{110}-layered B-cation ordering in the anion-deficient perovskite Pb2.4Ba2.6Fe2Sc2TiO13 with the crystallographic shear structureстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 19 сентября 2015 г.
Аннотация:Novel anion-deficient perovskite-based compound Pb2.4Ba2.6Fe2Sc2TiO13 was synthesized via the citrate-based route. This compound is an n = 5 member of the AnBnO3n-2 homologous series with unit-cell parameters related to the perovskite subcell ap ~ 4.0 Å as ap2×ap×5ap2. The crystal structure of Pb2.4Ba2.6Fe2Sc2TiO13 consists of quasi-2D perovskite blocks with a thickness of three octahedral layers separated by the 1/2[110](-101)p crystallographic shear (CS) planes, which are parallel to the {110} plane of the perovskite subcell. The CS planes transform the corner-sharing octahedra into chains of edge-sharing distorted tetragonal pyramids. Using a combination of neutron powder diffraction, 57Fe Mössbauer spectroscopy and atomic resolution electron energy-loss spectroscopy we demonstrate that the B-cations in Pb2.4Ba2.6Fe2Sc2TiO13 are ordered along the {110} perovskite layers with Fe3+ in distorted tetragonal pyramids along the CS planes, Ti4+ preferentially in the central octahedra of the perovskite blocks and Sc3+ in the outer octahedra of the perovskite blocks. Magnetic susceptibility and Möessbauer spectroscopy indicate a broadened magnetic transition around TN ~ 45 K and the onset of local magnetic fields at low temperatures. The magnetic order is probably reminiscent of that in other AnBnO3n-2 homologues, where G-type AFM order within the perovskite blocks has been observed.