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

Title: Towards spin-polarized two-dimensional electron gas at a surface of an antiferromagnetic insulating oxide

Abstract

Here, the surfaces of transition-metal oxides with the perovskite structure are fertile grounds for the discovery of novel electronic and magnetic phenomena. In this article, we combine scanning transmission electron microscopy (STEM) with density functional theory (DFT) calculations to obtain the electronic and magnetic properties of the (001) surface of a (LaFeO3)8/(SrFeO3)1 superlattice film capped with four layers of LaFeO3. Simultaneously acquired STEM images and electron-energy-loss spectra reveal the surface structure and a reduction in the oxidation state of iron from Fe3+ in the bulk to Fe2+ at the surface, extending over several atomic layers, which signals the presence of oxygen vacancies. The DFT calculations confirm the reduction in terms of oxygen vacancies and further demonstrate the stabilization of an exotic phase in which the surface layer is half metallic and ferromagnetic, while the bulk remains antiferromagnetic and insulating. Based on the calculations, we predict that the surface magnetism and conductivity can be controlled by tuning the partial pressure of oxygen.

Authors:
 [1];  [2];  [3];  [4];  [5];  [3];  [6];  [6];  [7];  [3]
  1. Vanderbilt Univ., Nashville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Washington Univ., St. Louis, MO (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Institute for Basic Science (IBS), Suwon (Republic of Korea); Sungkyunkwan Univ., (SKKU), Suwon (Republic of Korea)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Washington Univ., St. Louis, MO (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States); Korea Institute of Science and Technology, Seoul (Republic of Korea)
  6. Argonne National Lab. (ANL), Argonne, IL (United States)
  7. Vanderbilt Univ., Nashville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Argonne National Lab. (ANL), Argonne, IL (United States); Vanderbilt Univ., Nashville, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1329163
Alternate Identifier(s):
OSTI ID: 1263724; OSTI ID: 1352677; OSTI ID: 1597776
Grant/Contract Number:  
AC05-00OR22725; FG02-09ER46554; AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 94; Journal Issue: 4; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Mishra, Rohan, Kim, Young -Min, He, Qian, Huang, Xing, Kim, Seong Keun, Susner, Michael A., Bhattacharya, Anand, Fong, Dillon D., Pantelides, Sokrates T., and Borisevich, Albina Y. Towards spin-polarized two-dimensional electron gas at a surface of an antiferromagnetic insulating oxide. United States: N. p., 2016. Web. doi:10.1103/PhysRevB.94.045123.
Mishra, Rohan, Kim, Young -Min, He, Qian, Huang, Xing, Kim, Seong Keun, Susner, Michael A., Bhattacharya, Anand, Fong, Dillon D., Pantelides, Sokrates T., & Borisevich, Albina Y. Towards spin-polarized two-dimensional electron gas at a surface of an antiferromagnetic insulating oxide. United States. doi:10.1103/PhysRevB.94.045123.
Mishra, Rohan, Kim, Young -Min, He, Qian, Huang, Xing, Kim, Seong Keun, Susner, Michael A., Bhattacharya, Anand, Fong, Dillon D., Pantelides, Sokrates T., and Borisevich, Albina Y. Mon . "Towards spin-polarized two-dimensional electron gas at a surface of an antiferromagnetic insulating oxide". United States. doi:10.1103/PhysRevB.94.045123. https://www.osti.gov/servlets/purl/1329163.
@article{osti_1329163,
title = {Towards spin-polarized two-dimensional electron gas at a surface of an antiferromagnetic insulating oxide},
author = {Mishra, Rohan and Kim, Young -Min and He, Qian and Huang, Xing and Kim, Seong Keun and Susner, Michael A. and Bhattacharya, Anand and Fong, Dillon D. and Pantelides, Sokrates T. and Borisevich, Albina Y.},
abstractNote = {Here, the surfaces of transition-metal oxides with the perovskite structure are fertile grounds for the discovery of novel electronic and magnetic phenomena. In this article, we combine scanning transmission electron microscopy (STEM) with density functional theory (DFT) calculations to obtain the electronic and magnetic properties of the (001) surface of a (LaFeO3)8/(SrFeO3)1 superlattice film capped with four layers of LaFeO3. Simultaneously acquired STEM images and electron-energy-loss spectra reveal the surface structure and a reduction in the oxidation state of iron from Fe3+ in the bulk to Fe2+ at the surface, extending over several atomic layers, which signals the presence of oxygen vacancies. The DFT calculations confirm the reduction in terms of oxygen vacancies and further demonstrate the stabilization of an exotic phase in which the surface layer is half metallic and ferromagnetic, while the bulk remains antiferromagnetic and insulating. Based on the calculations, we predict that the surface magnetism and conductivity can be controlled by tuning the partial pressure of oxygen.},
doi = {10.1103/PhysRevB.94.045123},
journal = {Physical Review B},
number = 4,
volume = 94,
place = {United States},
year = {2016},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Giant spin splitting of the two-dimensional electron gas at the surface of SrTiO3
journal, October 2014

  • Santander-Syro, A. F.; Fortuna, F.; Bareille, C.
  • Nature Materials, Vol. 13, Issue 12
  • DOI: 10.1038/nmat4107

Inner shell edge profiles in electron energy loss spectroscopy
journal, January 1985


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

The crystal and magnetic structures of Sr2LaFe3O8
journal, February 1990


Projector augmented-wave method
journal, December 1994


Electron Transfer and Ionic Displacements at the Origin of the 2D Electron Gas at the LAO/STO Interface: Direct Measurements with Atomic-Column Spatial Resolution
journal, June 2012

  • Cantoni, Claudia; Gazquez, Jaume; Miletto Granozio, Fabio
  • Advanced Materials, Vol. 24, Issue 29
  • DOI: 10.1002/adma.201200667

Atomic-scale electrochemistry on the surface of a manganite by scanning tunneling microscopy
journal, April 2015

  • Vasudevan, Rama K.; Tselev, Alexander; Gianfrancesco, Anthony G.
  • Applied Physics Letters, Vol. 106, Issue 14
  • DOI: 10.1063/1.4917299

Oxygen-Vacancy-Induced Polar Behavior in (LaFeO 3 ) 2 /(SrFeO 3 ) Superlattices
journal, April 2014

  • Mishra, Rohan; Kim, Young-Min; Salafranca, Juan
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500601d

Spin-phonon coupling effects in transition-metal perovskites: A DFT +  U and hybrid-functional study
journal, February 2012


Fermi Surface and Superconductivity in Low-Density High-Mobility δ -Doped SrTiO 3
journal, August 2011


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

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Towards 3D Mapping of BO 6 Octahedron Rotations at Perovskite Heterointerfaces, Unit Cell by Unit Cell
journal, July 2015


Interaction Between the d Shells in the Transition Metals
journal, February 1951


The structure and chemistry of the TiO2-rich surface of SrTiO3 (001)
journal, September 2002

  • Erdman, Natasha; Poeppelmeier, Kenneth R.; Asta, Mark
  • Nature, Vol. 419, Issue 6902
  • DOI: 10.1038/nature01010

Oxygen-Induced Surface Reconstruction of SrRuO 3 and Its Effect on the BaTiO 3 Interface
journal, June 2010

  • Shin, Junsoo; Borisevich, Albina Y.; Meunier, Vincent
  • ACS Nano, Vol. 4, Issue 7
  • DOI: 10.1021/nn1008337

Electric modulation of conduction in multiferroic Ca-doped BiFeO3 films
journal, April 2009

  • Yang, C. -H.; Seidel, J.; Kim, S. Y.
  • Nature Materials, Vol. 8, Issue 6
  • DOI: 10.1038/nmat2432

Spin-state transition of iron in ( perovskite
journal, November 2009

  • Feldhoff, Armin; Martynczuk, Julia; Arnold, Mirko
  • Journal of Solid State Chemistry, Vol. 182, Issue 11
  • DOI: 10.1016/j.jssc.2009.07.058

Quantification of ferrous/ferric ratios in minerals: new evaluation schemes of Fe L 23 electron energy-loss near-edge spectra
journal, April 2002


Superexchange interaction and symmetry properties of electron orbitals
journal, July 1959


A homologous series of structures on the surface of SrTiO3(110)
journal, February 2010

  • Enterkin, James A.; Subramanian, Arun K.; Russell, Bruce C.
  • Nature Materials, Vol. 9, Issue 3
  • DOI: 10.1038/nmat2636

Atomic-resolution imaging of oxidation states in manganites
journal, February 2009


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Direct imaging of hydrogen-atom columns in a crystal by annular bright-field electron microscopy
journal, February 2011

  • Ishikawa, Ryo; Okunishi, Eiji; Sawada, Hidetaka
  • Nature Materials, Vol. 10, Issue 4
  • DOI: 10.1038/nmat2957

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


Surface Studies by Scanning Tunneling Microscopy
journal, July 1982


Oxygen 1 s x-ray-absorption edges of transition-metal oxides
journal, September 1989


Neutron-diffraction study of the magnetic properties of perovskite-like compounds LaBO3
journal, April 1957


Formation of titanium monoxide (001) single-crystalline thin film induced by ion bombardment of titanium dioxide (110)
journal, February 2015

  • Pabón, B. M.; Beltrán, J. I.; Sánchez-Santolino, G.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7147

Composition, structure, and stability of RuO 2 ( 110 ) as a function of oxygen pressure
journal, December 2001


Atomic Control of the SrTiO3 Crystal Surface
journal, December 1994


Two-dimensional electron gas with universal subbands at the surface of SrTiO3
journal, January 2011

  • Santander-Syro, A. F.; Copie, O.; Kondo, T.
  • Nature, Vol. 469, Issue 7329, p. 189-193
  • DOI: 10.1038/nature09720

MATERIALS SCIENCE: The Renaissance of Magnetoelectric Multiferroics
journal, July 2005


Reversible Chemical Switching of a Ferroelectric Film
journal, January 2009


Toward tuning the surface functionalization of small ceria nanoparticles
journal, February 2014

  • Huang, Xing; Wang, Binghui; Grulke, Eric A.
  • The Journal of Chemical Physics, Vol. 140, Issue 7
  • DOI: 10.1063/1.4864378

Creation and control of a two-dimensional electron liquid at the bare SrTiO3 surface
journal, January 2011

  • Meevasana, W.; King, P. D. C.; He, R. H.
  • Nature Materials, Vol. 10, Issue 2
  • DOI: 10.1038/nmat2943

Functional Ion Defects in Transition Metal Oxides
journal, August 2013


Surface Control of Epitaxial Manganite Films via Oxygen Pressure
journal, February 2015

  • Tselev, Alexander; Vasudevan, Rama K.; Gianfrancesco, Anthony G.
  • ACS Nano, Vol. 9, Issue 4
  • DOI: 10.1021/acsnano.5b00743

Chiral magnetic order at surfaces driven by inversion asymmetry
journal, May 2007


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

Surface Reconstruction with a Fractional Hole: ( 5 × 5 ) R 26.6 ° LaAlO 3 (001)
journal, February 2007


Strong Reciprocal Interaction between Polarization and Surface Stoichiometry in Oxide Ferroelectrics
journal, October 2014

  • Saidi, Wissam A.; Martirez, John Mark P.; Rappe, Andrew M.
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl5035013

Atomic-resolution spectroscopic imaging of oxide interfaces
journal, December 2010


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

Long Range Charge Ordering in Magnetite Below the Verwey Transition
journal, December 2001


Bonding and structure of a reconstructed (001) surface of SrTiO3 from TEM
journal, October 2012

  • Zhu, Guo-zhen; Radtke, Guillaume; Botton, Gianluigi A.
  • Nature, Vol. 490, Issue 7420
  • DOI: 10.1038/nature11563

Atomic-scale images of charge ordering in a mixed-valence manganite
journal, April 2002

  • Renner, Ch.; Aeppli, G.; Kim, B. -G.
  • Nature, Vol. 416, Issue 6880
  • DOI: 10.1038/416518a

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Ferroelectric surface chemistry: First-principles study of the PbTiO 3 surface
journal, July 2013


Electron-energy-loss-spectroscopy near-edge fine structures in the iron-oxygen system
journal, November 1991


Direct Imaging of Reconstructed Atoms on TiO2 (110) Surfaces
journal, October 2008


Enhancing Photocatalytic Activity of LaTiO 2 N by Removal of Surface Reconstruction Layer
journal, January 2014

  • Matsukawa, Michinori; Ishikawa, Ryo; Hisatomi, Takashi
  • Nano Letters, Vol. 14, Issue 2
  • DOI: 10.1021/nl404688h

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

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Electron-energy-loss core-edge structures in manganese oxides
journal, July 1993


Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991

  • Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
  • Physical Review B, Vol. 44, Issue 3, p. 943-954
  • DOI: 10.1103/PhysRevB.44.943

Lanthanum aluminate (110) 3 × 1 surface reconstruction
journal, March 2015


Emergent phenomena at oxide interfaces
journal, January 2012

  • Hwang, H. Y.; Iwasa, Y.; Kawasaki, M.
  • Nature Materials, Vol. 11, Issue 2
  • DOI: 10.1038/nmat3223

Highly conductive nanolayers on strontium titanate produced by preferential ion-beam etching
journal, July 2005

  • Reagor, David W.; Butko, Vladimir Y.
  • Nature Materials, Vol. 4, Issue 8, p. 593-596
  • DOI: 10.1038/nmat1402

Phase diagram of Sr on Si(001): A first-principles study
journal, August 2009


Beyond Condensed Matter Physics on the Nanoscale: The Role of Ionic and Electrochemical Phenomena in the Physical Functionalities of Oxide Materials
journal, November 2012

  • Kalinin, Sergei V.; Borisevich, Albina; Fong, Dillon
  • ACS Nano, Vol. 6, Issue 12
  • DOI: 10.1021/nn304930x

Atomic Polarization and Local Reactivity on Ferroelectric Surfaces:  A New Route toward Complex Nanostructures
journal, June 2002

  • Kalinin, S. V.; Bonnell, D. A.; Alvarez, T.
  • Nano Letters, Vol. 2, Issue 6
  • DOI: 10.1021/nl025556u

Electronic and crystal-field effects in the fine structure of electron energy-loss spectra of manganites
journal, February 2009


Direct Evidence of Surface Reduction in Monoclinic BiVO 4
journal, May 2015

  • Rossell, Marta D.; Agrawal, Piyush; Borgschulte, Andreas
  • Chemistry of Materials, Vol. 27, Issue 10
  • DOI: 10.1021/cm504248d

Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries
journal, June 2011

  • Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki
  • Nature Chemistry, Vol. 3, Issue 7, p. 546-550
  • DOI: 10.1038/nchem.1069

Ab initio energetics of La B O 3 ( 001 ) ( B = Mn , Fe, Co, and Ni) for solid oxide fuel cell cathodes
journal, December 2009


Physical Properties and Cation Arrangement of Oxides with Spinel Structures II. Electronic Conductivity
journal, April 1947

  • Verwey, E. J.; Haayman, P. W.; Romeijn, F. C.
  • The Journal of Chemical Physics, Vol. 15, Issue 4
  • DOI: 10.1063/1.1746466

Theory of the Role of Covalence in the Perovskite-Type Manganites [ La ,   M ( II ) ] Mn O 3
journal, October 1955