American Chemical Society
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Structural and Magnetic Phase Transitions in the AnBnO3n–2 Anion-Deficient Perovskites Pb2Ba2BiFe5O13 and Pb1.5Ba2.5Bi2Fe6O16

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journal contribution
posted on 2013-07-15, 00:00 authored by A. M. Abakumov, M. Batuk, A. A. Tsirlin, O. A. Tyablikov, D. V. Sheptyakov, D. S. Filimonov, K. V. Pokholok, V. S. Zhidal, M. G. Rozova, E. V. Antipov, J. Hadermann, G. Van Tendeloo
Novel anion-deficient perovskite-based ferrites Pb2Ba2BiFe5O13 and Pb1.5Ba2.5Bi2Fe6O16 were synthesized by solid-state reaction in air. Pb2Ba2BiFe5O13 and Pb1.5Ba2.5Bi2Fe6O16 belong to the perovskite-based AnBnO3n–2 homologous series with n = 5 and 6, respectively, with a unit cell related to the perovskite subcell ap as ap√2 × ap × nap√2. Their structures are derived from the perovskite one by slicing it with 1/2[110]p(1̅01)p crystallographic shear (CS) planes. The CS operation results in (1̅01)p-shaped perovskite blocks with a thickness of (n – 2) FeO6 octahedra connected to each other through double chains of edge-sharing FeO5 distorted tetragonal pyramids which can adopt two distinct mirror-related configurations. Ordering of chains with a different configuration provides an extra level of structure complexity. Above T ≈ 750 K for Pb2Ba2BiFe5O13 and T ≈ 400 K for Pb1.5Ba2.5Bi2Fe6O16 the chains have a disordered arrangement. On cooling, a second-order structural phase transition to the ordered state occurs in both compounds. Symmetry changes upon phase transition are analyzed using a combination of superspace crystallography and group theory approach. Correlations between the chain ordering pattern and octahedral tilting in the perovskite blocks are discussed. Pb2Ba2BiFe5O13 and Pb1.5Ba2.5Bi2Fe6O16 undergo a transition into an antiferromagnetically (AFM) ordered state, which is characterized by a G-type AFM ordering of the Fe magnetic moments within the perovskite blocks. The AFM perovskite blocks are stacked along the CS planes producing alternating FM and AFM-aligned Fe–Fe pairs. In spite of the apparent frustration of the magnetic coupling between the perovskite blocks, all n = 4, 5, 6 AnFenO3n–2 (A = Pb, Bi, Ba) feature robust antiferromagnetism with similar Néel temperatures of 623–632 K.