Structural relaxations around Ti, Cr and Fe impurities in alpha-Al2O3 probed by x-ray absorption near edge structure combined with first-principles calculations

We determine the structural relaxations around paramagnetic impurities (Ti, Cr, Fe) in corundum (alpha-Al2O3), by combining x-ray absorption near edge structure (XANES) experiments and ab initio calculations. The structural relaxations are found to be very local. We then show that XANES is sensitive to small variations in interatomic distances within the coordination shell of the absorbing atom. The experiments were carried out on single crystals of ruby and sapphires. Linear dichroic signals are essential to characterize the geometry of the impurity site. The calculations were performed within a self-consistent ``non muffin-tin'' framework, that uses pseudopotentials, plane-wave basis set, and the continued fraction for the absorption cross section

Unraveling Bulk and Grain Boundary Electrical Properties in La0.8Sr0.2Mn1-yO3 Thin Films

Grain boundaries in Sr-doped LaMnO3 thin films have been shown to strongly influence the electronic and oxygen mass transport properties, being able to profoundly modify the nature of the material. The unique behaviour of the grain boundaries can be correlated with substantial modifications of the cation concentration at the interfaces, which can be tuned by changing the overall cationic ratio in the films. In this work, we study the electronic properties of La0.8Sr0.2Mn1-yO3 thin films with variable Mn content. The influence of the cationic composition on the grain boundary and grain bulk electronic properties is elucidated by studying the manganese valence state evolution using spectroscopy techniques and by confronting the electronic properties of epitaxial and polycrystalline films. Substantial differences in the electronic conduction mechanism are found in the presence of grain boundaries and depending on the manganese content. Moreover, the unique defect chemistry of the nanomaterial is elucidated by measuring the electrical resistance of the thin films as a function of oxygen partial pressure, disclosing the importance of the cationic local non-stoichiometry on the thin films behavior

Structural and electronic relaxations around substitutional Cr3+ and Fe3+ ions in corundum

International audienceThe local arrangement of atoms surrounding a substitutional Cr3+ and Fe3+ ion in α-Al2O3: Cr3+ (ruby) and in α-Al2O3:(Fe−Ti) (blue sapphire) has been studied experimentally using natural x-ray linear dichroism absorption at the Cr and Fe K edge. The isotropic and dichroic signals have been recorded using single crystals and a reliable method has been applied to remove diffraction peaks. Results given by the analysis of both signals are compared with ab initio density functional calculations. This study reveals that the introduction of an impurity ion in the structure leads to relaxations that are very local in nature. The oxygen atoms in the coordination shell relax to an arrangement similar to that for Cr in α-Cr2O3 or for Fe in α-Fe2O3. Aluminum or oxygen atoms at a farther distance are weakly affected by the presence of the impurity