Resonant Auger spectromicroscopy in ultrathin Fe films on W(110)

L3M 2,3 M 2,3 Auger transition is measured near the L3 resonance of ferromagnetic Fe films on W(110). The kinetic energies of the Auger peaks display the typical Raman behaviour for photon energies well below the absorption threshold, where the Auger energy follows the changes in the photon energy. Classical Auger behaviour with constant kinetic energy sets in at about 1.5 eV below the L3 resonance independently from the number of Fe layers down to the monolayer thickness. Strong x-ray circular magnetic dichroism is observed at the L3 edge in the entire L3M 2,3 M 2,3 Auger spectrum. Different Auger features originating from the final state with two 3p core holes show slight variations in the dichroic signal, which is attributed to the exchange interaction between the core holes and the valence band. Finally, XMCD-PEEM magnetic domain imaging using Auger electrons is demonstrated with a high level of contrast and lateral resolution approaching that of imaging with secondary photoelectrons

Insight into intramolecular chemical structure modifications by on-surface reaction using photoemission tomography

The sensitivity of photoemission tomography (PT) to directly probe single molecule on-surface intramolecular reactions will be shown here. PT application in the study of molecules possessing peripheral ligands and structural flexibility is tested on the temperature-induced dehydrogenation intramolecular reaction on Ag(100), leading from CoOEP to the final product CoTBP. Along with the ring-closure reaction, the electronic occupancy and energy level alignment of the frontier orbitals, as well as the oxidation state of the metal ion, are elucidated for both the CoOEP and CoTBP systems

Semiconductor Halogenation in Molecular Highly-Oriented Layered p–n (n–p) Junctions

Organic p–n junctions attract widespread interest in the field of molecular electronics because of their unique optoelectronic singularities. Importantly, the molecular donor/acceptor character is strongly correlated to the degree of substitution, e.g., the introduction of electron-withdrawing groups. Herein, by gradually increasing the degree of peripheral fluorination on planar, D4h−symmetric iron(II) phthalocyanato (FePc) complexes, the energy level alignment and molecular order is defined in a metal-supported bilayered Pc-based junction using photoemission orbital tomography. This non-destructive method selectively allows identifying molecular levels of the hetero-architectures. It demonstrates that, while the symmetric fluorination of FePc does not disrupt the long-range order and degree of metal-to-molecule charge transfer in the first molecular layer, it strongly impacts the energy alignment in both the interface and topmost layer in the bilayered structures. The p–n junction formed in the bilayer of perhydrogenated FePc and perfluorinated FeF16Pc may serve as an ideal model for understanding the basic charge-transport phenomena at the metal-supported organic–organic interfaces, with possible application in photovoltaic devices

The impact of agricultural vehicles rolling system on soil

The paper establishes the value of the average pressure at the contact surface level between the soil and the tires of the following vehicles and trailers: the U- 650 and Valtra T-190 tractors, the 2RB5AT and 7RBAT trailers and the large dump capability Iveco Trakker 8x4. The wheelground pressure is determined as the report between wheel corresponding weight and the contact surface area with soil. This area was obtained by calculation, using 12 types of equations established by different authors. In this paper, we used the average of the 12 versions, both for the wheel-soil surface and for the wheel-ground pressure. It was found that the lowest wheel-ground pressures are recorded for the Valtra U-650 and T-190 tractors (63,535 ... 142,821 kPa) and the highest in the case of the 7RBAT and 2RB5AT trailers and the Iveco Trakker 8x4 dump (432,692. .. 623,414 kPa), the maximum imposed limit by agricultural requirements being 100 kPa. Regarding the tractors, the exceeding of the imposed limit (100 kPa) is recorded for all the wheels of the Valtra T-190 tractor and only for the front wheels of the U-650 tractor. These excesses are quite small (10 ... 42 kPa), so practically will not affect soil properties. For the trailers and dump, the wheel-ground pressure is 4,3 ... 6,2 times higher the upper limit imposed for agricultural soil, 100 kPa. These high pressures don’t affect the asphalt or concrete roads, but will adversely alter the physical properties of agricultural soils

Coupling Borophene to Graphene in Air-Stable Heterostructures

Artificial 2D van der Waals heterostructures with controllable vertical stacking and rotational orientation exhibit multifaceted electronic properties that are appealing for applications in fields ranging from optoelectronics to energy storage. Along with transition metal dichalcogenides and graphene, borophene has recently emerged as a promising building block for 2D devices due to its conductive nature as well as its exceptional mechanical and electronic properties. Here, it is demonstrated that the combination of the dissolution-segregation process and chemical vapor deposition allows for the synthesis of graphene/borophene heterostructures of the highest crystalline and chemical quality, in which graphene sits on top of the borophene layer with metallic character. The formation of laterally distinct micron-sized areas allows a comparative study of borophene, graphene, and the graphene–borophene heterostack in terms of their electronic properties and stability in a reactive environment. Whereas pristine borophene is particularly prone to oxidation, the graphene–borophene heterostack is chemically inert and enables the conservation of borophene's character even after exposure to air. This study opens up new perspectives for the scalable synthesis of graphene–borophene heterostacks with enhanced ability to preserve the metallic character and electronic properties of borophene

Reversible redox reactions in metal-supported porphyrin: The role of spin and oxidation state

On-surface molecular functionalization paved the way for the stabilization of chelated ions in different oxidation and spin states, allowing for the fine control of catalytic and magnetic properties of metalorganic networks. Considering two model systems, a reduced Co(i) and an open-shell Co(ii) metal-supported 2D molecular array, we investigate the interplay between the low valence oxidation and unpaired spin state in the molecular reactivity. We show that the redox reaction taking place at the cobalt tetraphenylporphyrin/Cu(100) interface, stabilizing the low-spin Co(i) state with no unpaired electrons in its valence shell, plays a pivotal role in changing the reactivity. This goes beyond the sole presence of unpaired electrons in the valence state of the Co(ii) metal-organic species, often designated as being responsible for the reactivity towards small molecules like NO and NO2. The reversible Co-NO2 interaction, established with the Co(i) leads to the stabilization of the Co(iii) oxidation state

Clarifying the apparent flattening of the graphene band near the van Hove singularity

Graphene band renormalization near the van Hove singularity (VHS) has been investigated by angle-resolved photoemission spectroscopy (ARPES) on Li-doped quasifreestanding graphene on a cobalt (0001) surface. The absence of graphene band hybridization with the substrate, the doping contribution well represented by a rigid energy shift, and the excellent electron-electron interaction screening ensured by the metallic substrate offer a privileged point of view for such an investigation. A clear ARPES signal is detected along the KMK direction of the graphene Brillouin zone, giving rise to an apparent flattened band. By simulating the graphene spectral function from the density functional theory calculated bands, we demonstrate that the photoemission signal around the M point originates from the "tail"of the spectral function of the unoccupied band above the Fermi level. Such an interpretation puts forward the absence of any additional strong correlation effects near the VHS, reconciling the mean-field description of the graphene band structure even in a highly doped scenario

Enhancing Electron Correlation at a 3d Ferromagnetic Surface

Spin-resolved momentum microscopy and theoretical calculations are combined beyond the one-electron approximation to unveil the spin-dependent electronic structure of the interface formed between iron (Fe) and an ordered oxygen (O) atomic layer, and an adsorbate-induced enhancement of electronic correlations is found. It is demonstrated that this enhancement is responsible for a drastic narrowing of the Fe d-bands close to the Fermi energy (EF) and a reduction of the exchange splitting, which is not accounted for in the Stoner picture of ferromagnetism. In addition, correlation leads to a significant spin-dependent broadening of the electronic bands at higher binding energies and their merging with satellite features, which are manifestations of a pure many-electron behavior. Overall, adatom adsorption can be used to vary the material parameters of transition metal surfaces to access different intermediate electronic correlated regimes, which will otherwise not be accessible. The results show that the concepts developed to understand the physics and chemistry of adsorbate–metal interfaces, relevant for a variety of research areas, from spintronics to catalysis, need to be reconsidered with many-particle effects being of utmost importance. These may affect chemisorption energy, spin transport, magnetic order, and even play a key role in the emergence of ferromagnetism at interfaces between non-magnetic systems

Electrochemical synthesis of nanowire anodes from spent lithium ion batteries

A novel process is proposed to produce nanostructured batteries anodes from spent lithium-ion batteries. The electrodic powder recovered by the mechanical treatment of spent batteries was leached and the dissolved metals were precipitated as cobalt carbonates. Two different precipitation routes were separately tested producing cobalt carbonates with different Cu and Fe contents. Nanowire anodes were produced by electrodeposition into nanoporous alumina templates from the electrolytic baths prepared by dissolution of the precipitated carbonates. The electrochemical performances of the produced anodes were evaluated as compared to nanowire anodes produced with the same electrodeposition method but using a synthetic cobalt bath. The application of the carbonates produced by directly precipitating all the leached metals gave nanowires with capacity about halved as compared to the nanowires electrodeposited from the synthetic bath. Selectively removing Cu and Fe prior cobalt carbonate precipitation yielded, in contrast, nanowires with capacity initially larger and then gradually approaching that attained by the nanowire electrodeposited from the synthetic bath. A detailed analysis is presented describing the role of metallic impurities in determining the capacity of the produced nanowires. The impact of the illustrated results for the development of sustainable recycling processes of lithium-ion batteries is discussed