Issue 23, 2015

{110}-Layered B-cation ordering in the anion-deficient perovskite Pb2.4Ba2.6Fe2Sc2TiO13 with the crystallographic shear structure

Abstract

A 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 ap√2 × ap × 5ap√2. 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]([1 with combining macron]01)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 Mössbauer 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.

Graphical abstract: {110}-Layered B-cation ordering in the anion-deficient perovskite Pb2.4Ba2.6Fe2Sc2TiO13 with the crystallographic shear structure

  • This article is part of the themed collection: Perovskites

Supplementary files

Article information

Article type
Paper
Submitted
16 Dec 2014
Accepted
22 Jan 2015
First published
26 Jan 2015

Dalton Trans., 2015,44, 10753-10762

{110}-Layered B-cation ordering in the anion-deficient perovskite Pb2.4Ba2.6Fe2Sc2TiO13 with the crystallographic shear structure

O. A. Tyablikov, D. Batuk, A. A. Tsirlin, M. Batuk, V. Yu. Verchenko, D. S. Filimonov, K. V. Pokholok, D. V. Sheptyakov, M. G. Rozova, J. Hadermann, E. V. Antipov and A. M. Abakumov, Dalton Trans., 2015, 44, 10753 DOI: 10.1039/C4DT03867C

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