Transformation of Structure, Electrical Conductivity, and Magnetism in AA'Fe2O6-δ, A = Sr, Ca and A' = Sr

Hona, Ram Krishna; Huq, Ashfia; Mulmi, Suresh; Ramezanipour, Farshid

doi:10.1021/acs.inorgchem.7b01228

Title: Transformation of Structure, Electrical Conductivity, and Magnetism in AA'Fe₂O_6-δ, A = Sr, Ca and A' = Sr

Journal Article · Wed Aug 09 00:00:00 EDT 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b01228· OSTI ID:1429186

Hona, Ram Krishna ^[1]; Huq, Ashfia ^[2]; Mulmi, Suresh ^[1];

^[1]

Univ. of Louisville, KY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The ability to control electrical properties and magnetism by varying the crystal structure using the effect of the A-site cation in oxygen-deficient perovskites has been studied in AA’Fe₂O_6-δ, where A=Sr, Ca and A’= Sr. The structure of Sr₂Fe₂O_6-δ, synthesized at 1250 °C in air, contains dimeric units of FeO₅ square-pyramids separated by FeO₆ octahedra. Here we show that this ordering scheme can be transformed by changing the A-site cations from Sr to Ca. This leads to a structure where layers of corner-sharing FeO₆ octahedra are separated by chains of FeO₄ tetrahedra. Through systematic variation of the A-site cations, we have determined the average ionic radius required for this conversion to be ~1.41 Å. We have demonstrated that the magnetic structure is also transformed. The Sr₂ compound has an incommensurate magnetic structure, where magnetic moments are in spin-density wave state, aligning perpendicular to the body diagonal of the unit cell. With the aid of neutron diffraction experiments at 10 K and 300 K, we have shown that the magnetic structure is converted into a long-range G-type antiferromagnetic system when one Sr is replaced by Ca. In this G-type ordering scheme, the magnetic moments align in the 001 direction, antiparallel to their nearest neighbors. We have also performed variable-temperature electrical conductivity studies on these materials in the temperature range 298 – 1073 K. These studies have revealed the transformation of charge transport properties, where the metallic behavior of the Sr₂-compound is converted into semiconductivity in the CaSr-material. The trend of conductivity as a function of temperature is reversed upon changing the A-site cation. The conductivity of the Sr₂ compound shows a downturn, while the conductivity of the CaSr material increases as a function of temperature. We have also shown that the CaSr-compound exhibits temperature-dependent behavior typical of a mixed ionic-electronic conducting system.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1429186

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 16; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 23 works

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Remarkable Oxygen-Evolution Activity of a Perovskite Oxide from the Ca _{2− x} Sr _x Fe ₂ O _{6− δ} Series Hona, Ram Krishna; Ramezanipour, Farshid Angewandte Chemie International Edition, Vol. 58, Issue 7 https://doi.org/10.1002/anie.201813000	journal	January 2019
Electrical properties of the ordered oxygen-deficient perovskite Ca2Fe0.5Ga1.5O5 Hona, Ram Krishna; Huq, Ashfia; Ramezanipour, Farshid Ionics, Vol. 25, Issue 3 https://doi.org/10.1007/s11581-018-2759-0	journal	October 2018
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Title: Transformation of Structure, Electrical Conductivity, and Magnetism in AA'Fe2O6-δ, A = Sr, Ca and A' = Sr

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Title: Transformation of Structure, Electrical Conductivity, and Magnetism in AA'Fe₂O_6-δ, A = Sr, Ca and A' = Sr