Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition
Abstract
In this work, we investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard x-ray photoelectron spectroscopy, soft x-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe sites undergo no observable spectroscopic change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ~5–10% in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. Finally, these results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates.
- Authors:
-
- Drexel Univ., Philadelphia, PA (United States)
- Temple Univ., Philadelphia, PA (United States)
- Czech Technical Univ., Prague (Czech Republic)
- Univ. of British Columbia, Vancouver, BC (Canada); Univ. of Saskatchewan, Saskatoon, SK (Canada)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Drexel Univ., Philadelphia, PA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Diamond Light Source, Ltd., Didcot, Oxfordshire (United Kingdom)
- Peter-Grunberg-Institut, Jülich (Germany); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1558569
- Alternate Identifier(s):
- OSTI ID: 1418712
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Materials
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2475-9953
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
Rogge, Paul C., Chandrasena, Ravini U., Cammarata, Antonio, Green, Robert J., Shafer, Padraic, Lefler, Benjamin, Huon, Amanda, Arab, Arian, Arenholz, Elke, Lee, Ho Nyung, Lee, Tien-Lin, Nemsak, Slavomir, Rondinelli, James M., Gray, Alexander, and May, Steven J. Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition. United States: N. p., 2018.
Web. doi:10.1103/PhysRevMaterials.2.015002.
Rogge, Paul C., Chandrasena, Ravini U., Cammarata, Antonio, Green, Robert J., Shafer, Padraic, Lefler, Benjamin, Huon, Amanda, Arab, Arian, Arenholz, Elke, Lee, Ho Nyung, Lee, Tien-Lin, Nemsak, Slavomir, Rondinelli, James M., Gray, Alexander, & May, Steven J. Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition. United States. https://doi.org/10.1103/PhysRevMaterials.2.015002
Rogge, Paul C., Chandrasena, Ravini U., Cammarata, Antonio, Green, Robert J., Shafer, Padraic, Lefler, Benjamin, Huon, Amanda, Arab, Arian, Arenholz, Elke, Lee, Ho Nyung, Lee, Tien-Lin, Nemsak, Slavomir, Rondinelli, James M., Gray, Alexander, and May, Steven J. Tue .
"Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition". United States. https://doi.org/10.1103/PhysRevMaterials.2.015002. https://www.osti.gov/servlets/purl/1558569.
@article{osti_1558569,
title = {Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition},
author = {Rogge, Paul C. and Chandrasena, Ravini U. and Cammarata, Antonio and Green, Robert J. and Shafer, Padraic and Lefler, Benjamin and Huon, Amanda and Arab, Arian and Arenholz, Elke and Lee, Ho Nyung and Lee, Tien-Lin and Nemsak, Slavomir and Rondinelli, James M. and Gray, Alexander and May, Steven J.},
abstractNote = {In this work, we investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard x-ray photoelectron spectroscopy, soft x-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe sites undergo no observable spectroscopic change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ~5–10% in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. Finally, these results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates.},
doi = {10.1103/PhysRevMaterials.2.015002},
journal = {Physical Review Materials},
number = 1,
volume = 2,
place = {United States},
year = {Tue Jan 30 00:00:00 EST 2018},
month = {Tue Jan 30 00:00:00 EST 2018}
}
Web of Science
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