TY - JOUR
T1 - Effect of fluoropolymer composition on topochemical synthesis of SrMn O3-δ Fγ oxyfluoride films
AU - Wang, Jiayi
AU - Shin, Yongjin
AU - Arenholz, Elke
AU - Lefler, Benjamin M.
AU - Rondinelli, James M.
AU - May, Steven J.
N1 - Funding Information:
Work at Drexel was supported by the National Science Foundation (NSF Grant No. CMMI-1562223). Film synthesis utilized deposition instrumentation acquired through an Army Research Office DURIP grant (Grant No. W911NF-14-1-0493). Y.S and J.M.R. were supported by NSF (Grant No. DMR-1454688). This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under Contract No. DE-AC02-05CH11231.
Publisher Copyright:
© 2018 American Physical Society.
PY - 2018/7/31
Y1 - 2018/7/31
N2 - We report the synthesis of SrMnO3-δFγ 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.
AB - We report the synthesis of SrMnO3-δFγ 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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U2 - 10.1103/PhysRevMaterials.2.073407
DO - 10.1103/PhysRevMaterials.2.073407
M3 - Article
AN - SCOPUS:85059619497
SN - 2475-9953
VL - 2
JO - Physical Review Materials
JF - Physical Review Materials
IS - 7
M1 - 073407
ER -