Structural modulation and spin glassiness upon oxidation in oxygen storage material LnFeMnO4+x for Ln = Y, Lu, and Yb
The mixed valence multiferroic LnFe2+Fe3+O4 (where Ln = Y, Lu, and Yb) can reversibly uptake oxygen into its lattice, which is evidenced by a crystallographic phase transition along with the appearance of structural modulations. In this study, we show that the Mn-substituted version of this multifer...
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AIP Publishing LLC
2023-06-01
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| Series: | APL Materials |
| Online Access: | http://dx.doi.org/10.1063/5.0144717 |
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| author | Tianyu Li Sz-Chian Liou Stephanie J. Hong Qiang Zhang H. Cein Mandujano Efrain E. Rodriguez |
| author_facet | Tianyu Li Sz-Chian Liou Stephanie J. Hong Qiang Zhang H. Cein Mandujano Efrain E. Rodriguez |
| author_sort | Tianyu Li |
| collection | DOAJ |
| description | The mixed valence multiferroic LnFe2+Fe3+O4 (where Ln = Y, Lu, and Yb) can reversibly uptake oxygen into its lattice, which is evidenced by a crystallographic phase transition along with the appearance of structural modulations. In this study, we show that the Mn-substituted version of this multiferroic can also be readily oxidized to LnFe3+Mn3+O4.5 revealing similar oxygen storage behavior. Through neutron, electron, and synchrotron x-ray diffraction studies, we observe a structural modulation that we attribute to a displacement wave in the fully oxidized compound. This wave exhibits commensurability with a wavevector q = (−2/7, 1/7, 0). Bond valence summation analysis of plausible interstitial oxygen positions suggests that oxygen insertion likely occurs at the middle of the Fe/Mn–O bipyramid layers. The structural modulation of LnFeMnO4.5 is two-dimensional, propagates along the ab-plane, and is highly symmetric as 12 identical modulation vectors are observed in the diffraction patterns. The nature of the lanthanide, Ln3+, does not seem to influence such modulations since we observe identical satellite reflections for all three samples of Ln = Y, Lu, and Yb. Both LnFeMnO4 and LnFeMnO4.5 display spin glassy behavior with 2D short-range magnetic ordering being observed in LnFeMnO4. Analysis of the neutron diffraction data reveals a correlation length of ∼10 nm. Upon oxidation to LnFeMnO4.5, the short-range magnetic order is significantly suppressed. |
| first_indexed | 2024-03-12T21:42:15Z |
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| id | doaj.art-4d5e7e44436842e2bc358123a5b4b155 |
| institution | Directory Open Access Journal |
| issn | 2166-532X |
| language | English |
| last_indexed | 2024-03-12T21:42:15Z |
| publishDate | 2023-06-01 |
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| record_format | Article |
| series | APL Materials |
| spelling | doaj.art-4d5e7e44436842e2bc358123a5b4b1552023-07-26T16:22:28ZengAIP Publishing LLCAPL Materials2166-532X2023-06-01116061120061120-1510.1063/5.0144717Structural modulation and spin glassiness upon oxidation in oxygen storage material LnFeMnO4+x for Ln = Y, Lu, and YbTianyu Li0Sz-Chian Liou1Stephanie J. Hong2Qiang Zhang3H. Cein Mandujano4Efrain E. Rodriguez5Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USAAdvanced Imaging and Microscopy Laboratory, Maryland NanoCenter, University of Maryland, College Park, Maryland 20742, USADepartment of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USANeutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USADepartment of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USADepartment of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USAThe mixed valence multiferroic LnFe2+Fe3+O4 (where Ln = Y, Lu, and Yb) can reversibly uptake oxygen into its lattice, which is evidenced by a crystallographic phase transition along with the appearance of structural modulations. In this study, we show that the Mn-substituted version of this multiferroic can also be readily oxidized to LnFe3+Mn3+O4.5 revealing similar oxygen storage behavior. Through neutron, electron, and synchrotron x-ray diffraction studies, we observe a structural modulation that we attribute to a displacement wave in the fully oxidized compound. This wave exhibits commensurability with a wavevector q = (−2/7, 1/7, 0). Bond valence summation analysis of plausible interstitial oxygen positions suggests that oxygen insertion likely occurs at the middle of the Fe/Mn–O bipyramid layers. The structural modulation of LnFeMnO4.5 is two-dimensional, propagates along the ab-plane, and is highly symmetric as 12 identical modulation vectors are observed in the diffraction patterns. The nature of the lanthanide, Ln3+, does not seem to influence such modulations since we observe identical satellite reflections for all three samples of Ln = Y, Lu, and Yb. Both LnFeMnO4 and LnFeMnO4.5 display spin glassy behavior with 2D short-range magnetic ordering being observed in LnFeMnO4. Analysis of the neutron diffraction data reveals a correlation length of ∼10 nm. Upon oxidation to LnFeMnO4.5, the short-range magnetic order is significantly suppressed.http://dx.doi.org/10.1063/5.0144717 |
| spellingShingle | Tianyu Li Sz-Chian Liou Stephanie J. Hong Qiang Zhang H. Cein Mandujano Efrain E. Rodriguez Structural modulation and spin glassiness upon oxidation in oxygen storage material LnFeMnO4+x for Ln = Y, Lu, and Yb APL Materials |
| title | Structural modulation and spin glassiness upon oxidation in oxygen storage material LnFeMnO4+x for Ln = Y, Lu, and Yb |
| title_full | Structural modulation and spin glassiness upon oxidation in oxygen storage material LnFeMnO4+x for Ln = Y, Lu, and Yb |
| title_fullStr | Structural modulation and spin glassiness upon oxidation in oxygen storage material LnFeMnO4+x for Ln = Y, Lu, and Yb |
| title_full_unstemmed | Structural modulation and spin glassiness upon oxidation in oxygen storage material LnFeMnO4+x for Ln = Y, Lu, and Yb |
| title_short | Structural modulation and spin glassiness upon oxidation in oxygen storage material LnFeMnO4+x for Ln = Y, Lu, and Yb |
| title_sort | structural modulation and spin glassiness upon oxidation in oxygen storage material lnfemno4 x for ln y lu and yb |
| url | http://dx.doi.org/10.1063/5.0144717 |
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