Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Magnetism in Mixed Valence, Defect, Cubic Perovskites: BaIn1–xFexO2.5+δ, x = 0.25, 0.50, and 0.75. Local and Average Structures

Abstract

The series BaIn1–xFexO2.5+δ, x = 0.25, 0.50, and 0.75, has been prepared under air-fired and argon-fired conditions and studied using X-ray diffraction, d.c. and a.c. susceptibility, Mössbauer spectroscopy, neutron diffraction, X-ray near edge absorption spectroscopy (XANES), and X-ray pair distribution (PDF) methods. While Ba2In2O5 (BaInO2.5) crystallizes in an ordered brownmillerite structure, Ibm2, and Ba2Fe2O5 (BaFeO2.5) crystallizes in a complex monoclinic structure, P21/c, showing seven Fe3+ sites with tetrahedral, square planar, and octahedral environments, all phases studied here crystallize in the cubic perovskite structure, Pm$$\bar{}3}$$m, with long-range disorder on the small cation and oxygen sites. 57Fe Mössbauer studies indicate a mixed valency, Fe4+/Fe3+, for both the air-fired and argon-fired samples. The increased Fe3+ content for the argon-fired samples is reflected in increased cubic cell constants and in the increased Mössbauer fraction. It appears that the Pm$$\bar{}3}$$m phases are only metastable when fired in argon. From a slightly modified percolation theory for a primitive cubic lattice (taking into account the presence of random O atom vacancies), long-range spin order is permitted for the x = 0.50 and 0.75 phases. Instead, the d.c. susceptibility shows only zero-field-cooled (ZFC) and field-cooled (FC) divergences at ~6 K [5 K] for x = 0.50 and at ~22 K [21 K] for x = 0.75, with values for the argon-fired samples in [ ]. Neutron diffraction data for the air-fired samples confirm the absence of long-range magnetic order at any studied temperature. For the air-fired x = 0.50, a.c. susceptibility data show a frequency-dependent χ'(max) and spin glass behavior, while for x = 0.75, χ'(max) is invariant with frequency, ruling out either a spin glass or a superparamagnetic ground state. These behaviors are discussed in terms of competing Fe3+–Fe3+ antiferromagnetic exchange and ferromagnetic Fe3+–Fe4+ exchange. The PDF and 57Fe Mössbauer data indicate a local structure at short interatomic distances, which deviates strongly from the average Pm$$\bar{}3}$$m model. Fe Mössbauer, PDF, and XANES data show a systematic dependence on x and indicate that the Fe3+ sites are largely fourfold-coordinated and Fe4+ sites are fivefold- or sixfold-coordinated.

Authors:
 [1];  [2];  [2];  [2];  [2]; ORCiD logo [3];  [4];  [1];  [5]; ORCiD logo [6]; ORCiD logo [2]
+ Show Author Affiliations
  1. Univ. de La Laguna, Tenerife (Spain)
  2. McMaster Univ., Hamilton, ON (Canada)
  3. Canadian Light Source, Saskatoon (Canada)
  4. McGill Univ., Montreal, QC (Canada)
  5. Canadian Neutron Beam Centre, Chalk River (Canada)
  6. Univ. of Saskatchewan, Saskatoon, SK (Canada)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1778984
Alternate Identifier(s):
OSTI ID: 1780622; OSTI ID: 1781741
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Omega
Additional Journal Information:
Journal Volume: 6; Journal Issue: 8; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Crystal structure; Magnetic properties; Order; Particulate matter; Quantum mechanics

Citation Formats

Lozano-Gorrín, Antonio D., Wright, Bradley, Dube, Paul A., Marjerrison, Casey A., Yuan, Fang, King, Graham, Ryan, Dominic H., Gonzalez-Silgo, Cristina, Cranswick, Lachlan D., Grosvenor, Andrew P., and Greedan, John E. Magnetism in Mixed Valence, Defect, Cubic Perovskites: BaIn1–xFexO2.5+δ, x = 0.25, 0.50, and 0.75. Local and Average Structures. United States: N. p., 2021. Web. doi:10.1021/acsomega.1c00416.
Copy to clipboard
Lozano-Gorrín, Antonio D., Wright, Bradley, Dube, Paul A., Marjerrison, Casey A., Yuan, Fang, King, Graham, Ryan, Dominic H., Gonzalez-Silgo, Cristina, Cranswick, Lachlan D., Grosvenor, Andrew P., & Greedan, John E. Magnetism in Mixed Valence, Defect, Cubic Perovskites: BaIn1–xFexO2.5+δ, x = 0.25, 0.50, and 0.75. Local and Average Structures. United States. https://doi.org/10.1021/acsomega.1c00416
Copy to clipboard
Lozano-Gorrín, Antonio D., Wright, Bradley, Dube, Paul A., Marjerrison, Casey A., Yuan, Fang, King, Graham, Ryan, Dominic H., Gonzalez-Silgo, Cristina, Cranswick, Lachlan D., Grosvenor, Andrew P., and Greedan, John E. Wed . "Magnetism in Mixed Valence, Defect, Cubic Perovskites: BaIn1–xFexO2.5+δ, x = 0.25, 0.50, and 0.75. Local and Average Structures". United States. https://doi.org/10.1021/acsomega.1c00416. https://www.osti.gov/servlets/purl/1778984.
Copy to clipboard
@article{osti_1778984,
title = {Magnetism in Mixed Valence, Defect, Cubic Perovskites: BaIn1–xFexO2.5+δ, x = 0.25, 0.50, and 0.75. Local and Average Structures},
author = {Lozano-Gorrín, Antonio D. and Wright, Bradley and Dube, Paul A. and Marjerrison, Casey A. and Yuan, Fang and King, Graham and Ryan, Dominic H. and Gonzalez-Silgo, Cristina and Cranswick, Lachlan D. and Grosvenor, Andrew P. and Greedan, John E.},
abstractNote = {The series BaIn1–xFexO2.5+δ, x = 0.25, 0.50, and 0.75, has been prepared under air-fired and argon-fired conditions and studied using X-ray diffraction, d.c. and a.c. susceptibility, Mössbauer spectroscopy, neutron diffraction, X-ray near edge absorption spectroscopy (XANES), and X-ray pair distribution (PDF) methods. While Ba2In2O5 (BaInO2.5) crystallizes in an ordered brownmillerite structure, Ibm2, and Ba2Fe2O5 (BaFeO2.5) crystallizes in a complex monoclinic structure, P21/c, showing seven Fe3+ sites with tetrahedral, square planar, and octahedral environments, all phases studied here crystallize in the cubic perovskite structure, Pm$\bar{}3}$m, with long-range disorder on the small cation and oxygen sites. 57Fe Mössbauer studies indicate a mixed valency, Fe4+/Fe3+, for both the air-fired and argon-fired samples. The increased Fe3+ content for the argon-fired samples is reflected in increased cubic cell constants and in the increased Mössbauer fraction. It appears that the Pm$\bar{}3}$m phases are only metastable when fired in argon. From a slightly modified percolation theory for a primitive cubic lattice (taking into account the presence of random O atom vacancies), long-range spin order is permitted for the x = 0.50 and 0.75 phases. Instead, the d.c. susceptibility shows only zero-field-cooled (ZFC) and field-cooled (FC) divergences at ~6 K [5 K] for x = 0.50 and at ~22 K [21 K] for x = 0.75, with values for the argon-fired samples in [ ]. Neutron diffraction data for the air-fired samples confirm the absence of long-range magnetic order at any studied temperature. For the air-fired x = 0.50, a.c. susceptibility data show a frequency-dependent χ'(max) and spin glass behavior, while for x = 0.75, χ'(max) is invariant with frequency, ruling out either a spin glass or a superparamagnetic ground state. These behaviors are discussed in terms of competing Fe3+–Fe3+ antiferromagnetic exchange and ferromagnetic Fe3+–Fe4+ exchange. The PDF and 57Fe Mössbauer data indicate a local structure at short interatomic distances, which deviates strongly from the average Pm$\bar{}3}$m model. Fe Mössbauer, PDF, and XANES data show a systematic dependence on x and indicate that the Fe3+ sites are largely fourfold-coordinated and Fe4+ sites are fivefold- or sixfold-coordinated.},
doi = {10.1021/acsomega.1c00416},
journal = {ACS Omega},
number = 8,
volume = 6,
place = {United States},
year = {Wed Feb 17 00:00:00 EST 2021},
month = {Wed Feb 17 00:00:00 EST 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsomega.1c00416
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Tetrahedral Chain Order in the Sr 2 Fe 2 O 5 Brownmillerite
journal, November 2008

  • D’Hondt, Hans; Abakumov, Artem M.; Hadermann, Joke
  • Chemistry of Materials, Vol. 20, Issue 22
  • DOI: 10.1021/cm801723b

Crystallographic and Magnetic Structure of the Perovskite-Type Compound BaFeO 2.5 : Unrivaled Complexity in Oxygen Vacancy Ordering
journal, May 2014

  • Clemens, Oliver; Gröting, Melanie; Witte, Ralf
  • Inorganic Chemistry, Vol. 53, Issue 12
  • DOI: 10.1021/ic402988y

Synthesis and Structural Characterization of La 1− x A x MnO 2.5 (A = Ba, Sr, Ca) Phases: Mapping the Variants of the Brownmillerite Structure
journal, November 2009

  • Parsons, Thomas G.; D’Hondt, Hans; Hadermann, Joke
  • Chemistry of Materials, Vol. 21, Issue 22
  • DOI: 10.1021/cm902535m

Crystal and magnetic structures of the brownmillerite compound Ca2Fe1.039(8)Mn0.962(8)O5
journal, January 2009

  • Ramezanipour, Farshid; Cowie, Bradley; Derakhshan, Shahab
  • Journal of Solid State Chemistry, Vol. 182, Issue 1
  • DOI: 10.1016/j.jssc.2008.10.010

Crystal and Magnetic Structures of Sr2Fe2O5 at Elevated Temperature
journal, February 2001

  • Schmidt, M.; Campbell, S. J.
  • Journal of Solid State Chemistry, Vol. 156, Issue 2
  • DOI: 10.1006/jssc.2000.8998

Intralayer Cation Ordering in a Brownmillerite Superstructure: Synthesis, Crystal, and Magnetic Structures of Ca 2 FeCoO 5
journal, November 2010

  • Ramezanipour, Farshid; Greedan, John E.; Grosvenor, Andrew P.
  • Chemistry of Materials, Vol. 22, Issue 21
  • DOI: 10.1021/cm1023025

A Vacancy-Disordered, Oxygen-Deficient Perovskite with Long-Range Magnetic Ordering: Local and Average Structures and Magnetic Properties of Sr 2 Fe 1.5 Cr 0.5 O 5
journal, January 2012

  • Ramezanipour, Farshid; Greedan, John E.; Siewenie, Joan
  • Inorganic Chemistry, Vol. 51, Issue 4
  • DOI: 10.1021/ic202590r

The crystal and magnetic structures of Ca2Cr0.5Fe1.5O5 at 2.1 K
journal, January 1991

Local and Average Structures and Magnetic Properties of Sr 2 FeMnO 5+ y , y = 0.0, 0.5. Comparisons with Ca 2 FeMnO 5 and the Effect of the A-Site Cation
journal, August 2011

  • Ramezanipour, Farshid; Greedan, John E.; Siewenie, Joan
  • Inorganic Chemistry, Vol. 50, Issue 16
  • DOI: 10.1021/ic200919m

On the Néel temperature of Ca2Fe2O5
journal, November 1967

Systematic Study of Compositional and Synthetic Control of Vacancy and Magnetic Ordering in Oxygen-Deficient Perovskites Ca 2 Fe 2– x Mn x O 5+ y and CaSrFe 2– x Mn x O 5+ y ( x = 1/2, 2/3, and 1; y = 0–1/2)
journal, February 2012

  • Ramezanipour, Farshid; Greedan, John E.; Cranswick, Lachlan M. D.
  • Journal of the American Chemical Society, Vol. 134, Issue 6
  • DOI: 10.1021/ja210985t

Transformation of Structure, Electrical Conductivity, and Magnetism in AA′Fe 2 O 6−δ , A = Sr, Ca and A′ = Sr
journal, July 2017

Phases in the System Ba2M2-xCuxO4+δ, M = In, Sc: Structure and Oxygen Stoichiometry
journal, November 1993

  • Gregory, D. H.; Weller, M. T.
  • Journal of Solid State Chemistry, Vol. 107, Issue 1
  • DOI: 10.1006/jssc.1993.1331

A neutron diffraction study of the temperature dependence of Ca2Fe2O5
journal, January 1999

Enhancement of the oxygen desorption/absorption property of BaFe 1− x In x O 3−δ by In substitution for Fe site
journal, November 2017

  • Fujishiro, Fumito; Izaki, Minako; Hashimoto, Takuya
  • Journal of the American Ceramic Society, Vol. 101, Issue 4
  • DOI: 10.1111/jace.15329
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: