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Intrinsic Triple Order in A‐site Columnar‐Ordered Quadruple Perovskites: Proof of Concept
Author(s) -
Belik Alexei A.,
Khalyavin Dmitry D.,
Zhang Lei,
Matsushita Yoshitaka,
Katsuya Yoshio,
Tanaka Masahiko,
Johnson Roger D.,
Yamaura Kazunari
Publication year - 2018
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201800593
Subject(s) - order (exchange) , perovskite (structure) , chemistry , materials science , crystallography , business , finance
There is an emerging topic in the science of perovskite materials: A‐site columnar‐ordered A 2 A′A′′B 4 O 12 quadruple perovskites, which have an intrinsic triple order at the A sites. However, in many examples reported so far, A′ and A′′ cations are the same, and the intrinsic triple order is hidden. Here, we investigate structural properties of Dy 2 CuMnMn 4 O 12 (1) and Ho 2 MnGaMn 4 O 12 (2) by neutron and X‐ray powder diffraction and prove the triple order at the A sites. The cation distributions determined are [Ho 2 ] A [Mn] A′ [Ga 0.66 Mn 0.34 ] A′′ [Mn 3.66 Ga 0.34 ] B O 12 and [Dy 2 ] A [Cu 0.73 Mn 0.27 ] A′ [Mn 0.80 Dy 0.20 ] A′′ [Mn 1.89 Cu 0.11 ] B1 [Mn 2 ] B2 O 12 . There are clear signatures of Jahn‐Teller distortions in 1 and 2, and the orbital pattern is combined with an original type of charge ordering in 1. Columnar‐ordered quadruple perovskites represent a new playground to study complex interactions between different electronic degrees of freedom. No long‐range magnetic order was found in 2 by neutron diffraction, and its magnetic properties in low fields are dominated by an impurity with negative magnetization or magnetization reversal. On the other hand, 1 shows three magnetic transitions at 21, 125, and 160 K.