RESUMO
Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy-carboxylate metal-organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X-ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface-supported metal-organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in-plane easy magnetization axis despite the out-of-plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal-organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces.
RESUMO
The adsorption of purely organic chiral molecules on ferromagnetic Co thin films is studied under ultra high vacuum conditions by means of synchrotron radiation-based electron spectroscopies, namely X-ray absorption and ultraviolet photoemission. X-ray absorption reveals that enantiomers with opposite handedness (R,R)- and (S,S)- of two different molecules adsorb with different strength on the Co surfaces and their valence band photoemission spectra also display distinctive features. In view of the recent reports describing the chiral-induced spin selectivity (CISS) effect these results lead us to consider the possibility that some enantiosensitivity may appear when bonding chiral molecules to a substrate with an initial asymmetry in the population of the different spin orientations.
RESUMO
The fundamental limits currently faced by traditional computing devices necessitate the exploration of ways to store, compute, and transmit information going beyond the current CMOS-based technologies. Here, we propose a three-dimensional (3D) magnetic interconnector that exploits geometry-driven automotion of domain walls (DWs), for the transfer of magnetic information between functional magnetic planes. By combining state-of-the-art 3D nanoprinting and standard physical vapor deposition, we prototype 3D helical DW conduits. We observe the automotion of DWs by imaging their magnetic state under different field sequences using X-ray microscopy, observing a robust unidirectional motion of DWs from the bottom to the top of the spirals. From experiments and micromagnetic simulations, we determine that the large thickness gradients present in the structure are the main mechanism for 3D DW automotion. We obtain direct evidence of how this tailorable magnetic energy gradient is imprinted in the devices, and how it competes with pinning effects that are due to local changes in the energy landscape. Our work also predicts how this effect could lead to high DW velocities, reaching the Walker limit during automotion. This work demonstrates a possible mechanism for efficient transfer of magnetic information in three dimensions.
RESUMO
We have investigated a recently developed method of patterning Ag surfaces. The method uses an electron beam to irradiate Ag surfaces during NO(2) dosing at 300 K and leads to sharp oxide patterns on otherwise metallic surfaces. Investigations were performed on an Ag(111) single crystal and on an Ag foil with LEEM (low-energy electron microscopy), LEED (low-energy electron diffraction), MEM (mirror electron microscopy), and XPEEM (X-ray photo-emission electron microscopy). The oxidation reaction, which is based on the electron-induced desorption of NO molecules, proceeds in steps, from a layer of O atoms adsorbed on the metallic Ag via an intermediate phase to an amorphous Ag(2)O film. Our measurements evidence a high cross section for electron-induced NO desorption with 30-40 eV electrons, indicating that only a few electrons per adsorbing NO(2) molecule are required to initiate the process. The intermediate phase, which forms a partially ordered quadratic structure, contains oxygen species in an oxide-like environment, coexisting with an adsorbate covered metallic Ag(111) surface. While the intermediate phase dissolves within hours under UHV conditions, fully developed oxide patches, consisting of several layers of thick, amorphous Ag(2)O, are kinetically stable. The oxidation method also works with 40 eV (and 700 eV) photons instead of electrons. In preliminary experiments local patterns could also be created with photons, suggesting that mask techniques can be applied for the process.
RESUMO
The reactivity of an iron monosulfide surface exposed at room temperature to molecular nitrogen and hydrogen sulfide has been investigated using X-ray photoemission spectroscopy (XPS) and thermal desorption spectroscopy (TDS). We have observed adsorption of nitrogen at room temperature that depends on the surface nanostructure and on the electronic state of nitrogen. The subsequent reaction of this adsorbed nitrogen with hydrogen sulfide results in depletion of the nitrogen surface content which can be interpreted in terms of ammonia formation. The XPS nitrogen N 1s core level line shape shows different components one of which seems to be the most reactive one in the ensuing H2S reaction.
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The growth and reaction of Fe on a ZnS(1 0 0) substrate are studied in situ and with high lateral resolution using low energy electron microscopy (LEEM), micro low energy electron diffraction ( µLEED), x-ray photoemission electron microscopy (XPEEM), microprobe x-ray photoelectron spectroscopy ( µXPS) and x-ray magnetic circular dichroism PEEM (XMCDPEEM) for complementary structural, chemical, and magnetic characterization. Initially, a two-dimensional (Fe, Zn)S reaction layer forms with thickness that depends on growth temperature. Further growth results in the formation of a variety of three-dimensional crystals, most of them strongly elongated in the form of 'nanowires' of two distinct types, labeled as A and B. Type A nanowires are oriented near the ZnS[1 1 0] direction and are composed of Fe. Type B nanowires are oriented predominantly along directions a few degrees off the ZnS[0 0 1] direction and are identified as Greigite (Fe3S4). Both types of nanowires are magnetic with Curie temperatures above 450 °C. The understanding of the reactive growth mechanism in this system that is provided by these investigations may help to develop growth methods for other elemental and transition metal chalcogenide nanostructures on ZnS and possibly on other II-VI semiconductor surfaces.
RESUMO
A combined use of low energy electron microscopy (LEEM) and microprobe LEED (micro-LEED) allows the in-situ observation of dynamical processes at the TiOx/Pt(111) interface. The transformations between different surface-stabilized phases are investigated in the case of room temperature TiOx reactive deposition with subsequent post-annealing. For a coverage of 0.6 MLeq, UHV annealing to 400 degrees C leads to the formation of the zigzag-like z-TiO1.33 layer. At higher temperatures a rotated z-TiO1.33 phase is observed, its lateral distribution being strongly influenced by surface morphology. Concurrently, the z-TiO1.33 layer partially transforms into a kagomé-like TiO1.5 structure. The resulting oxygen enrichment of the interface is interpreted by invoking Ti interdiffusion into the substrate. At a coverage of 0.45 MLeq, UHV annealing at 500 degrees C transforms the z-TiO1.33 layer into a different zigzag-like z'-TiO1.25 layer. Post-annealing in oxygen of the reduced phases or direct reactive deposition at high temperature both produce the rect-TiO2 stoichiometric phase, showing characteristic needle-like domains aligned according to the rect-TiO2 unit cell orientation.
RESUMO
Understanding size/dimensionality-dependent phenomena and processes relevant to chemical sensing and catalysis requires analytical methods with high surface sensitivity, which can exploit the structure and composition of nanomaterials at their natural length scales and working conditions. In the present study, we explored the potentials and complementary capabilities of several surface-sensitive microscopy approaches to shed light on the properties of individual SnO(2) nanowires and their networks. Our results demonstrate the unique opportunities provided by synchrotron-based photoelectron microscopies for surface-sensitive structural and chemical analysis, including in situ characterization of electron transport properties of a nanostructure wired as an active element in chemiresistor devices.