Jahn–Teller-driven phase segregation in MnxCo3–xO4 spinel thin films

Blanchet, Miles D.; Matthews, Bethany E.; Spurgeon, Steven R.; Heald, Steve M.; Isaacs-Smith, Tamara; Comes, Ryan B.

doi:10.1116/6.0002329

Jahn–Teller-driven phase segregation in Mn_xCo_3–xO₄ spinel thin films

Journal Article · Wed Jul 12 00:00:00 EDT 2023 · Journal of Vacuum Science and Technology A

DOI:https://doi.org/10.1116/6.0002329· OSTI ID:2000700

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Auburn Univ., AL (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Transition metal spinel oxides comprised of earth-abundant Mn and Co have long been explored for their use in catalytic reactions and energy storage. However, understanding functional properties can be challenging due to differences in sample preparation and the ultimate structural properties of the materials. Epitaxial thin film synthesis provides a novel means of producing precisely controlled materials to explore the variations reported in the literature. In this work, Mn_xCo_3–xO₄ samples from x = 0 to x = 1.28 were synthesized through molecular beam epitaxy and characterized to develop a material properties map as a function of stoichiometry. Here, films were characterized via in situ x-ray photoelectron spectroscopy, x-ray diffraction, scanning transmission electron microscopy, and polarized K-edge x-ray absorption spectroscopy. Mn cations within this range were found to be octahedrally coordinated, in line with an inverse spinel structure. Samples largely show mixed Mn³⁺ and Mn⁴⁺ character with evidence of phase segregation tendencies with the increasing Mn content and increasing Mn³⁺ formal charge. Phase segregation may occur due to structural incompatibility between cubic and tetragonal crystal structures associated with Mn⁴⁺ and Jahn–Teller active Mn³⁺ octahedra, respectively. Our results help in explaining the reported differences across samples in these promising materials for renewable energy technologies.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-06CH11357; AC05-76RL01830

OSTI ID:: 2000700

Report Number(s):: PNNL-SA--179218

Journal Information:: Journal of Vacuum Science and Technology A, Journal Name: Journal of Vacuum Science and Technology A Journal Issue: 5 Vol. 41; ISSN 0734-2101

Publisher:: American Vacuum Society / AIPCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Jahn-Teller distortion
epitaxy
stoichiometry
thin films
transmission electron microscopy
x-ray absorption spectroscopy
x-ray diffraction
x-ray photoelectron spectroscopy