Local electronic structure and photoelectrochemical activity of partial chemically etched Ti-doped hematite

International audienceThe direct conversion of solar light into chemical energy or fuel through photoelectrochemical water splitting is promising as a clean hydrogen production solution. Ti-doped hematite (Ti:α-Fe 2 O 3) is a potential key photoanode material, which despite its optimal band gap, excellent chemical stability, abundance, non-toxicity and low cost, still has to be improved. Here we give evidence of a drastic improvement of the water splitting performances of Ti-doped hematite photoanodes upon a HCl wet-etching. In addition to the topography investigation by atomic force microscopy, a detailed determination of the local electronic structure has been carried out in order to understand the phenomenon and to provide new insights in the understanding of solar water splitting. Using synchrotron radiation based spectromicroscopy (X-PEEM), we investigated the X-ray absorption spectral features at the L 3 Fe edge of the as grown surface and of the wet-etched surface on the very same sample thanks to patterning. We show that HCl wet etching leads to substantial surface modifications of the oxide layer including increased roughness and chemical reduction (presence of Fe 2+) without changing the band gap. We demonstrate that these changes are profitable and correlated to the drastic changes of the photocatalytic activity

Biomineral shell formation under ocean acidification: A shift from order to chaos

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO2 leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 μatm pCO2) compared to present day conditions (380 μatm pCO2). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments. © 2016, Nature Publishing Group. All rights reserved

Magnetic iron oxide nanowires formed by reactive dewetting

The growth and reactive dewetting of ultra-thin films of iron oxides supported on Re(0001) surfaces have been imaged in-situ in real time. Initial growth forms a non-magnetic stable FeO (wüstite like) layer in a commensurate network upon which high aspect ratio nanowires of several microns length but less than 40nm width can be fabricated. The nanowires are closely aligned with the substrate crystallography and imaging by X-ray magnetic circular dichroism shows that each contain a single magnetic domain. The driving force for dewetting appears to be the minimization of strain energy of the Fe3O4 crystallites and follows the Tersoff and Tromp model in which strain is minimized at constant height by extending in one epitaxially matched direction. Such wires are promising in spintronic applications and we predict that the growth will also occur on other hexagonal substrates

Nanoscale self-organization and metastable non-thermal metallicity in Mott insulators

Mott transitions in real materials are first order and almost always associated with lattice distortions, both features promoting the emergence of nanotextured phases. This nanoscale self-organization creates spatially inhomogeneous regions, which can host and protect tran- sient non-thermal electronic and lattice states triggered by light excitation. Here, we combine time-resolved X-ray microscopy with a Landau-Ginzburg functional approach for calculating the strain and electronic real-space configurations. We investigate V2O3, the archetypal Mott insulator in which nanoscale self-organization already exists in the low-temperature monoclinic phase and strongly affects the transition towards the high-temperature corundum metallic phase. Our joint experimental-theoretical approach uncovers a remarkable out-of- equilibrium phenomenon: the photo-induced stabilisation of the long sought monoclinic metal phase, which is absent at equilibrium and in homogeneous materials, but emerges as a metastable state solely when light excitation is combined with the underlying nanotexture of the monoclinic lattice

Fabrication of Isolated Iron Nanowires

Nanoscale interconnects are an important component of molecular electronics. Here we use X-ray spectromicroscopy techniques as well as scanning probe methods to explore the self-assembled growth of insulated iron nanowires as a potential means of supplying an earth abundant solution. The intrinsic anisotropy of a TiO2(110) substrate directs the growth of micron length iron wires at elevated temperatures, with a strong metal-support interaction giving rise to ilmenite (FeTiO3) encapsulation. Iron nanoparticles that decorate the nanowires display magnetic properties that suggest other possible applications

Perpendicular local magnetization under voltage control in Ni films on ferroelectric BaTiO₃ substrates.

High-resolution magnetoelectric imaging is used to demonstrate electrical control of the perpendicular local magnetization associated with 125 nm-wide magnetic stripe domains in 100-nm-thick Ni films. This magnetoelectric coupling is achieved in zero magnetic field using strain from ferroelectric BaTiO3 substrates to control perpendicular anisotropy imposed by the growth stress. These findings may be exploited for perpendicular recording in nanopatterned hybrid media.This work was funded by Isaac Newton Trust grants 10.26(u) and 11.35 (u), UK EPSRC grant EP/G031509/1, a Herchel Smith Fellowship (X.M.), the Spanish MEC Ramón y Cajal programme (X.M.), and the Royal Society (X.M.). The authors thank Luis Hueso and Raffaele Pellicelli for discussions.This is the final published version. It first appeared at http://onlinelibrary.wiley.com/doi/10.1002/adma.201404799/abstract

Resolving the effect of oxygen vacancies on Co nanostructures using soft XAS/X-PEEM

Improving both the extent of metallic Co nanoparticle (Co NP) formation and their stability is necessary to ensure good catalytic performance, particularly for Fischer–Tropsch synthesis (FTS). Here, we observe how the presence of surface oxygen vacancies (Ovac) on TiO2 can readily reduce individual Co3O4 NPs directly into CoO/Co0 in the freshly prepared sample by using a combination of X-ray photoemission electron microscopy (X-PEEM) coupled with soft X-ray absorption spectroscopy. The Ovac are particularly good at reducing the edge of the NPs as opposed to their center, leading to smaller particles being more reduced than larger ones. We then show how further reduction (and Ovac consumption) is achieved during heating in H2/syngas (H2 + CO) and reveal that Ovac also prevents total reoxidation of Co NPs in syngas, particularly the smallest (∼8 nm) particles, thus maintaining the presence of metallic Co, potentially improving catalyst performance

Strain‐modulated ferromagnetism at an intrinsic van der Waals heterojunction

The van der Waals interaction enables atomically thin layers of exfoliated 2D materials to be interfaced in heterostructures with relaxed epitaxy conditions, however, the ability to exfoliate and freely stack layers without any strain or structural modification is by no means ubiquitous. In this work, the piezoelectricity of the exfoliated van der Waals piezoelectric α-In2Se3 is utilized to modify the magnetic properties of exfoliated Fe3GeTe2, a van der Waals ferromagnet, resulting in increased domain wall density, reductions in the transition temperature ranging from 5 to 20 K, and an increase in the magnetic coercivity. Structural modifications at the atomic level are corroborated by a comparison to a graphite/α-In2Se3 heterostructure, for which a decrease in the Tuinstra-Koenig ratio is found. Magnetostrictive ferromagnetic domains are also observed, which may contribute to the enhanced magnetic coercivity. Density functional theory calculations and atomistic spin dynamic simulations show that the Fe3GeTe2 layer is compressively strained by 0.4%, reducing the exchange stiffness and magnetic anisotropy. The incorporation of α-In2Se3 may be a general strategy to electrostatically strain interfaces within the paradigm of hexagonal boron nitride-encapsulated heterostructures, for which the atomic flatness is both an intrinsic property and paramount requirement for 2D van der Waals heterojunctions

Atomically sharp domain walls in an antiferromagnet

The interest in understanding scaling limits of magnetic textures such as domain walls spans the entire field of magnetism from its relativistic quantum fundamentals to applications in information technologies. The traditional focus of the field on ferromagnets has recently started to shift towards antiferromagnets which offer a rich materials landscape and utility in ultra-fast and neuromorphic devices insensitive to magnetic field perturbations. Here we report the observation that domain walls in an epitaxial crystal of antiferromagnetic CuMnAs can be atomically sharp. We reveal this ultimate domain wall scaling limit using differential phase contrast imaging within aberrationcorrected scanning transmission electron microscopy, which we complement by X-ray magnetic dichroism microscopy and ab initio calculations. We highlight that the atomically sharp domain walls are outside the remits of established spin-Hamiltonian theories and can offer device functionalities unparalleled in ferromagnets.Comment: 8 pages, 4 figures, Supplementary informatio