Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition

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.

doi:10.1103/PhysRevMaterials.2.015002

Title: Electronic structure of negative charge transfer CaFeO₃ across the metal-insulator transition

Journal Article · Tue Jan 30 00:00:00 EST 2018 · Physical Review Materials

DOI:https://doi.org/10.1103/PhysRevMaterials.2.015002· OSTI ID:1558569

Rogge, Paul C. ^[1]; Chandrasena, Ravini U. ^[2]; Cammarata, Antonio ^[3]; Green, Robert J. ^[4]; Shafer, Padraic ^[5]; Lefler, Benjamin ^[1]; Huon, Amanda ^[6]; Arab, Arian ^[2]; Arenholz, Elke ^[5];

^[7]; Lee, Tien-Lin ^[8]; Nemsak, Slavomir ^[9]; Rondinelli, James M. ^[10]; Gray, Alexander ^[2]; May, Steven J. ^[1]

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)

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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1558569

Alternate ID(s):: OSTI ID: 1418712

Journal Information:: Physical Review Materials, Vol. 2, Issue 1; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 27 works

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A computational study of hydrogen doping induced metal-to-insulator transition in CaFeO ₃ , SrFeO ₃ , BaFeO ₃ and SmMnO ₃ Yao, Shukai; Yoo, Pilsun; Liao, Peilin Physical Chemistry Chemical Physics, Vol. 21, Issue 45 https://doi.org/10.1039/c9cp04669k	journal	January 2019
Itinerancy-dependent noncollinear spin textures in ${SrFeO}_{3}, {CaFeO}_{3}$ , and ${CaFeO}_{3} / {SrFeO}_{3}$ heterostructures probed via resonant x-ray scattering Rogge, Paul C.; Green, Robert J.; Sutarto, Ronny Physical Review Materials, Vol. 3, Issue 8 https://doi.org/10.1103/physrevmaterials.3.084404	journal	August 2019

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Title: Electronic structure of negative charge transfer CaFeO₃ across the metal-insulator transition