Tobias M. Huber

Apparent Oxygen Uphill Diffusion in La0.8Sr0.2MnO3 Thin Films upon Cathodic Polarization

Abstract The impact of cathodic bias on oxygen transport in La0.8Sr0.2MnO3 (LSM) thin films was investigated. Columnar‐grown LSM thin films with different microstructures were deposited by pulsed laser deposition. 18O tracer experiments were performed on thin film microelectrodes with an applied cathodic bias of −300 or −450 mV, and the microelectrodes were subsequently analyzed by time‐of‐flight secondary ion mass spectrometry. The 18O concentration in the cathodically polarized LSM microelectrodes was strongly increased relative to that in the thermally annealed film (without bias). Most remarkable, however, was the appearance of a pronounced 18O fraction maximum in the center of the films. This strongly depended on the applied bias and on the microstructure of the LSM thin layers. The unusual shape of the 18O depth profiles was caused by a combination of Wagner–Hebb‐type stoichiometry polarization of the LSM bulk, fast grain boundary transport and voltage‐induced modification of the oxygen incorporation kinetics,

Dislocations Accelerate Oxygen Ion Diffusion in La0.8Sr0.2MnO3 Epitaxial Thin Films

Revealing whether dislocations accelerate oxygen ion transport is important for providing abilities in tuning the ionic conductivity of ceramic materials. In this study, we report how dislocations affect oxygen ion diffusion in Sr-doped LaMnO3 (LSM), a model perovskite oxide that serves in energy conversion technologies. LSM epitaxial thin films with thicknesses ranging from 10 nm to more than 100 nm were prepared by pulsed laser deposition on single-crystal LaAlO3 and SrTiO3 substrates. The lattice mismatch between the film and substrates induces compressive or tensile in-plane strain in the LSM layers. This lattice strain is partially reduced by dislocations, especially in the LSM films on LaAlO3. Oxygen isotope exchange measured by secondary ion mass spectrometry revealed the existence of at least two very different diffusion coefficients in the LSM films on LaAlO3. The diffusion profiles can be quantitatively explained by the existence of fast oxygen ion diffusion along threading dislocations that is faster by up to 3 orders of magnitude compared to that in LSM bulk.