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Effect of fluoropolymer composition on topochemical synthesis of SrMnO3-delta F gamma oxyfluoride films
Journal article   Open access   Peer reviewed

Effect of fluoropolymer composition on topochemical synthesis of SrMnO3-delta F gamma oxyfluoride films

Jiayi Wang, Yongjin Shin, Elke Arenholz, Benjamin M. Lefler, James M. Rondinelli and Steven J. May
Physical review materials, v 2(7)
31 Jul 2018
url
https://doi.org/10.1103/physrevmaterials.2.073407View
Accepted (AM)Open Access (Publisher-Specific) Open

Abstract

Materials Science Materials Science, Multidisciplinary Science & Technology Technology
We report the synthesis of SrMnO3-delta F gamma perovskite oxyfluoride thin films using a vapor transport method to fluorinate as-grown SrMnO2.5 epitaxial thin films. The influence of the fluoropolymer, which acts as a fluorine vapor source, was investigated by utilizing polyvinyl fluoride (PVF), polyvinylidene difluoride (PVDF), and polytetrafluoroethylene (PTFE) in the reaction. The same process was carried out with polyethylene to isolate the role of carbon in the vapor transport process. The F distribution was probed by x-ray photoemission spectroscopy, which confirmed the incorporation of F into the films and revealed higher F concentrations in films exposed to PVF and PVDF compared to PTFE. The c-axis parameter expands after fluorination, a result consistent with density functional theory calculations that attribute the volume expansion to elongated Mn-F bonds compared to shorter Mn-O bonds. Using x-ray absorption spectroscopy, we show that the fluorination process reduces the nominal Mn oxidation state suggesting that F substitutes on O sites in the lattice as opposed to filling anion vacancy sites, a finding further supported by calculated formation energies of different F site occupancies. These results provide insights into topochemical fluorination of perovskite oxides, which should enable future synthesis and design efforts focused on oxyfluoride heterostructures.

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Domestic collaboration
Web of Science research areas
Materials Science, Multidisciplinary
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