Imaging Oxygen Defects and their Motion at a Manganite Surface

Manganites are technologically important materials, used widely as solid oxide fuel cell cathodes: they have also been shown to exhibit electroresistance. Oxygen bulk diffusion and surface exchange processes are critical for catalytic action, and numerous studies of manganites have linked electroresistance to electrochemical oxygen migration. Direct imaging of individual oxygen defects is needed to underpin understanding of these important processes. It is not currently possible to collect the required images in the bulk, but scanning tunnelling microscopy could provide such data for surfaces. Here we show the first atomic resolution images of oxygen defects at a manganite surface. Our experiments also reveal defect dynamics, including oxygen adatom migration, vacancy-adatom recombination and adatom bistability. Beyond providing an experimental basis for testing models describing the microscopics of oxygen migration at transition metal oxide interfaces, our work resolves the long-standing puzzle of why scanning tunnelling microscopy is more challenging for layered manganites than for cuprates.Comment: 7 figure

The surface layer of cleaved bilayer manganites

Recently, several informative reports have been published on spectroscopy experiments performed on cleaved surfaces of the bilayered colossal magnetoresistive manganite La2-2xSr1+2xMn2O7 (Konoto et al 2004 Phys. Rev. Lett. 93 107201, Freeland et al 2005 Nat. Mater. 4 62, Mannella et al 2005 Nature 438 474, Ronnow et al 2006 Nature 440 1025). For the detailed interpretation of these results, it is of importance to know exactly which layer within the crystal structure is exposed to the surface upon cleavage. Here we combine crystal structure arguments, scanning tunnelling microscopy and x-ray photoelectron spectroscopy measurements to demonstrate that the crystals cleave between the rare-earth rock-salt oxide layers, leaving one outermost rare-earth oxide layer before the first electronically active MnO bilayer

The surface layer of cleaved bilayer manganites

Recently, several informative reports have been published on spectroscopy experiments performed on cleaved surfaces of the bilayered colossal magnetoresistive manganite La2−2x Sr1+2x Mn2O7 (Konoto et al 2004 Phys. Rev. Lett. 93 107201, Freeland et al 2005 Nat. Mater. 4 62, Mannella et al 2005 Nature 438 474, Rønnow et al 2006 Nature 440 1025). For the detailed interpretation of these results, it is of importance to know exactly which layer within the crystal structure is exposed to the surface upon cleavage. Here we combine crystal structure arguments, scanning tunnelling microscopy and x-ray photoelectron spectroscopy measurements to demonstrate that the crystals cleave between the rare-earth rock-salt oxide layers, leaving one outermost rare-earth oxide layer before the first electronically active MnO bilayer

Analysis of the electronic configuration of the pulsed laser deposited La 0.7 Ca 0.3 MnO 3 thin films

Abstract The electronic properties of La 0.7 Ca 0.3 MnO 3Àd thin films grown by the pulsed reactive crossed beam laser ablation method are investigated. The effects of post-deposition annealing of epitaxial La 0.7 Ca 0.3 MnO 3Àd thin films have been investigated using X-ray photoelectron spectroscopy (surface sensitive) and hard X-ray absorption spectroscopy (bulk sensitive). The films deposited in the high vacuum are oxygen deficient and contain mostly Mn 3+ . High temperature annealing in a flowing oxygen atmosphere partially changes the Mn oxidation state from +3 towards +3.4. These changes should favor a metal-like conduction and a ferromagnetic double exchange transport mechanism in the annealed thin films.