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

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:

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)

Publication Date:: Tue Jan 30 00:00:00 EST 2018

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.

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                    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

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                    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.

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@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}

}

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Depth‐Resolved Modulation of Metal–Oxygen Hybridization and Orbital Polarization across Correlated Oxide Interfaces
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Itinerancy-dependent noncollinear spin textures in ${SrFeO}_{3}, {CaFeO}_{3}$ , and ${CaFeO}_{3} / {SrFeO}_{3}$ heterostructures probed via resonant x-ray scattering
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Rogge, Paul C.; Green, Robert J.; Sutarto, Ronny
Physical Review Materials, Vol. 3, Issue 8
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Title: Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition

Abstract

Citation Formats

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O 1 s near-edge x-ray absorption of La 2 − x Sr x NiO 4 + δ : Holes, polarons, and excitons journal, April 1996

Different routes to charge disproportionation in perovskite-type Fe oxides journal, November 2002

The Fe K-edge X-ray absorption characteristics of La1−xSrxFeO3−δ prepared by solid state reaction journal, June 2009

Control of Functional Responses Via Reversible Oxygen Loss in La 1- x Sr x FeO 3-δ Films journal, November 2013

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Valence Band Structure and X-ray Spectra of Oxygen-Deficient Ferrites SrFeO x journal, March 2010

Controlled-valence properties of La 1 − x Sr x FeO 3 and La 1 − x Sr x MnO 3 studied by soft-x-ray absorption spectroscopy journal, August 1992

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal, January 1998

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal, April 2008

First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method journal, January 1997

Bond disproportionation and dynamical charge fluctuations in the perovskite rare-earth nickelates journal, November 2016

Charge-Ordered State in Single-Crystalline C a F e O 3 Thin Film Studied by X-Ray Anomalous Diffraction journal, October 2003

Energy Level Alignment and Cation Charge States at the LaFeO 3 /LaMnO 3 (001) Heterointerface journal, April 2017

Covalency-driven unusual metal-insulator transition in nickelates journal, March 1994

Spin-assisted covalent bond mechanism in “charge-ordering” perovskite oxides journal, November 2012

Chemical Expansivity of Electrochemical Ceramics journal, September 2001

X-ray spectroscopic study of BaFeO 3 thin films: An Fe 4 + ferromagnetic insulator journal, March 2015

BaFeO 3 cubic single crystalline thin film: A ferromagnetic insulator journal, September 2013

Variation of charge dynamics upon the helimagnetic and metal-insulator transitions for perovskite A FeO 3 ( A = Sr and Ca) journal, April 2012

Phase Transitions in Fe 4+ (3 d 4 )-Perovskite Oxides Dominated by Oxygen-Hole Character journal, May 1998

Strain-mediated metal-insulator transition in epitaxial ultrathin films of NdNiO3 journal, June 2010

Electronic structure of SrFe 4 + O 3 and related Fe perovskite oxides journal, January 1992

Oxygen Storage Properties of La 1– x Sr x FeO 3−δ for Chemical-Looping Reactions—An In Situ Neutron and Synchrotron X-ray Study journal, May 2016

Practical expressions for the mean escape depth, the information depth, and the effective attenuation length in Auger-electron spectroscopy and x-ray photoelectron spectroscopy journal, March 2009

X-ray absorption and dichroism of transition metals and their compounds journal, August 1994

Formal Valence, 3 d -Electron Occupation, and Charge-Order Transitions journal, November 2012

Depth‐Resolved Modulation of Metal–Oxygen Hybridization and Orbital Polarization across Correlated Oxide Interfaces journal, September 2019

A computational study of hydrogen doping induced metal-to-insulator transition in CaFeO 3 , SrFeO 3 , BaFeO 3 and SmMnO 3 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 journal, August 2019

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

Density functional study of the insulating ground states in $Ca Fe O_{3}$ and ${La}_{1 ∕ 3} {Sr}_{2 ∕ 3} Fe O_{3}$ compounds
journal, July 2005

Charge Disproportionation without Charge Transfer in the Rare-Earth-Element Nickelates as a Possible Mechanism for the Metal-Insulator Transition
journal, March 2014

Electronic transitions in strained SmNiO ₃ thin films
journal, November 2014

Lattice normal modes and electronic properties of the correlated metal LaNiO $_{3}$
journal, October 2011

Strain controlled metal-insulator transition in epitaxial NdNiO ₃ thin films
journal, December 2013

Electric and Magnetic Properties of the Strontium Ferrates
journal, September 1965

Projector augmented-wave method
journal, December 1994

Structural studies of charge disproportionation and magnetic order in ${CaFeO}_{3}$
journal, July 2000

Experimental and theoretical study of the electronic structure of single-crystal ${BaBiO}_{3}$
journal, October 2017

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Band gaps and electronic structure of transition-metal compounds
journal, July 1985

Metal–semiconductor transition, charge disproportionation, and low-temperature structure of Ca1–xSrxFeO3 synthesized under high-oxygen pressure
journal, November 2000

Estimating Hybridization of Transition Metal and Oxygen States in Perovskites from O K -edge X-ray Absorption Spectroscopy
journal, January 2014

Interpretation of XPS O (1s) in Mixed Oxides Proved on Mixed Perovskite Crystals
journal, January 2002

Structure and Properties of Functional Oxide Thin Films: Insights From Electronic-Structure Calculations
journal, July 2011

Spin and charge ordering in self-doped Mott insulators
journal, May 2000

Site-Selective Mott Transition in Rare-Earth-Element Nickelates
journal, October 2012

Metal-insulator transitions
journal, October 1998

Heterointerface engineered electronic and magnetic phases of NdNiO3 thin films
journal, November 2013

Charge disproportionation in CaFeO3 studied with the Mössbauer effect
journal, September 1977

Out-of-plane orbital characters of intrinsic and doped holes in ${La}_{2 - x}$ ${Sr}_{x}$ ${CuO}_{4}$
journal, April 1992

O 1 s near-edge x-ray absorption of ${La}_{2 - x}$ ${Sr}_{x}$ ${NiO}_{4 + δ}$ : Holes, polarons, and excitons
journal, April 1996

Different routes to charge disproportionation in perovskite-type Fe oxides
journal, November 2002

The Fe K-edge X-ray absorption characteristics of La1−xSrxFeO3−δ prepared by solid state reaction
journal, June 2009

Control of Functional Responses Via Reversible Oxygen Loss in La _{1- x} Sr _x FeO _3-δ Films
journal, November 2013

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Valence Band Structure and X-ray Spectra of Oxygen-Deficient Ferrites SrFeO _x
journal, March 2010

Controlled-valence properties of ${La}_{1 - x}$ ${Sr}_{x}$ ${FeO}_{3}$ and ${La}_{1 - x}$ ${Sr}_{x}$ ${MnO}_{3}$ studied by soft-x-ray absorption spectroscopy
journal, August 1992

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method
journal, January 1997

Bond disproportionation and dynamical charge fluctuations in the perovskite rare-earth nickelates
journal, November 2016

Charge-Ordered State in Single-Crystalline ${C a F e O}_{3}$ Thin Film Studied by X-Ray Anomalous Diffraction
journal, October 2003

Energy Level Alignment and Cation Charge States at the LaFeO ₃ /LaMnO ₃ (001) Heterointerface
journal, April 2017

Covalency-driven unusual metal-insulator transition in nickelates
journal, March 1994

Spin-assisted covalent bond mechanism in “charge-ordering” perovskite oxides
journal, November 2012

Chemical Expansivity of Electrochemical Ceramics
journal, September 2001

X-ray spectroscopic study of $BaFeO_{3}$ thin films: An ${Fe}^{4 +}$ ferromagnetic insulator
journal, March 2015

BaFeO ₃ cubic single crystalline thin film: A ferromagnetic insulator
journal, September 2013

Variation of charge dynamics upon the helimagnetic and metal-insulator transitions for perovskite $A$ FeO $_{3}$ ( $A$ = Sr and Ca)
journal, April 2012

Phase Transitions in Fe ⁴⁺ (3 d ⁴ )-Perovskite Oxides Dominated by Oxygen-Hole Character
journal, May 1998

Strain-mediated metal-insulator transition in epitaxial ultrathin films of NdNiO3
journal, June 2010

Electronic structure of ${SrFe}^{4 +}$ $O_{3}$ and related Fe perovskite oxides
journal, January 1992

Oxygen Storage Properties of La _{1– x} Sr _x FeO _3−δ for Chemical-Looping Reactions—An In Situ Neutron and Synchrotron X-ray Study
journal, May 2016

Practical expressions for the mean escape depth, the information depth, and the effective attenuation length in Auger-electron spectroscopy and x-ray photoelectron spectroscopy
journal, March 2009

X-ray absorption and dichroism of transition metals and their compounds
journal, August 1994

Formal Valence, $3 d$ -Electron Occupation, and Charge-Order Transitions
journal, November 2012

Depth‐Resolved Modulation of Metal–Oxygen Hybridization and Orbital Polarization across Correlated Oxide Interfaces
journal, September 2019

A computational study of hydrogen doping induced metal-to-insulator transition in CaFeO ₃ , SrFeO ₃ , BaFeO ₃ and SmMnO ₃
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
journal, August 2019