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Dy2CuZnMn4O12 perovskite, belonging to the A-site columnar-ordered quadruple perovskite family with the general composition of A2A'A''B4O12, was prepared by a high-pressure, high-temperature method at 6 GPa and 1500 K. Its crystal structure was studied by synchrotron powder X-ray diffraction between 100 K and 800 K. The ideal cation distribution (without antisite disorder) was found to realize within the sensitivity of the synchrotron X-ray diffraction method. Between 100 K and 400 K it crystallizes in space group Pmmn (No. 59) and has layered charge ordering of Mn3+ and Mn4+ at the B sites. Above 425 K, it crystallizes in space group P42/nmc (No. 137) with one crystallographic B site and an average Mn3.5+ oxidation state. The charge ordering transition (at TCO = 425 K) appears to be of the second order as no anomalies were found on differential scanning calorimetry curves and temperature dependence of the unit cell volume, and the orthorhombic a and b lattice parameters merger gradually. The compound demonstrates anisotropic thermal expansion with the c lattice parameter decreasing with increasing temperature above 280 K. A ferrimagnetic transition occurs at TC = 116 K with an additional, gradual rise of magnetic susceptibilities below 45 K, probably due to increases of the ordered moments of the Dy sublattices.

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• Creative Commons BY-NC-ND Attribution-NonCommercial-NoDerivs 4.0 International
  

Keyword: crystal structure, magnetic properties, A-site columnar-ordered perovskites, ferrimagnets, high-pressure synthesis

Date published: 2023-12-11

Publisher: American Chemical Society (ACS)

Journal:

• Inorganic Chemistry (ISSN: 1520510X) vol. 62 issue. 49 p. 20042-20049

Funding:

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1021/acs.inorgchem.3c02835

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Updated at: 2024-10-02 12:30:22 +0900

Published on MDR: 2024-10-02 12:30:22 +0900