Entropy Engineering and Tunable Magnetic Order in the Spinel High-Entropy Oxide

Johnstone, Graham H. J.; González-Rivas, Mario U.; Taddei, Keith M.; Sutarto, Ronny; Sawatzky, George A.; Green, Robert J.; Oudah, Mohamed; Hallas, Alannah M.

doi:10.1021/jacs.2c06768

Entropy Engineering and Tunable Magnetic Order in the Spinel High-Entropy Oxide

Journal Article · Wed Nov 02 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c06768· OSTI ID:1923148

Johnstone, Graham H. J. ^[1]; ^[1]; ^[2]; Sutarto, Ronny ^[3]; Sawatzky, George A. ^[1]; Green, Robert J. ^[4]; Oudah, Mohamed ^[1]; ^[1]

Univ. of British Columbia, Vancouver, BC (Canada). Stewart Blusson Quantum Matter Institute
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Saskatchewan, Saskatoon, SK (Canada). Canadian Light Source, Inc.
Univ. of British Columbia, Vancouver, BC (Canada). Stewart Blusson Quantum Matter Institute; Univ. of Saskatchewan, Saskatoon, SK (Canada)

Spinel oxides are an ideal setting to explore the interplay between configurational entropy, site selectivity, and magnetism in high-entropy oxides (HEOs). In this work, we characterize the magnetic properties of the spinel (Cr, Mn, Fe, Co, Ni)₃O₄ and study the evolution of its magnetism as a function of nonmagnetic gallium substitution. Across the range of compositions studied here, from 0 to 40% Ga, magnetic susceptibility and powder neutron diffraction measurements show that ferrimagnetic order is robust in the spinel HEO. However, we also find that the ferrimagnetic order is highly tunable, with the ordering temperature, saturated and sublattice moments, and magnetic hardness all varying significantly as a function of Ga concentration. Through X-ray absorption and magnetic circular dichroism, we are able to correlate this magnetic tunability with strong site selectivity between the various cations and the tetrahedral and octahedral sites in the spinel structure. In particular, we find that while Ni and Cr are largely unaffected by the substitution with Ga, the occupancies of Mn, Co, and Fe are each significantly redistributed. Ga substitution also requires an overall reduction in the transition metal valence, and this is entirely accommodated by Mn. Finally, we show that while site selectivity has an overall suppressing effect on the configurational entropy, over a certain range of compositions, Ga substitution yields a striking increase in the configurational entropy and may confer additional stabilization. In conclusion, spinel oxides can be tuned seamlessly from the low-entropy to the high-entropy regime, making this an ideal platform for entropy engineering.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: CIFAR Azrieli Global Scholars Program; Canada First Research Excellence Fund; Canada Foundation for Innovation; Canadian Institutes of Health Research; Government of Saskatchewan; National Research Council Canada; Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Science (SC), Basic Energy Sciences (BES); University of Saskatchewan

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1923148

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 45 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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