Electronic and structural properties of single-crystal Jahn–Teller active Co1+xMn2–xO4 thin films

Blanchet, Miles D.; Heath, Jonathan J.; Kaspar, Tiffany C.; Matthews, Bethany E.; Spurgeon, Steven R.; Bowden, Mark E.; Heald, Steve M.; Issacs-Smith, Tamara; Kuroda, Marcelo A.; Comes, Ryan B.

doi:10.1088/1361-648x/abd573

Electronic and structural properties of single-crystal Jahn–Teller active Co_1+xMn_2–xO₄ thin films

Journal Article · Tue Jan 12 00:00:00 EST 2021 · Journal of Physics. Condensed Matter

DOI:https://doi.org/10.1088/1361-648x/abd573· OSTI ID:1764737

Blanchet, Miles D. ^[1]; Heath, Jonathan J. ^[1]; ^[2]; ^[2]; ^[2]; Bowden, Mark E. ^[2]; Heald, Steve M. ^[3]; ^[1]; ^[1]; ^[1]

Auburn Univ., AL (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Recent investigations on spinel CoMn₂O₄ have shown its potential for applications in water splitting and fuel cell technologies as it exhibits strong catalytic behavior through oxygen reduction reactivity. To further understand this material, we report for the first time the synthesis of single-crystalline Co_1+xMn_2-xO₄ thin films using molecular beam epitaxy. By varying sample composition, we establish links between cation stoichiometry and material properties using in-situ x-ray photoelectron spectroscopy, x-ray diffraction, scanning transmission electron microscopy, x-ray absorption spectroscopy, and spectroscopic ellipsometry. Our results indicate that excess Co ions occupy interstitial tetrahedral sites up to a certain stoichiometry, then are substitutional for octahedrally-coordinated Mn beyond this threshold. Here, we compare these results with density functional theory models of stoichiometric CoMn₂O₄ to understand how the Jahn-Teller distortion and hybridization in Mn-O bonds impact the ability to hole dope the material with excess Co. The findings provide important insights into CoMn₂O₄ and related spinel oxides for future application as inexpensive oxygen reduction reaction catalysts.

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 Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

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

OSTI ID:: 1764737

Alternate ID(s):: OSTI ID: 1774810
OSTI ID: 23186444

Report Number(s):: PNNL-SA--156954

Journal Information:: Journal of Physics. Condensed Matter, Journal Name: Journal of Physics. Condensed Matter Journal Issue: 12 Vol. 33; ISSN 0953-8984

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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Electronic and structural properties of single-crystal Jahn–Teller active Co1+xMn2–xO4 thin films

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