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

Electrical detection of the spin reorientation transition in antiferromagnetic TmFeO3 thin films by spin Hall magnetoresistance

TmFeO3 (TFO) is a canted antiferromagnet that undergoes a spin reorientation transition (SRT) with temperature between 82 and 94 K in single crystals. In this temperature region, the Neel vector continuously rotates from the crystallographic c axis (below 82 K) to the a axis (above 94 K). The SRT allows for a temperature control of distinct antiferromagnetic states without the need for a magnetic field, making it apt for applications working at terahertz frequencies. For device applications, thin films of TFO are required as well as an electrical technique for read-out of the magnetic state. Here, we demonstrate that orthorhombic TFO thin films can be grown by pulsed laser deposition and the detection of the SRT in TFO thin films can be accessed by making use of the all-electrical spin Hall magnetoresistance, in good agreement for the temperature range where the SRT occurs in bulk crystals. Our results demonstrate that one can electrically detect the SRT in insulators

An insulating doped antiferromagnet with low magnetic symmetry as a room temperature spin conduit

We report room-temperature long-distance spin transport of magnons in antiferromagnetic thin-film hematite doped with Zn. The additional dopants significantly alter the magnetic anisotropies, resulting in a complex equilibrium spin structure that is capable of efficiently transporting spin angular momentum at room temperature without the need for a well-defined, pure easy-axis or easy-plane anisotropy. We find intrinsic magnon spin-diffusion lengths of up to 1.5 mu m, and magnetic domain governed decay lengths of 175nm for the low-frequency magnons, through electrical transport measurements demonstrating that the introduction of nonmagnetic dopants does not strongly reduce the transport length scale, showing that the magnetic damping of hematite is not significantly increased. We observe a complex field dependence of the nonlocal signal independent of the magnetic state visible, in the local magnetoresistance and direct magnetic imaging of the antiferromagnetic domain structure. We explain our results in terms of a varying and applied field-dependent ellipticity of the magnon modes reaching the detector electrode allowing us to tune the spin transport. Published under license by AIP Publishing

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