Strong anisotropic influence of local-field effects on the dielectric response of {\alpha}-MoO3

Dielectric properties of {\alpha}-MoO3 are investigated by a combination of valence electron-energy loss spectroscopy and ab initio calculation at the random phase approximation level with the inclusion of local-field effects (LFE). A meticulous comparison between experimental and calculated spectra is performed in order to interpret calculated dielectric properties. The dielectric function of MoO3 has been obtained along the three axes and the importance of LFE has been shown. In particular, taking into account LFE is shown to be essential to describe properly the intensity and position of the Mo-N2,3 edges as well as the low energy part of the spectrum. A detailed study of the energy-loss function in connection with the dielectric response function also shows that the strong anisotropy of the energy-loss function of {\alpha}-MoO3 is driven by an anisotropic influence of LFE. These LFE significantly dampen a large peak in {\epsilon}2, but only along the [010] direction. Thanks to a detailed analysis at specific k-points of the orbitals involved in this transition, the origin of this peak has not only been evidenced but a connection between the inhomogeneity of the electron density and the anisotropic influence of local-field effects has also been established. More specifically, this anisotropy is governed by a strongly inhomogeneous spatial distribution of the empty states. This depletion of the empty states is localized around the terminal oxygens and accentuates the electron inhomogeneity.Comment: Supplemental Material include

Oxidation-assisted graphene heteroepitaxy on copper foil

We propose an innovative, easy-to-implement approach to synthesize large-area singlecrystalline graphene sheets by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.Comment: Main text (18 pages, 6 figures) + supplementary information (26 pages, 15 figures

Electrochemical Decalcification-Exfoliation of Two-Dimensional Siligene, SixGey: Material Characterization and Perspectives for Lithium-Ion Storage

A two-dimensional (2D) silicene-germanene alloy, siligene (SixGey), a single-phase material, has attracted increased attention due to its two-elemental low-buckled composition and unique physics and chemistry. This 2D material has the potential to address the challenges caused by low electrical conductivity and the environmental instability of corresponding monolayers. Yet, the siligene structure was studied in theory, demonstrating the material’s great electrochemical potential for energy storage applications. The synthesis of free-standing siligene remains challenging and therefore hinders the research and its application. Herein we demonstrate nonaqueous electrochemical exfoliation of a few-layer siligene from a Ca1.0Si1.0Ge1.0 Zintl phase precursor. The procedure was conducted in an oxygen-free environment applying a −3.8 V potential. The obtained siligene exhibits a high quality, high uniformity, and excellent crystallinity; the individual flake is within the micrometer lateral size. The 2D SixGey was further explored as an anode material for lithium-ion storage. Two types of anode have been fabricated and integrated into lithium-ion battery cells, namely, (1) siligene-graphene oxide sponges and (2) siligene-multiwalled carbon nanotubes. The as-fabricated batteries both with/without siligene exhibit similar behavior; however there is an increase in the electrochemical characteristics of SiGe-integrated batteries by 10%. The corresponding batteries exhibit a 1145.0 mAh·g-1 specific capacity at 0.1 A·g-1. The SiGe-integrated batteries demonstrate a very low polarization, confirmed by their good stability after 50 working cycles and a decrease in the solid electrolyte interphase level that occurs after the first discharge/charge cycle. We anticipate the growing potential of emerging two-component 2D materials and their great promise for energy storage and beyond.10 página

Multiscale Analysis of the Gold Dust Defect in AISI 430 Industrial Stainless Steels: Influence of the Aluminum Content

The "Gold Dust Defect" affects the surface quality of AISI 430 ferritic stainless steels. However, there is a very limited number of studies focusing on it. To better understand its nature, we have combined several techniques, such as x-ray photoelectron spectroscopy, atomic force microscopy, and transmission electron microscopy, in order to extract a maximum of structural and compositional information. Our results show that the surface quality, microstructure, and chemistry of the samples are strongly affected by the aluminum content, the severity of the defect being the highest at the lowest Al concentration. Not only is the concentration of the defects at the surface strongly reduced when increasing the Al. at.% but the depth of the cavities is also reduced by a factor of 3 when the Al content is increased from 0.09 at.% to 0.59 at.%. Our results provide new information on the nature of this defect, and show that an increase of the aluminum content allows the Cr concentration to be maintained in the range of values required to maintain the passivity of the steel, thus improving the surface quality

Au-MoS2 Hybrids as Hydrogen Evolution Electrocatalysts

Core-shell nanoparticles provide a unique morphology to exploit electronic interactions between dissimilar materials, conferring upon them new or improved functionalities. MoS2 is a layered transition-metal disulfide that has been studied extensively for the hydrogen evolution reaction (HER) but still suffers from low electrocatalytic activity due to its poor electronic conductivity. To understand the fundamental aspects of the MoS2-Au hybrids with regard to their electrocatalytic activity, a single to a few layers of MoS2 were deposited over Au nanoparticles via a versatile procedure that allows for complete encapsulation of Au nanoparticles of arbitrary geometries. High-resolution transmission electron microscopy of the Au@MoS2 nanoparticles provides direct evidence for the core-shell morphology and also reveals the presence of morphological defects and irregularities in the MoS2 shell that are known to be more active for HER than the pristine MoS2 basal plane. Electrochemical measurements show a significant improvement in the HER activity of Au@MoS2 nanoparticles relative to freestanding MoS2 or Au-decorated MoS2. The best electrochemical performance was demonstrated by the Au nanostars - the largest Au core employed here - encapsulated in a MoS2 shell. Density-functional theory calculations show that charge transfer occurs from the Au to the MoS2 layers, producing a more conductive catalyst layer and a better electrode for electrochemical HER. The strategies to further improve the catalytic properties of such hybrid nanoparticles are discussed

Improved electrochemical conversion of CO2 to multicarbon products by using molecular doping

The conversion of CO2 into desirable multicarbon products via the electrochemical reduction reaction holds promise to achieve a circular carbon economy. Here, we report a strategy in which we modify the surface of bimetallic silver-copper catalyst with aromatic heterocycles such as thiadiazole and triazole derivatives to increase the conversion of CO2 into hydrocarbon molecules. By combining operando Raman and X-ray absorption spectroscopy with electrocatalytic measurements and analysis of the reaction products, we identified that the electron withdrawing nature of functional groups orients the reaction pathway towards the production of C2+ species (ethanol and ethylene) and enhances the reaction rate on the surface of the catalyst by adjusting the electronic state of surface copper atoms. As a result, we achieve a high Faradaic efficiency for the C2+ formation of approximate to 80% and full-cell energy efficiency of 20.3% with a specific current density of 261.4 mA cm(-2) for C2+ products. Strategies to systematically tune CO2 electroreduction to multicarbon products are of high interests. Here the authors report electron withdrawing functional group alters the reaction pathway towards C2+ products by adjusting the oxidation state of surface copper.D.V., K.Q., and H.L.W. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement no. 804320). L.L., D.V., and H.L.W acknowledge the use of TEM instrumentation provided by the Nation Facility ELECMI ICTS (`Division de Microscopia Electronica', Universidad de Cadiz, DME-UCA). L.L. acknowledges funding from the Andalusian regional government (FEDER-UCA-18-106613), the European Union's Horizon 2020 research and innovation program (grant agreement 823717-ESTEEM3), and the Spanish Ministerio de Economia y Competitividad (PID2019-107578GA-I00). K.Q. and Y.Z. acknowledge financial support from the China Postdoctoral Science Foundation (2018M633127) and the Natural Science Foundation of Guangdong Province (2018A030310602). J.L. acknowledge financial support from the National Natural Science Foundation of China (21808134). We thank Soleil Synchrotron and Andrea Zitolo for allocating beamtime at beamline Samba within the proposal 20200732

Photocatalytic removal of benzene over Ti3C2Tx MXene and TiO2–MXene composite materials under solar and NIR irradiation

MXenes, a family of two-dimensional (2D) transition metal carbides, nitrides and carbonitrides based on earth-abundant constituents, are prospective candidates for energy conversion applications, including photocatalysis. While the activity of individual MXenes towards various photocatalytic processes is still debatable, these materials were proved to be excellent co-catalysts, accelerating the charge separation and suppressing the exciton recombination. Titanium-containing MXenes are well compatible with the classical TiO2 photocatalyst. The TiO2 component can be directly grown on MXene sheets by in situ oxidation, representing a mainstream processing approach for such composites. In this study, an essentially different approach has been implemented: a series of TiO2-MXene composite materials with controlled composition and both reference end members were prepared, involving two different strategies for mixing sol-gel-derived TiO2 nanopowder with the Ti3C2Tx component, which was obtained by HF etching of self-propagating high-temperature synthesis products containing modified MAX phase Ti3C2Alz (z > 1) with nominal aluminium excess. The prospects of such composites for the degradation of organic pollutants under simulated solar light, using benzene as a model system, were demonstrated and analysed in combination with their structural, microstructural and optical properties. A notable photocatalytic activity of bare MXene under near infrared light was discovered, suggesting further prospects for light-to-energy harvesting spanning from UV-A to NIR and applications in biomedical imaging and sensors.publishe

Influence of surface preparation on physical properties of Co based contacts on n-Ge

L'influence de différentes méthodes de préparation de surface sur la microstructure et les propriétés électriques des contacts à base Co sur n-Ge a été étudiée. Il a été montré que les nettoyages thermiques s'accompagnent de la diffusion d'impuretés métalliques dans le substrat. Lors du recuit, ces impuretés sont piégées par la formation des germaniures de cobalt. Un nettoyage à 700C ou une attaque au HF permettent d'éliminer l'oxyde de germanium natif à l'interface M/SC, contrairement à un nettoyage thermique à 400C qui cependant modifie la nature chimique de l oxyde. Pour tous les échantillons, une microstructure complexe est observée après formation des germaniures. Les échantillons présentent une augmentation de la rugosité de l'interface M/SC et la coexistence des phases Co5Ge7 et CoGe2. Après un nettoyage à 400C, une microstructure particulière, attribuée à l'oxyde restant après "nettoyage" est observée. Dans tous les cas, le modèle thermoïonique ne suffit pas à expliquer le comportement des diodes Schottky. En particulier, les valeurs obtenues pour la constante de Richardson sont très en deçà de la valeur attendue. Par une analyse en température des hauteurs de barrières, nous avons montré la nécessité de raisonner en terme d'inhomogénéités de barrière, ces dernières étant influencées par la microstructure. De plus, un fort ancrage du niveau de Fermi est observé pour les contacts directs M/SC alors qu'il est partiellement levé par l'oxyde de germanium natif présent à l'interface M/SC. Finalement, nous avons montré que ce désencrage du niveau de Fermi est lié à la nature chimique de l oxyde.The influence of various surface cleaning procedures on both electrical properties and microstructure of Co based n-Ge Schottky contacts has been studied. In-depth diffusion of metallic impurities into the Ge substrate has been reported after thermal pre-treatments. After germanidation, gettering of the metallic impurities by the germanide phases has been observed. While no more oxide interlayer is observed after HF etching and thermal pre-treatment at 700C, a temperature of 400C has been found to be not enough to remove the oxide interlayer. However, it modifies the chemical nature of the oxide interlayer. A complex microstructure is reported for all the samples after germanidation. For most of the samples, the coexistence of Co5Ge7 and CoGe2 structures and an increase of the roughness of the M/SC interface have been observed. The particular microstructure observed, after germanidation, for the sample pre-treated at 400C has been ascribed to the remaining oxide interlayer. Whatever the pre-treatments, the behaviours of all the Schottky diodes could not be explained by the thermionic model only. This model leads to a large underestimation of the Richardson s constant. By a detailed analysis of the temperature dependence of the Schottky barrier heights, we have pointed out the necessity to reason in term of barrier inhomogeneity, these last being strongly influenced by the microstructure. The electrical results have been explained in the framework of the Fermi level pinning concept. While a strong Fermi level pinning is observed for intimate contacts, the presence of the native Ge oxide at the M/SC interface yields a depinning of the Fermi level. However, this depinning has been found to be dependent on the chemical nature of the oxide interlayer.POITIERS-BU Sciences (861942102) / SudocSudocFranceF

Transmission Electron Microscopy And Electron Energy-Loss Spectroscopy Studies Of Hole-Selective Molybdenum Oxide Contacts In Silicon Solar Cells

In this study, substochiometric hole-selective molybdenum oxide (MoOx) contacts in crystalline silicon (c-Si) solar cells were investigated by a combination of transmission electron microscopy (TEM) and spatially resolved electron energy-loss spectroscopy (SR-EELS). It was observed that a ≈ 4 nm SiOx interlayer grows at the MoOx/c-Si interface during the evaporation of MoOx over a c-Si substrate. SR-EELS analyses revealed the presence of a 1.5 nm diffused MoOx/indium tin oxide (ITO) interface in both as-deposited and annealed samples. Moreover, the presence of a 1 nm thin layer with a lower oxidation state of Mo was detected at the SiOx/MoOx interface in an as-deposited state, which disappears upon annealing. Overall, it was evident that no hole-blocking interlayer is formed at the MoOx/ITO interface during annealing and homogenization of the MoOx layer takes place during the annealing process. Furthermore, device simulations revealed that efficient hole collection is dependent on MoOx work function and that reduction in the work function of MoOx results in loss of band bending and negatively impacts hole selectivity