves reveal ferromagnetic (FM) coupling of the Mn sites with similar single-ion anisotropy energies, but different coupling constants. Low-temperature XMCD spectra show that the local environment of the Mn centers differs appreciably for the two substrates. Multiplet structure calculations were used to derive the corresponding ligand field parameters confirming an in-plane uniaxial anisotropy. The observed interatomic coupling is discussed in terms of superexchange as well as substrate-mediated magnetic interactions.Comment: J. Phys. Chem. C 201

Atomic-Scale Study of Metal–Oxide Interfaces and Magnetoelastic Coupling in Self-Assembled Epitaxial Vertically Aligned Magnetic Nanocomposites

Vertically aligned nanocomposites (VANs) of metal/oxide type have recently emerged as a novel class of heterostructures with great scientific and technological potential in the fields of nanomagnetism, multiferroism, and catalysis. One of the salient features of these hybrid materials is their huge vertical metal/oxide interface, which plays a key role in determining the final magnetic and/or transport properties of the composite structure. However, in contrast to their well‐studied planar counterparts, detailed information on the structural features of vertical interfaces encountered in VANs is scarce. In this work, high resolution scanning transmission electron microscopy (STEM) and electron energy‐loss spectroscopy (EELS) are used to provide an element selective atomic‐scale analysis of the interface in a composite consisting of ultrathin, self‐assembled Ni nanowires, vertically epitaxied in a SrTiO3/SrTiO3(001) matrix. Spectroscopic EELS measurements evidence rather sharp interfaces (6–7 Å) with the creation of metallic NiTi bonds and the absence of nickel oxide formation is confirmed by X‐ray absorption spectroscopy measurements. The presence of these well‐defined phase boundaries, combined with a large lattice mismatch between the oxide and metallic species, gives rise to pronounced magnetoelastic effects. Self‐assembled columnar Ni:SrTiO3 composites thus appear as ideal model systems to explore vertical strain engineering in metal/oxide nanostructures

Ultralow-temperature device dedicated to soft X-ray magnetic circular dichroism experiments

A new ultralow-temperature setup dedicated to soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) experiments is described. Two experiments, performed on the DEIMOS beamline (SOLEIL synchrotron), demonstrate the outstanding performance of this new platform in terms of the lowest achievable temperature under X-ray irradiation (T = 220 mK), the precision in controlling the temperature during measurements as well as the speed of the cooling-down and warming-up procedures. Moreover, owing to the new design of the setup, the eddy-current power is strongly reduced, allowing fast scanning of the magnetic field in XMCD experiments; these performances lead to a powerful device for X-ray spectroscopies on synchrotron-radiation beamlines facilities

Suppression of the critical thickness threshold for conductivity at the LaAlO3/SrTiO3 interface

Perovskite materials engineered in epitaxial heterostructures have been intensely investigated during the last decade. The interface formed by an LaAlO3 thin film grown on top of a TiO2-terminated SrTiO3 substrate hosts a two-dimensional electronic system and has become the prototypical example of this field. Although controversy exists regarding some of its physical properties and their precise origin, it is universally found that conductivity only appears beyond an LaAlO3 thickness threshold of four unit cells. Here, we experimentally demonstrate that this critical thickness can be reduced to just one unit cell when a metallic film of cobalt is deposited on top of LaAlO3. First-principles calculations indicate that Co modifies the electrostatic boundary conditions and induces a charge transfer towards the Ti 3d bands, supporting the electrostatic origin of the electronic system at the LaAlO3/SrTiO3 interface. Our results expand the interest of this low-dimensional oxide system from in-plane to perpendicular transport and to the exploration of elastic and inelastic tunnel-type transport of (spin-polarized) carriers

DEIMOS: A beamline dedicated to dichroism measurements in the 350-2500 eV energy range:

The DEIMOS (Dichroism Experimental Installation for Magneto-Optical Spectroscopy) beamline was part of the second phase of the beamline development at French Synchrotron SOLEIL (Source Optimisee de Lumiere a Energie Intermediaire du LURE) and opened to users in March 2011. It delivers polarized soft x-rays to perform x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and x-ray linear dichroism in the energy range 350-2500 eV. The beamline has been optimized for stability and reproducibility in terms of photon flux and photon energy. The main end-station consists in a cryo-magnet with 2 split coils providing a 7 T magnetic field along the beam or 2 T perpendicular to the beam with a controllable temperature on the sample from 370 K down to 1.5 K. (C) 2014 AIP Publishing LLC

First glimpse of the soft x-ray induced excited spin-state trapping effect dynamics on spin cross-over molecules

The dynamics of the soft x-ray induced excited spin state trapping (SOXIESST) effect of Fe(phen)(2)(NCS)(2) (Fe-phen) powder have been investigated by x-ray absorption spectroscopy (XAS) using the total electron yield method, in a wide temperature range. The low-spin (LS) state is excited into the metastable high-spin (HS) state at a rate that depends on the intensity of the x-ray illumination it receives, and both the temperature and the intensity of the x-ray illumination will affect the maximum HS proportion that is reached. We find that the SOXIESST HS spin state transforms back to the LS state at a rate that is similar to that found for the light induced excited spin state trapping (LIESST) effect. We show that it is possible to use the SOXIESST effect in combination with the LIESST effect to investigate the influence of cooperative behavior on the dynamics of both effects. To investigate the impact of molecular cooperativity, we compare our results on Fe-phen with those obtained for Fe[Me(2)Pyrz](3)BH(2) (Fe-pyrz) powder, which exhibits a similar thermal transition temperature but with a hysteresis. We find that, while the time constant of the dynamic is identical for both molecules, the SOXIESST effect is less efficient at exciting the HS state in Fe-pyrz than in Fe-phen. (C) 2013 AIP Publishing LLC