skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hole-induced electronic and optical transitions in L a 1 - x S r x Fe O 3 epitaxial thin films

Abstract

We have investigated the electronic and optical properties of epitaxial La 1-xSr xFeO 3 for 0 = x = 1 prepared by molecular beam epitaxy. Core-level and valence-band x-ray photoemission features monotonically shift to lower binding energy with increasing x, indicating downward movement of the Fermi level toward to the valence band maximum. Both Fe 2p and O 1s spectra broaden to higher binding energy with increasing x, consistent with delocalization of Sr-induced holes in the Fe 3d – O 2p hybridized valence band. Combining X-ray valence band photoemission and O K-edge x-ray absorption data, we map the evolution of the occupied and unoccupied bands and observe a narrowing of the gap, along with a transfer of state density from just below to just above the Fermi level, resulting from hole doping. In-plane transport measurements confirm that the material becomes a p-type semiconductor at lower doping levels and exhibits a insulator-to-metal transition at x = 1. Sub-gap optical transitions revealed by spectroscopic ellipsometry are explained based on insight from theoretical densities of states and first-principles calculations of optical absorption spectra.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1501850
Report Number(s):
PNNL-SA-139953
Journal ID: ISSN 2475-9953; PRMHAR
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 2; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
Holed doping, optical absorption, DFT calculation, epitaxial thin films, LaFeO3

Citation Formats

Wang, Le, Du, Yingge, Sushko, Peter V., Bowden, Mark E., Stoerzinger, Kelsey A., Heald, Steven M., Scafetta, Mark D., Kaspar, Tiffany C., and Chambers, Scott A. Hole-induced electronic and optical transitions in La1-xSrxFeO3 epitaxial thin films. United States: N. p., 2019. Web. doi:10.1103/PhysRevMaterials.3.025401.
Wang, Le, Du, Yingge, Sushko, Peter V., Bowden, Mark E., Stoerzinger, Kelsey A., Heald, Steven M., Scafetta, Mark D., Kaspar, Tiffany C., & Chambers, Scott A. Hole-induced electronic and optical transitions in La1-xSrxFeO3 epitaxial thin films. United States. doi:10.1103/PhysRevMaterials.3.025401.
Wang, Le, Du, Yingge, Sushko, Peter V., Bowden, Mark E., Stoerzinger, Kelsey A., Heald, Steven M., Scafetta, Mark D., Kaspar, Tiffany C., and Chambers, Scott A. Fri . "Hole-induced electronic and optical transitions in La1-xSrxFeO3 epitaxial thin films". United States. doi:10.1103/PhysRevMaterials.3.025401.
@article{osti_1501850,
title = {Hole-induced electronic and optical transitions in La1-xSrxFeO3 epitaxial thin films},
author = {Wang, Le and Du, Yingge and Sushko, Peter V. and Bowden, Mark E. and Stoerzinger, Kelsey A. and Heald, Steven M. and Scafetta, Mark D. and Kaspar, Tiffany C. and Chambers, Scott A.},
abstractNote = {We have investigated the electronic and optical properties of epitaxial La1-xSrxFeO3 for 0 = x = 1 prepared by molecular beam epitaxy. Core-level and valence-band x-ray photoemission features monotonically shift to lower binding energy with increasing x, indicating downward movement of the Fermi level toward to the valence band maximum. Both Fe 2p and O 1s spectra broaden to higher binding energy with increasing x, consistent with delocalization of Sr-induced holes in the Fe 3d – O 2p hybridized valence band. Combining X-ray valence band photoemission and O K-edge x-ray absorption data, we map the evolution of the occupied and unoccupied bands and observe a narrowing of the gap, along with a transfer of state density from just below to just above the Fermi level, resulting from hole doping. In-plane transport measurements confirm that the material becomes a p-type semiconductor at lower doping levels and exhibits a insulator-to-metal transition at x = 1. Sub-gap optical transitions revealed by spectroscopic ellipsometry are explained based on insight from theoretical densities of states and first-principles calculations of optical absorption spectra.},
doi = {10.1103/PhysRevMaterials.3.025401},
journal = {Physical Review Materials},
issn = {2475-9953},
number = 2,
volume = 3,
place = {United States},
year = {2019},
month = {2}
}

Works referenced in this record:

Impact of built-in potential across LaFeO3/SrTiO3 heterojunctions on photocatalytic activity
journal, May 2016

  • Nakamura, Kentarou; Mashiko, Hisanori; Yoshimatsu, Kohei
  • Applied Physics Letters, Vol. 108, Issue 21
  • DOI: 10.1063/1.4952736

Effect of doping and chemical ordering on the optoelectronic properties of complex oxides: Fe 2 O 3 –V 2 O 3 solid solutions and hetero-structures
journal, January 2017

  • Nayyar, Iffat H.; Chamberlin, Sara E.; Kaspar, Tiffany C.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 2
  • DOI: 10.1039/C6CP06087K

X-Ray Absorption Spectroscopy Studies of La 1- x Sr x FeO 3
journal, January 1999

  • Chang, C. L.; Chern, G.; Tai, M. F.
  • Japanese Journal of Applied Physics, Vol. 38, Issue S1
  • DOI: 10.7567/JJAPS.38S1.108

Band alignment and electrocatalytic activity at the p - n La 0.88 Sr 0.12 FeO 3 /SrTiO 3 (001) heterojunction
journal, June 2018

  • Wang, L.; Du, Y.; Chang, L.
  • Applied Physics Letters, Vol. 112, Issue 26
  • DOI: 10.1063/1.5030897

Projector augmented-wave method
journal, December 1994


Optical Absorption and Band Gap Reduction in (Fe 1– x Cr x ) 2 O 3 Solid Solutions: A First-Principles Study
journal, November 2013

  • Wang, Yong; Lopata, Kenneth; Chambers, Scott A.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 48
  • DOI: 10.1021/jp407496w

Spontaneous Polarization and Bulk Photovoltaic Effect Driven by Polar Discontinuity in LaFeO 3 / SrTiO 3 Heterojunctions
journal, April 2016


Bandgap tuning of multiferroic oxide solar cells
journal, November 2014


Strongly correlated perovskite fuel cells
journal, May 2016


Strong localization of doped holes in La 1 x Sr x FeO 3 from angle-resolved photoemission spectra
journal, September 2006


Oxygen Vacancy Induced Room-Temperature Metal–Insulator Transition in Nickelate Films and Its Potential Application in Photovoltaics
journal, April 2016

  • Wang, Le; Dash, Sibashisa; Chang, Lei
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 15
  • DOI: 10.1021/acsami.6b00650

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


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


Core-level photoemission measurements of the chemical potential shift as a probe of correlated electron systems
journal, July 2002

  • Fujimori, A.; Ino, A.; Matsuno, J.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 124, Issue 2-3
  • DOI: 10.1016/S0368-2048(02)00049-X

Systematic Study of Oxygen Evolution Activity and Stability on La 1– x Sr x FeO 3−δ Perovskite Electrocatalysts in Alkaline Media
journal, March 2018

  • She, Sixuan; Yu, Jie; Tang, Wanqi
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 14
  • DOI: 10.1021/acsami.8b00682

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

In vacuo photoemission study of atomically controlled La 1 x Sr x Mn O 3 thin films: Composition dependence of the electronic structure
journal, April 2005


Crystal Structure and Thermal Expansion of La1−xSrxFeO3−δ Materials
journal, October 2004


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

  • Chakraverty, S.; Matsuda, T.; Ogawa, N.
  • Applied Physics Letters, Vol. 103, Issue 14
  • DOI: 10.1063/1.4824210

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Unit cell for a lattice electrostatic potential
journal, October 2007


A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011


Microwave-assisted synthesis of nanoparticulate perovskite LaFeO3 as a high active visible-light photocatalyst
journal, March 2013


Electronic Reconstruction at the Isopolar LaTiO 3 / LaFeO 3 Interface: An X-Ray Photoemission and Density-Functional Theory Study
journal, December 2014


Epitaxial BiFeO3 Multiferroic Thin Film Heterostructures
journal, March 2003


Thickness-Dependent Photoelectrochemical Water Splitting on Ultrathin LaFeO 3 Films Grown on Nb:SrTiO 3
journal, March 2015

  • May, Kevin J.; Fenning, David P.; Ming, Tian
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 6
  • DOI: 10.1021/acs.jpclett.5b00169

Surface termination, composition and reconstruction of Fe3O4(001) and γ-Fe2O3(001)
journal, January 1999


Electronic phase diagram of epitaxial La 1− x Sr x FeO 3 films
journal, August 2014

  • Xie, Y. J.; Scafetta, M. D.; Moon, E. J.
  • Applied Physics Letters, Vol. 105, Issue 6
  • DOI: 10.1063/1.4893139

Static and Dynamic Optical Properties of La 1– x Sr x FeO 3−δ : The Effects of A-Site and Oxygen Stoichiometry
journal, December 2015


Ab Initio DFT+U Analysis of Oxygen Vacancy Formation and Migration in La 1-x Sr x FeO 3-δ ( x = 0, 0.25, 0.50)
journal, July 2013

  • Ritzmann, Andrew M.; Muñoz-García, Ana B.; Pavone, Michele
  • Chemistry of Materials, Vol. 25, Issue 15
  • DOI: 10.1021/cm401052w

Possible highT c superconductivity in the Ba?La?Cu?O system
journal, June 1986

  • Bednorz, J. G.; M�ller, K. A.
  • Zeitschrift f�r Physik B Condensed Matter, Vol. 64, Issue 2
  • DOI: 10.1007/BF01303701

Perovskites in catalysis and electrocatalysis
journal, November 2017


Metal-insulator transitions
journal, October 1998

  • Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori
  • Reviews of Modern Physics, Vol. 70, Issue 4, p. 1039-1263
  • DOI: 10.1103/RevModPhys.70.1039

Fermi level shift in La1−xSrxMO3 (M=Mn, Fe, Co, and Ni) probed by Schottky-like heteroepitaxial junctions with SrTi0.99Nb0.01O3
journal, June 2007

  • Sawa, A.; Yamamoto, A.; Yamada, H.
  • Applied Physics Letters, Vol. 90, Issue 25
  • DOI: 10.1063/1.2749431

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

  • Xie, Yujun; Scafetta, Mark D.; Sichel-Tissot, Rebecca J.
  • Advanced Materials, Vol. 26, Issue 9
  • DOI: 10.1002/adma.201304374

Synthesis and characterization of the La1−xSrxFeO3−δ system and the fluorinated phases La1−xSrxFeO3−xFx
journal, November 2011

  • Clemens, Oliver; Kuhn, Melanie; Haberkorn, Robert
  • Journal of Solid State Chemistry, Vol. 184, Issue 11
  • DOI: 10.1016/j.jssc.2011.08.037

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


Time-dependent density functional theory within the Tamm–Dancoff approximation
journal, December 1999


Multiband Optical Absorption Controlled by Lattice Strain in Thin-Film LaCrO 3
journal, February 2013


Electronic structure of negative charge transfer CaFeO 3 across the metal-insulator transition
journal, January 2018


Mixed-valence manganites
journal, March 1999


Linking surface chemistry to photovoltage in Sr-substituted LaFeO 3 for water oxidation
journal, January 2018

  • Stoerzinger, Kelsey A.; Wang, Le; Ye, Yifan
  • Journal of Materials Chemistry A, Vol. 6, Issue 44
  • DOI: 10.1039/C8TA05741A

Band structure and optical transitions in LaFeO 3 : theory and experiment
journal, November 2014


General Purpose Electrostatic Embedding Potential
journal, February 2010

  • Sushko, Peter V.; Abarenkov, Igor V.
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 4
  • DOI: 10.1021/ct900480p

Versatile helimagnetic phases under magnetic fields in cubic perovskite SrFeO 3
journal, August 2011


Optical absorption in epitaxial La1−xSrxFeO3 thin films
journal, February 2013

  • Scafetta, M. D.; Xie, Y. J.; Torres, M.
  • Applied Physics Letters, Vol. 102, Issue 8
  • DOI: 10.1063/1.4794145

Hole-induced insulator-to-metal transition in L a 1 x S r x Cr O 3 epitaxial films
journal, April 2015