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Title: Electronic and Optical Properties of a Semiconducting Spinel (Fe 2 CrO 4 )

Abstract

Epitaxial chromium ferrite (Fe 2 CrO 4 ), prepared by state‐of‐the‐art oxygen plasma assisted molecular beam epitaxy, is shown to exhibit unusual electronic transport properties driven by the crystallographic structure and composition of the material. Replacing 1/3 of the Fe cations with Cr converts the host ferrimagnet from a metal into a semiconductor by virtue of its fixed valence (3+); Cr substitutes for Fe at B sites in the spinel lattice. By contrast, replacing 2/3 of the Fe cations with Cr results in an insulator. Three candidate conductive paths, all involving electron hopping between Fe 2+ and Fe 3+ , are identified in Fe 2 CrO 4 . Moreover, Fe 2 CrO 4 is shown to be photoconductive across the visible portion of the electromagnetic spectrum. As a result, this material is of potential interest for important photo‐electrochemical processes such as water splitting.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [2];  [3];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab.
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1389315
Alternate Identifier(s):
OSTI ID: 1401506
Grant/Contract Number:  
AC02-06CH11357; #10122
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 9; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; chromium ferrite; expitaxial film; photoelectronic properties

Citation Formats

Chambers, Scott A., Droubay, Timothy C., Kaspar, Tiffany C., Nayyar, Iffat H., McBriarty, Martin E., Heald, Steve M., Keavney, David J., Bowden, Mark E., and Sushko, Peter V. Electronic and Optical Properties of a Semiconducting Spinel (Fe 2 CrO 4 ). United States: N. p., 2017. Web. doi:10.1002/adfm.201605040.
Chambers, Scott A., Droubay, Timothy C., Kaspar, Tiffany C., Nayyar, Iffat H., McBriarty, Martin E., Heald, Steve M., Keavney, David J., Bowden, Mark E., & Sushko, Peter V. Electronic and Optical Properties of a Semiconducting Spinel (Fe 2 CrO 4 ). United States. https://doi.org/10.1002/adfm.201605040
Chambers, Scott A., Droubay, Timothy C., Kaspar, Tiffany C., Nayyar, Iffat H., McBriarty, Martin E., Heald, Steve M., Keavney, David J., Bowden, Mark E., and Sushko, Peter V. Fri . "Electronic and Optical Properties of a Semiconducting Spinel (Fe 2 CrO 4 )". United States. https://doi.org/10.1002/adfm.201605040. https://www.osti.gov/servlets/purl/1389315.
@article{osti_1389315,
title = {Electronic and Optical Properties of a Semiconducting Spinel (Fe 2 CrO 4 )},
author = {Chambers, Scott A. and Droubay, Timothy C. and Kaspar, Tiffany C. and Nayyar, Iffat H. and McBriarty, Martin E. and Heald, Steve M. and Keavney, David J. and Bowden, Mark E. and Sushko, Peter V.},
abstractNote = {Epitaxial chromium ferrite (Fe 2 CrO 4 ), prepared by state‐of‐the‐art oxygen plasma assisted molecular beam epitaxy, is shown to exhibit unusual electronic transport properties driven by the crystallographic structure and composition of the material. Replacing 1/3 of the Fe cations with Cr converts the host ferrimagnet from a metal into a semiconductor by virtue of its fixed valence (3+); Cr substitutes for Fe at B sites in the spinel lattice. By contrast, replacing 2/3 of the Fe cations with Cr results in an insulator. Three candidate conductive paths, all involving electron hopping between Fe 2+ and Fe 3+ , are identified in Fe 2 CrO 4 . Moreover, Fe 2 CrO 4 is shown to be photoconductive across the visible portion of the electromagnetic spectrum. As a result, this material is of potential interest for important photo‐electrochemical processes such as water splitting.},
doi = {10.1002/adfm.201605040},
journal = {Advanced Functional Materials},
number = 9,
volume = 27,
place = {United States},
year = {Fri Jan 13 00:00:00 EST 2017},
month = {Fri Jan 13 00:00:00 EST 2017}
}

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Works referenced in this record:

Spin-polarized conduction in localized ferromagnetic materials: The case of Fe3O4 on MgO(100)
journal, October 2005

  • Vescovo, E.; Kim, H. -J.; Ablett, J. M.
  • Journal of Applied Physics, Vol. 98, Issue 8
  • DOI: 10.1063/1.2085316

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Role of oxide ionicity in electronic screening at oxide/metal interfaces
journal, July 2001


Projector augmented-wave method
journal, December 1994


Molecular beam epitaxial growth and properties of CoFe2O4 on MgO(001)
journal, April 2002

  • Chambers, S. A.; Farrow, R. F. C.; Maat, S.
  • Journal of Magnetism and Magnetic Materials, Vol. 246, Issue 1-2
  • DOI: 10.1016/S0304-8853(02)00039-2

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


X-Ray Diffraction and Magnetic Measurements of the Fe-Cr Spinels
journal, December 1958


Many-electron singularity in X-ray photoemission and X-ray line spectra from metals
journal, February 1970


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Magnetic properties and site distributions in the system FeCr2O4-Fe3O4(Fe2+Cr2−xFex3+O4
journal, January 1971


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


The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges
journal, October 2010


XAS AND MCD STUDIES OF CrFe 2 O 4
journal, April 2002

  • Mizumaki, Masaichiro; Agui, Akane; Saitoh, Yuji
  • Surface Review and Letters, Vol. 09, Issue 02
  • DOI: 10.1142/S0218625X02003044

Iron oxide surfaces
journal, March 2016


Lattice Parameters of the FeFe (2— x ) Cr x O 4 Spinel System
journal, July 1954

  • Yearian, H. J.; Kortright, J. M.; Langenheim, R. H.
  • The Journal of Chemical Physics, Vol. 22, Issue 7
  • DOI: 10.1063/1.1740331

Photoelectrochemical Investigation of Ultrathin Film Iron Oxide Solar Cells Prepared by Atomic Layer Deposition
journal, January 2011

  • Klahr, Benjamin M.; Martinson, Alex B. F.; Hamann, Thomas W.
  • Langmuir, Vol. 27, Issue 1
  • DOI: 10.1021/la103541n

Vanishing Fe 3d orbital moments in single-crystalline magnetite
journal, January 2006


Electronic Structures of New Half-Metal Material CrFe2O4
journal, January 2009


Exchange Interactions in Ferromagnetic Chromium Chalcogenide Spinels
journal, November 1966


The impact of crystal symmetry on the electronic structure and functional properties of complex lanthanum chromium oxides
journal, January 2013

  • Qiao, L.; Xiao, H. Y.; Heald, S. M.
  • Journal of Materials Chemistry C, Vol. 1, Issue 30
  • DOI: 10.1039/c3tc30883a

Photoelectrochemical H2-generation over Spinel FeCr2O4 in X2− solutions (X2−=S2− and )
journal, July 2009


Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981


Subsurface cation vacancy stabilization of the magnetite (001) surface
journal, December 2014


Absorption spectroscopy and XMCD at the Verwey transition of Fe3O4
journal, March 2007

  • Goering, E. J.; Lafkioti, M.; Gold, S.
  • Journal of Magnetism and Magnetic Materials, Vol. 310, Issue 2
  • DOI: 10.1016/j.jmmm.2006.10.197

Magnetic and structural phase transitions in the spinel compound Fe 1 + x Cr 2 x O 4
journal, April 2014


Ferromagnetism in CdCr 2 Se 4 and CdCr 2 S 4
journal, March 1966

  • Menyuk, N.; Dwight, K.; Arnott, R. J.
  • Journal of Applied Physics, Vol. 37, Issue 3
  • DOI: 10.1063/1.1708484

Surface structure of α-Cr2O3(0001) after activated oxygen exposure
journal, December 2013


Magnetic structures in substituted ferrites
journal, February 1990


Optical absorption and spectral photoconductivity in α-(Fe 1− x Cr x ) 2 O 3 solid-solution thin films
journal, September 2013


Impact of lattice mismatch and stoichiometry on the structure and bandgap of (Fe,Cr) 2 O 3 epitaxial thin films
journal, March 2014


Works referencing / citing this record:

Probing the CZTS/CdS heterojunction utilizing photoelectrochemistry and x-ray absorption spectroscopy
journal, April 2018

  • Turnbull, Matthew J.; Vaccarello, Daniel; Wong, Jonathan
  • The Journal of Chemical Physics, Vol. 148, Issue 13
  • DOI: 10.1063/1.5016351

Chromium substituted iron oxide nanowires as affordable electrocatalysts for oxygen evolution reaction
journal, June 2019

  • Kocabas, Serra; Cetin, Asude; Önal, Ahmet M.
  • Journal of Nanoparticle Research, Vol. 21, Issue 7
  • DOI: 10.1007/s11051-019-4591-5

Reversible Oxidation Quantified by Optical Properties in Epitaxial Fe 2 CrO 4+δ Films on (001) MgAl 2 O 4
journal, February 2020