Crystal Structure, Defects, Magnetic and Dielectric Properties of the Layered Bi3n+1Ti7Fe3n-3O9n+11 Perovskite-Anatase Intergrowths

Dmitry Batuk; Maria Batuk; Dmitry S Filimonov; Konstantin V Zakharov; Olga S Volkova; Alexander N Vasiliev; Oleg A Tyablikov; Joke Hadermann; Artem M Abakumov

doi:10.1021/acs.inorgchem.6b02559

Crystal Structure, Defects, Magnetic and Dielectric Properties of the Layered Bi_3n+1Ti₇Fe_3n-3O_9n+11 Perovskite-Anatase Intergrowths

Inorg Chem. 2017 Jan 17;56(2):931-942. doi: 10.1021/acs.inorgchem.6b02559. Epub 2016 Dec 23.

Authors

Dmitry Batuk¹, Maria Batuk¹, Dmitry S Filimonov², Konstantin V Zakharov³, Olga S Volkova^{3

4

5}, Alexander N Vasiliev^{3

4

5}, Oleg A Tyablikov², Joke Hadermann¹, Artem M Abakumov^{1

2

6}

Affiliations

¹ Electron Microscopy for Material Science (EMAT), University of Antwerp , Groenenborgerlaan 171, B-2020 Antwerp, Belgium.
² Chemistry Department, Moscow State University , 119991 Moscow, Russia.
³ Physics Department, Moscow State University , 119991 Moscow, Russia.
⁴ Theoretical Physics and Applied Mathematics Department, Ural Federal University , 620002 Ekaterinburg, Russia.
⁵ National University of Science and Technology "MISiS″ , 119049 Moscow, Russia.
⁶ Skolkovo Institute of Science and Technology , Nobel str. 3, 143026 Moscow, Russia.

PMID: 28009509
DOI: 10.1021/acs.inorgchem.6b02559

Abstract

The Bi_3n+1Ti₇Fe_3n-3O_9n+11 materials are built of (001)_p plane-parallel perovskite blocks with a thickness of n (Ti,Fe)O₆ octahedra, separated by periodic translational interfaces. The interfaces are based on anatase-like chains of edge-sharing (Ti,Fe)O₆ octahedra. Together with the octahedra of the perovskite blocks, they create S-shaped tunnels stabilized by lone pair Bi³⁺ cations. In this work, the structure of the n = 4-6 Bi_3n+1Ti₇Fe_3n-3O_9n+11 homologues is analyzed in detail using advanced transmission electron microscopy, powder X-ray diffraction, and Mössbauer spectroscopy. The connectivity of the anatase-like chains to the perovskite blocks results in a 3a_p periodicity along the interfaces, so that they can be located either on top of each other or with shifts of ±a_p along [100]_p. The ordered arrangement of the interfaces gives rise to orthorhombic Immm and monoclinic A2/m polymorphs with the unit cell parameters a = 3a_p, b = b_p, c = 2(n + 1)c_p and a = 3a_p, b = b_p, c = 2(n + 1)c_p - a_p, respectively. While the n = 3 compound is orthorhombic, the monoclinic modification is more favorable in higher homologues. The Bi_3n+1Ti₇Fe_3n-3O_9n+11 structures demonstrate intricate patterns of atomic displacements in the perovskite blocks, which are supported by the stereochemical activity of the Bi³⁺ cations. These patterns are coupled to the cationic coordination of the oxygen atoms in the (Ti,Fe)O₂ layers at the border of the perovskite blocks. The coupling is strong in the n = 3, 4 homologues, but gradually reduces with the increasing thickness of the perovskite blocks, so that, in the n = 6 compound, the dominant mode of atomic displacements is aligned along the interface planes. The displacements in the adjacent perovskite blocks tend to order antiparallel, resulting in an overall antipolar structure. The Bi_3n+1Ti₇Fe_3n-3O_9n+11 materials demonstrate an unusual diversity of structure defects. The n = 4-6 homologues are robust antiferromagnets below T_N = 135, 220, and 295 K, respectively. They show a high dielectric constant that weakly increases with temperature and is relatively insensitive to the Ti/Fe ratio.