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Register a new userInterrelation of epitaxial strain and oxygen deficiency in La0.7Ca0.3MnO3-{delta} thin films
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Added by
Hanns-Ulrich Habermeier
Publication date
2014
fields
Physics
and research's language is
English
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The interrelation between the epitaxial strain and oxygen deficiency in La0.7Ca0.3MnO3-{delta} thin films was studied in terms of structural and functional properties. The films with a thickness of 1000{AA} were prepared using a PLD system equipped with a RHEED facility and a pyrometric film temperature control. The epitaxial strain and the oxygen deficiency in the samples were systematically modified using three different substrates: SrTiO3, (LaAlO3)0.3-(Sr2AlTaO6)0.7 and LaSrAlO4, and four different oxygen pressures during film growth ranging from 0.27mbar to 0.1mbar. It could be demonstrated that the oxygen incorporation depends on the epitaxial strain: oxygen vacancies were induced to accommodate tensile strain whereas the compressive strain suppressed the generation of oxygen vacancies.
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The ability to manipulate oxygen anion defects rather than metal cations in complex oxides can facilitate creating new functionalities critical for emerging energy and device technologies. However, the difficulty in activating oxygen at reduced temperatures hinders the deliberate control of important defects, oxygen vacancies. Here, strontium cobaltite (SrCoOx) is used to demonstrate that epitaxial strain is a powerful tool for manipulating the oxygen vacancy concentration even under highly oxidizing environments and at annealing temperatures as low as 300 C. By applying a small biaxial tensile strain (2%), the oxygen activation energy barrier decreases by ~30%, resulting in a tunable oxygen deficient steady-state under conditions that would normally fully oxidize unstrained cobaltite. These strain-induced changes in oxygen stoichiometry drive the cobaltite from a ferromagnetic metal towards an antiferromagnetic insulator. The ability to decouple the oxygen vacancy concentration from its typical dependence on the operational environment is useful for effectively designing oxides materials with a specific oxygen stoichiometry.
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We report a giant resistance drop induced by dc electrical currents in La0.67Ca0.33MnO3 epitaxial thin films. Resistance of the patterned thin films decreases exponentially with increasing current and a maximum drop shows at the temperature of resistance peak Tp. Variation of resistance with current densities can be scaled below and above Tp, respectively. This work can be useful for the future applications of electroresistance.
Solid oxide oxygen ion and proton conductors are a highly important class of materials for renewable energy conversion devices like solid oxide fuel cells. Ba2In2O5 (BIO) exhibits both oxygen ion and proton conduction, in dry and humid environment, respectively. In dry environment, the brownmillerite crystal structure of BIO exhibits an ordered oxygen ion sublattice, which has been speculated to result in anisotropic oxygen ion conduction. The hydrated structure of BIO, however, resembles a perovskite and the protons in it were predicted to be ordered in layers. To complement the significant theoretical and experimental efforts recently reported on the potentially anisotropic conductive properties in BIO, we measure here the proton and oxygen ion conductivity along different crystallographic directions. Using epitaxial thin films with different crystallographic orientations the charge transport for both charge carriers is shown to be anisotropic. The anisotropy of the oxygen ion conduction can indeed be explained through the layered structure of the oxygen sublattice in brownmillerite BIO. The anisotropic proton conduction however, further supports the suggested ordering of the protonic defects in the material. The differences in proton conduction along different crystallographic directions attributed to proton ordering in BIO are of a similar extent as those observed along different crystallographic directions in materials where proton ordering is not present but where protons find preferential conduction pathways through chain-like or layered structures.
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