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Growth and surface modification of LaFeO₃ thin films induced by reductive annealing Public Deposited

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  • The mixed electronic and ionic conductivity of perovskite oxides has enabled their use in diverse applications such as automotive exhaust catalysts, solid oxide fuel cell cathodes, and visible light photocatalysts. The redox chemistry at the surface of perovskite oxides is largely dependent on the oxidation state of the metal cations as well as the oxide surface stoichiometry. In this study, LaFeO₃ (LFO) thin films grown on yttria-stabilized zirconia (YSZ) was characterized using both bulk and surface sensitive techniques. A combination of in situ reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), and Rutherford backscattering spectrometry (RBS) demonstrated that the film is primarily textured in the [1 0 0] direction and is stoichiometric. High-resolution transmission electron microscopy measurements show regions that are dominated by [1 0 0] oriented LFO grains that are oriented with respect to the substrates lattice. However, selected regions of the film show multiple domains of grains that are not [1 0 0] oriented. The film was annealed in an ultra-high vacuum chamber to simulate reducing conditions and studied by angle-resolved X-ray photoelectron spectroscopy (XPS). Iron was found to exist as Fe(0), Fe(II), and Fe(III) depending on the annealing conditions and the depth within the film. A decrease in the concentration of surface oxygen species was correlated with iron reduction. These results should help guide and enhance the design of LFO materials for catalytic applications.
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  • Flynn, B. T., Zhang, K. H. L., Shutthanandan, V., Varga, T., Colby, R. J., Oleksak, R. P., ... Thevuthasan, S. (2015). Growth and surface modification of LaFeO₃ thin films induced by reductive annealing. Applied Surface Science, 330, 309-315. doi:10.1016/j.apsusc.2015.01.028
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  • 330
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  • B.T.F. and G.S.H. gratefully acknowledge support from theSemiconductor Research Corporation under contract number2013-OJ-2438.001 and the Center for Sustainable Materials Chemistry,which is supported by the US National Science Foundationunder grant number CHE-1102637. S.A.C. and M.A.H. were supportedby BES, Division of Chemical Sciences, Geosciences, andBiosciences. The research was performed using EMSL, a national scientificuser facility sponsored by the Department of Energy’s Officeof Biological and Environmental Research and located at PacificNorthwest National Laboratory.
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