Abstract
To synthetically target a specific material with select performance, the underlying relationship between structure and function must be understood. For targeting magnetic properties, such understanding is underdeveloped for a relatively new class of layered hexagonal perovskites, the 12R-Ba4MMn3O12 family. Here, we perform a detailed magnetostructural study of the layered hexagonal perovskite materials 12R-Ba4MMn3O12, where M = diamagnetic Ce4+ or paramagnetic Jeff ≈ 1/2 Pr4+. The material with M = Ce4+ is an antiferromagnet below TN ≈ 7.75 K, while the material with M = Pr4+ exhibits more complex behavior, with a net moment below 200 K and a sharp peak in the susceptibility at TN ≈ 12.15 K. Guided by the susceptibility data, we conduct variable-temperature powder neutron diffraction measurements to determine the magnetic structure of these two materials. The introduction of a magnetic interlayer cation cants the spins in the Mn3O12 trimers out of plane. We further characterize the crystal and electronic structures in these compounds using powder X-ray diffraction and X-ray absorption spectroscopy measurements coupled with first-principles theoretical calculations. The resulting detailed picture of the magnetic, crystal, and electronic structure will be useful for understanding the magnetism in similar 12R hexagonal perovskites and related materials.
| Original language | English |
|---|---|
| Journal | Inorganic Chemistry |
| DOIs | |
| State | Accepted/In press - 2024 |
Funding
This work is dedicated to the memory of the late Professor Miguel A\u0301ngel Alario Franco. This article has been authored in part by an employee of National Technology & Engineering Solutions of Sandia, LLC under Contract No. DE-NA0003525 with the U.S. Department of Energy (DOE). This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding provided by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Division of Materials Science, through the Office of Science Funding Opportunity Announcement (FOA) Number DE-FOA-0002676: Chemical and Materials Sciences to Advance Clean-Energy Technologies and Transform Manufacturing. This research used HPC resources at NREL, sponsored by DOE, Office of Energy Efficiency and Renewable Energy. A portion of this research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to HB-2A on proposal number IPTS-32018.1. This research used beamline 28-ID-2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Use of the Stanford Synchrotron Radiation Light source, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. R.A.K. gratefully acknowledges funding from the U.S. DOE, Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Office (HFTO) contract no. DE-AC36-8GO28308 to the National Renewable Energy Laboratory (NREL). Certain commercial equipment, instruments, or materials are identified in this document. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology nor does it imply that the products identified are necessarily the best available for the purpose. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government.