Hole-induced electronic and optical transitions in La1-xSrxFeO3 epitaxial thin films

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.

doi:10.1103/PhysRevMaterials.3.025401

Title: Hole-induced electronic and optical transitions in $L a_{1 - x} S r_{x} Fe O_{3}$ epitaxial thin films

Journal Article · Mon Feb 04 00:00:00 EST 2019 · Physical Review Materials

DOI:https://doi.org/10.1103/PhysRevMaterials.3.025401· OSTI ID:1510080

Wang, Le ^[1]; Du, Yingge ^[1]; Sushko, Peter V. ^[1]; Bowden, Mark E. ^[1]; Stoerzinger, Kelsey A. ^[1]; Heald, Steven M. ^[2]; Scafetta, Mark D. ^[1]; Kaspar, Tiffany C. ^[1]; Chambers, Scott A. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

We have investigated the electronic and optical properties of epitaxial La_1-xSr_xFeO₃ 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 the valence-band maximum. Combining 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 as a result of hole doping. In-plane transport measurements confirm that the material becomes a p-type semiconductor at lower doping levels and exhibits a conversion from semiconducting to metallic behavior at x = 1. As a result, low-energy optical transitions revealed by spectroscopic ellipsometry are explained based on insight from theoretical densities of states and first-principles calculations of optical absorption spectra.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357; AC02-05CH11231; PNNL LDRD 69319

OSTI ID:: 1510080

Alternate ID(s):: OSTI ID: 1493381

Journal Information:: Physical Review Materials, Vol. 3, Issue 2; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 33 works

Citation information provided by
Web of Science

References (48)

Impact of built-in potential across LaFeO3/SrTiO3 heterojunctions on photocatalytic activity Nakamura, Kentarou; Mashiko, Hisanori; Yoshimatsu, Kohei Applied Physics Letters, Vol. 108, Issue 21 https://doi.org/10.1063/1.4952736	journal	May 2016
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 Nayyar, Iffat H.; Chamberlin, Sara E.; Kaspar, Tiffany C. Physical Chemistry Chemical Physics, Vol. 19, Issue 2 https://doi.org/10.1039/C6CP06087K	journal	January 2017
X-Ray Absorption Spectroscopy Studies of La _{1- x} Sr _x FeO ₃ Chang, C. L.; Chern, G.; Tai, M. F. Japanese Journal of Applied Physics, Vol. 38, Issue S1 https://doi.org/10.7567/JJAPS.38S1.108	journal	January 1999
Band alignment and electrocatalytic activity at the p - n La _0.88 Sr _0.12 FeO ₃ /SrTiO ₃ (001) heterojunction Wang, L.; Du, Y.; Chang, L. Applied Physics Letters, Vol. 112, Issue 26 https://doi.org/10.1063/1.5030897	journal	June 2018
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Optical Absorption and Band Gap Reduction in (Fe _{1– x} Cr _x ) ₂ O ₃ Solid Solutions: A First-Principles Study Wang, Yong; Lopata, Kenneth; Chambers, Scott A. The Journal of Physical Chemistry C, Vol. 117, Issue 48 https://doi.org/10.1021/jp407496w	journal	November 2013
Spontaneous Polarization and Bulk Photovoltaic Effect Driven by Polar Discontinuity in ${LaFeO}_{3} / {SrTiO}_{3}$ Heterojunctions Nakamura, M.; Kagawa, F.; Tanigaki, T. Physical Review Letters, Vol. 116, Issue 15 https://doi.org/10.1103/PhysRevLett.116.156801	journal	April 2016
Bandgap tuning of multiferroic oxide solar cells Nechache, R.; Harnagea, C.; Li, S. Nature Photonics, Vol. 9, Issue 1 https://doi.org/10.1038/nphoton.2014.255	journal	November 2014
Strongly correlated perovskite fuel cells Zhou, You; Guan, Xiaofei; Zhou, Hua Nature, Vol. 534, Issue 7606 https://doi.org/10.1038/nature17653	journal	May 2016
Strong localization of doped holes in ${La}_{1 - x} {Sr}_{x} {FeO}_{3}$ from angle-resolved photoemission spectra Wadati, H.; Chikamatsu, A.; Takizawa, M. Physical Review B, Vol. 74, Issue 11 https://doi.org/10.1103/PhysRevB.74.115114	journal	September 2006
Oxygen Vacancy Induced Room-Temperature Metal–Insulator Transition in Nickelate Films and Its Potential Application in Photovoltaics Wang, Le; Dash, Sibashisa; Chang, Lei ACS Applied Materials & Interfaces, Vol. 8, Issue 15 https://doi.org/10.1021/acsami.6b00650	journal	April 2016
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	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 Abbate, M.; de Groot, F. M. F.; Fuggle, J. C. Physical Review B, Vol. 46, Issue 8 https://doi.org/10.1103/PhysRevB.46.4511	journal	August 1992
Core-level photoemission measurements of the chemical potential shift as a probe of correlated electron systems Fujimori, A.; Ino, A.; Matsuno, J. Journal of Electron Spectroscopy and Related Phenomena, Vol. 124, Issue 2-3 https://doi.org/10.1016/S0368-2048(02)00049-X	journal	July 2002
Systematic Study of Oxygen Evolution Activity and Stability on La _{1– x} Sr _x FeO _3−δ Perovskite Electrocatalysts in Alkaline Media She, Sixuan; Yu, Jie; Tang, Wanqi ACS Applied Materials & Interfaces, Vol. 10, Issue 14 https://doi.org/10.1021/acsami.8b00682	journal	March 2018
A new mixing of Hartree–Fock and local density‐functional theories Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 2 https://doi.org/10.1063/1.464304	journal	January 1993
In vacuo photoemission study of atomically controlled ${La}_{1 - x} {Sr}_{x} Mn O_{3}$ thin films: Composition dependence of the electronic structure Horiba, K.; Chikamatsu, A.; Kumigashira, H. Physical Review B, Vol. 71, Issue 15 https://doi.org/10.1103/PhysRevB.71.155420	journal	April 2005
Crystal Structure and Thermal Expansion of La1−xSrxFeO3−δ Materials Fossdal, Anita; Menon, Mohan; Waernhus, Ivar Journal of the American Ceramic Society, Vol. 87, Issue 10 https://doi.org/10.1111/j.1151-2916.2004.tb06346.x	journal	October 2004
BaFeO ₃ cubic single crystalline thin film: A ferromagnetic insulator Chakraverty, S.; Matsuda, T.; Ogawa, N. Applied Physics Letters, Vol. 103, Issue 14 https://doi.org/10.1063/1.4824210	journal	September 2013
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations Valiev, M.; Bylaska, E. J.; Govind, N. Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489 https://doi.org/10.1016/j.cpc.2010.04.018	journal	September 2010
Unit cell for a lattice electrostatic potential Abarenkov, I. V. Physical Review B, Vol. 76, Issue 16 https://doi.org/10.1103/PhysRevB.76.165127	journal	October 2007
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles Suntivich, J.; May, K. J.; Gasteiger, H. A. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1212858	journal	October 2011
Microwave-assisted synthesis of nanoparticulate perovskite LaFeO3 as a high active visible-light photocatalyst Tang, Peisong; Tong, Yi; Chen, Haifeng Current Applied Physics, Vol. 13, Issue 2 https://doi.org/10.1016/j.cap.2012.08.006	journal	March 2013
Hole-doping-induced changes in the electronic structure of ${La}_{1 - x} {Sr}_{x} {FeO}_{3}$ : Soft x-ray photoemission and absorption study of epitaxial thin films Wadati, H.; Kobayashi, D.; Kumigashira, H. Physical Review B, Vol. 71, Issue 3 https://doi.org/10.1103/PhysRevB.71.035108	journal	January 2005
Electronic Reconstruction at the Isopolar ${LaTiO}_{3} / {LaFeO}_{3}$ Interface: An X-Ray Photoemission and Density-Functional Theory Study Kleibeuker, J. E.; Zhong, Z.; Nishikawa, H. Physical Review Letters, Vol. 113, Issue 23 https://doi.org/10.1103/PhysRevLett.113.237402	journal	December 2014
Epitaxial BiFeO₃ Multiferroic Thin Film Heterostructures Wang, J.; Neaton, J. B.; Zheng, H. Science, Vol. 299, Issue 5613, p. 1719-1722 https://doi.org/10.1126/science.1080615	journal	March 2003
Thickness-Dependent Photoelectrochemical Water Splitting on Ultrathin LaFeO ₃ Films Grown on Nb:SrTiO ₃ May, Kevin J.; Fenning, David P.; Ming, Tian The Journal of Physical Chemistry Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acs.jpclett.5b00169	journal	March 2015
Surface termination, composition and reconstruction of Fe3O4(001) and γ-Fe2O3(001) Chambers, S. A.; Joyce, S. A. Surface Science, Vol. 420, Issue 2-3 https://doi.org/10.1016/S0039-6028(98)00657-8	journal	January 1999
Electronic phase diagram of epitaxial La ₁₋ _x Sr _x FeO ₃ films Xie, Y. J.; Scafetta, M. D.; Moon, E. J. Applied Physics Letters, Vol. 105, Issue 6 https://doi.org/10.1063/1.4893139	journal	August 2014
Static and Dynamic Optical Properties of La _{1– x} Sr _x FeO _3−δ : The Effects of A-Site and Oxygen Stoichiometry Smolin, Sergey Y.; Scafetta, Mark D.; Choquette, Amber K. Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b03273	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) Ritzmann, Andrew M.; Muñoz-García, Ana B.; Pavone, Michele Chemistry of Materials, Vol. 25, Issue 15 https://doi.org/10.1021/cm401052w	journal	July 2013
Possible highT c superconductivity in the Ba?La?Cu?O system Bednorz, J. G.; M�ller, K. A. Zeitschrift f�r Physik B Condensed Matter, Vol. 64, Issue 2 https://doi.org/10.1007/BF01303701	journal	June 1986
Perovskites in catalysis and electrocatalysis Hwang, Jonathan; Rao, Reshma R.; Giordano, Livia Science, Vol. 358, Issue 6364 https://doi.org/10.1126/science.aam7092	journal	November 2017
Metal-insulator transitions Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori Reviews of Modern Physics, Vol. 70, Issue 4, p. 1039-1263 https://doi.org/10.1103/RevModPhys.70.1039	journal	October 1998
Fermi level shift in La1−xSrxMO3 (M=Mn, Fe, Co, and Ni) probed by Schottky-like heteroepitaxial junctions with SrTi0.99Nb0.01O3 Sawa, A.; Yamamoto, A.; Yamada, H. Applied Physics Letters, Vol. 90, Issue 25 https://doi.org/10.1063/1.2749431	journal	June 2007
Control of Functional Responses Via Reversible Oxygen Loss in La _{1- x} Sr _x FeO _3-δ Films Xie, Yujun; Scafetta, Mark D.; Sichel-Tissot, Rebecca J. Advanced Materials, Vol. 26, Issue 9 https://doi.org/10.1002/adma.201304374	journal	November 2013
Synthesis and characterization of the La1−xSrxFeO3−δ system and the fluorinated phases La1−xSrxFeO3−xFx Clemens, Oliver; Kuhn, Melanie; Haberkorn, Robert Journal of Solid State Chemistry, Vol. 184, Issue 11 https://doi.org/10.1016/j.jssc.2011.08.037	journal	November 2011
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Time-dependent density functional theory within the Tamm–Dancoff approximation Hirata, So; Head-Gordon, Martin Chemical Physics Letters, Vol. 314, Issue 3-4 https://doi.org/10.1016/S0009-2614(99)01149-5	journal	December 1999
Multiband Optical Absorption Controlled by Lattice Strain in Thin-Film ${LaCrO}_{3}$ Sushko, Peter V.; Qiao, Liang; Bowden, Mark Physical Review Letters, Vol. 110, Issue 7 https://doi.org/10.1103/PhysRevLett.110.077401	journal	February 2013
Electronic structure of negative charge transfer ${CaFeO}_{3}$ across the metal-insulator transition Rogge, Paul C.; Chandrasena, Ravini U.; Cammarata, Antonio Physical Review Materials, Vol. 2, Issue 1 https://doi.org/10.1103/PhysRevMaterials.2.015002	journal	January 2018
Mixed-valence manganites Coey, J. M. D.; Viret, M.; von Molnár, S. Advances in Physics, Vol. 48, Issue 2 https://doi.org/10.1080/000187399243455	journal	March 1999
Linking surface chemistry to photovoltage in Sr-substituted LaFeO ₃ for water oxidation Stoerzinger, Kelsey A.; Wang, Le; Ye, Yifan Journal of Materials Chemistry A, Vol. 6, Issue 44 https://doi.org/10.1039/C8TA05741A	journal	January 2018
Perovskite Oxide for Solid Oxide Fuel Cells Ishihara, Tatsumi Fuel Cells and Hydrogen Energy https://doi.org/10.1007/978-0-387-77708-5	book	January 2009
Band structure and optical transitions in LaFeO ₃ : theory and experiment Scafetta, Mark D.; Cordi, Adam M.; Rondinelli, James M. Journal of Physics: Condensed Matter, Vol. 26, Issue 50 https://doi.org/10.1088/0953-8984/26/50/505502	journal	November 2014
General Purpose Electrostatic Embedding Potential Sushko, Peter V.; Abarenkov, Igor V. Journal of Chemical Theory and Computation, Vol. 6, Issue 4 https://doi.org/10.1021/ct900480p	journal	February 2010
Versatile helimagnetic phases under magnetic fields in cubic perovskite ${SrFeO}_{3}$ Ishiwata, S.; Tokunaga, M.; Kaneko, Y. Physical Review B, Vol. 84, Issue 5 https://doi.org/10.1103/PhysRevB.84.054427	journal	August 2011
Optical absorption in epitaxial La1−xSrxFeO3 thin films Scafetta, M. D.; Xie, Y. J.; Torres, M. Applied Physics Letters, Vol. 102, Issue 8 https://doi.org/10.1063/1.4794145	journal	February 2013

Cited By (2)

Brownmillerite phase formation and evolution in epitaxial strontium ferrite heterostructures Wang, Le; Yang, Zhenzhong; Bowden, Mark E. Applied Physics Letters, Vol. 114, Issue 23 https://doi.org/10.1063/1.5096769	journal	June 2019
Confined polaronic transport in (LaFeO ₃ ) _n /(SrFeO ₃ ) ₁ superlattices Chang, Seo Hyoung; Kim, Seong Keun; Kim, Young-Min APL Materials, Vol. 7, Issue 7 https://doi.org/10.1063/1.5110190	journal	July 2019

Similar Records

Hole-induced electronic and optical transitions in

L a_{1 - x} S r_{x} Fe O_{3}

epitaxial thin films

Journal Article · Fri Feb 01 00:00:00 EST 2019 · Physical Review Materials · OSTI ID:1510080

Wang, Le; Du, Yingge; Sushko, Peter V.; +6 more

Closure of the Mott gap and formation of a superthermal metal in the Fröhlich-type nonequilibrium polaron Bose-Einstein condensate in

U O_{2 + x}

Journal Article · Fri Sep 01 00:00:00 EDT 2017 · Physical Review B · OSTI ID:1510080

Conradson, Steven D.; Andersson, David A.; Boland, Kevin S.; +24 more

Doping dependence of the magnitude of fluctuating spin moments in the normal state of the pnictide superconductor

Sr {(F e_{1 - x} C o_{x})}_{2} A s_{2}

inferred from photoemission spectroscopy

Journal Article · Thu Apr 18 00:00:00 EDT 2019 · Physical Review B · OSTI ID:1510080

Vilmercati, P.; Kim, Yeongkwan; Mo, Sung-Kwan; +7 more

Related Subjects

36 MATERIALS SCIENCE
Epitaxial oxide films
Hole doping
Hybrid functional calculations
LaFeO3
Moleclar beam epitaxy
Optical absorption

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

Citation Formats

References (48)

Cited By (2)

Similar Records

Related Subjects

Title: Hole-induced electronic and optical transitions in $L a_{1 - x} S r_{x} Fe O_{3}$ epitaxial thin films