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Title
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{110}-Layered B-cation ordering in the anion-deficient perovskite with the crystallographic shear structure
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Author
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Abstract
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| 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 A(n)B(n)O(3n-2) homologous series with unit-cell parameters related to the perovskite subcell a(p) approximate to 4.0 angstrom as a(p)root 2 x a(p) x 5a(p)root 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) over bar 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, Fe-57 Mossbauer 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 Mossbauer spectroscopy indicate a broadened magnetic transition around T-N similar to 45 K and the onset of local magnetic fields at low temperatures. The magnetic order is probably reminiscent of that in other A(n)B(n)O(3n-2) homologues, where G-type AFM order within the perovskite blocks has been observed. |
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Language
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English
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Source (journal)
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Dalton Transactions : an international journal of inorganic chemistry / Royal Society of Chemistry [London] - Cambridge, 2003, currens
Journal of the Chemical Society : Dalton transactions. - London, 1972 - 1999
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Publication
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Cambridge
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Royal Society of Chemistry
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2015
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ISSN
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1477-9226
[print]
1477-9234
[online]
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DOI
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10.1039/C4DT03867C
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Volume/pages
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44
:23
(2015)
, p. 10753-10762
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ISI
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000355701000026
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Pubmed ID
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25695142
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Full text (Publisher's DOI)
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Full text (open access)
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Full text (publisher's version - intranet only)
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