Oxygen-Vacancy-Induced Polar Behavior in (LaFeO3)2/(SrFeO3) Superlattices
Abstract
Complex oxides displaying ferroelectric and/or multiferroic behavior are of high fundamental and applied interest. In this work, for the first time, we show that it is possible to achieve polar order in a superlattice made up of two nonpolar oxides by means of oxygen vacancy ordering. Using scanning transmission electron microscopy imaging, we show the polar displacement of magnetic Fe ions in a superlattice of (LaFeO3)2/(SrFeO3) grown on a SrTiO3 substrate. Using density functional theory calculations, we systematically study the effect of epitaxial strain, octahedral rotations, and surface terminations in the superlattice and find them to have a negligible effect on the antipolar displacements of the Fe ions lying in between SrO and LaO layers of the superlattice (i.e., within La0.5Sr0.5FeO3 unit cells). The introduction of oxygen vacancies, on the other hand, triggers a polar displacement of the Fe ions. We confirm this important result using electron energy loss spectroscopy, which shows partial oxygen vacancy ordering in the region where polar displacements are observed and an absence of vacancy ordering outside of that area.
- Authors:
-
- Vanderbilt Univ., Nashville, TN (United States). Dept. of Physics and Astronomy; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division; Korea Basic Science Inst., Daejeon (Korea). Division of Electron Microscopic Research
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division; Univ. Complutense Madrid (Spain). Complex Materials Physics Group
- Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Korea Inst. of Science and Technology, Seoul (Korea). Electronic Materials Research Center
- Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
- Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1357051
- Grant/Contract Number:
- AC02-06CH11357; FG02-09ER46554; AC02-05CH11231; 239739; AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 14; Journal Issue: 5; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; DFT calculations; Multiferroics; Oxygen vacancies; Polar oxides; Scanning transmission electron microscopy; Transition-metal oxides
Citation Formats
Mishra, Rohan, Kim, Young-Min, Salafranca, Juan, Kim, Seong Keun, Chang, Seo Hyoung, Bhattacharya, Anand, Fong, Dillon D., Pennycook, Stephen J., Pantelides, Sokrates T., and Borisevich, Albina Y. Oxygen-Vacancy-Induced Polar Behavior in (LaFeO3)2/(SrFeO3) Superlattices. United States: N. p., 2014.
Web. doi:10.1021/nl500601d.
Mishra, Rohan, Kim, Young-Min, Salafranca, Juan, Kim, Seong Keun, Chang, Seo Hyoung, Bhattacharya, Anand, Fong, Dillon D., Pennycook, Stephen J., Pantelides, Sokrates T., & Borisevich, Albina Y. Oxygen-Vacancy-Induced Polar Behavior in (LaFeO3)2/(SrFeO3) Superlattices. United States. https://doi.org/10.1021/nl500601d
Mishra, Rohan, Kim, Young-Min, Salafranca, Juan, Kim, Seong Keun, Chang, Seo Hyoung, Bhattacharya, Anand, Fong, Dillon D., Pennycook, Stephen J., Pantelides, Sokrates T., and Borisevich, Albina Y. Tue .
"Oxygen-Vacancy-Induced Polar Behavior in (LaFeO3)2/(SrFeO3) Superlattices". United States. https://doi.org/10.1021/nl500601d. https://www.osti.gov/servlets/purl/1357051.
@article{osti_1357051,
title = {Oxygen-Vacancy-Induced Polar Behavior in (LaFeO3)2/(SrFeO3) Superlattices},
author = {Mishra, Rohan and Kim, Young-Min and Salafranca, Juan and Kim, Seong Keun and Chang, Seo Hyoung and Bhattacharya, Anand and Fong, Dillon D. and Pennycook, Stephen J. and Pantelides, Sokrates T. and Borisevich, Albina Y.},
abstractNote = {Complex oxides displaying ferroelectric and/or multiferroic behavior are of high fundamental and applied interest. In this work, for the first time, we show that it is possible to achieve polar order in a superlattice made up of two nonpolar oxides by means of oxygen vacancy ordering. Using scanning transmission electron microscopy imaging, we show the polar displacement of magnetic Fe ions in a superlattice of (LaFeO3)2/(SrFeO3) grown on a SrTiO3 substrate. Using density functional theory calculations, we systematically study the effect of epitaxial strain, octahedral rotations, and surface terminations in the superlattice and find them to have a negligible effect on the antipolar displacements of the Fe ions lying in between SrO and LaO layers of the superlattice (i.e., within La0.5Sr0.5FeO3 unit cells). The introduction of oxygen vacancies, on the other hand, triggers a polar displacement of the Fe ions. We confirm this important result using electron energy loss spectroscopy, which shows partial oxygen vacancy ordering in the region where polar displacements are observed and an absence of vacancy ordering outside of that area.},
doi = {10.1021/nl500601d},
journal = {Nano Letters},
number = 5,
volume = 14,
place = {United States},
year = {Tue Apr 15 00:00:00 EDT 2014},
month = {Tue Apr 15 00:00:00 EDT 2014}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 53 works
Citation information provided by
Web of Science
Web of Science
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:
Why Are There so Few Magnetic Ferroelectrics?
journal, July 2000
- Hill, Nicola A.
- The Journal of Physical Chemistry B, Vol. 104, Issue 29
Origin of ferroelectricity in perovskite oxides
journal, July 1992
- Cohen, Ronald E.
- Nature, Vol. 358, Issue 6382
Epitaxial BiFeO3 Multiferroic Thin Film Heterostructures
journal, March 2003
- Wang, J.; Neaton, J. B.; Zheng, H.
- Science, Vol. 299, Issue 5613, p. 1719-1722
Magnetic and Electric Phase Control in Epitaxial from First Principles
journal, December 2006
- Fennie, Craig J.; Rabe, Karin M.
- Physical Review Letters, Vol. 97, Issue 26
A strong ferroelectric ferromagnet created by means of spin–lattice coupling
journal, August 2010
- Lee, June Hyuk; Fang, Lei; Vlahos, Eftihia
- Nature, Vol. 466, Issue 7309
The origin of ferroelectricity in magnetoelectric YMnO3
journal, February 2004
- Van Aken, Bas B.; Palstra, Thomas T. M.; Filippetti, Alessio
- Nature Materials, Vol. 3, Issue 3
Ferroelectric transition in from first principles
journal, September 2005
- Fennie, Craig J.; Rabe, Karin M.
- Physical Review B, Vol. 72, Issue 10
Ferroelectricity from iron valence ordering in the charge-frustrated system LuFe2O4
journal, August 2005
- Ikeda, Naoshi; Ohsumi, Hiroyuki; Ohwada, Kenji
- Nature, Vol. 436, Issue 7054
Magnetic control of ferroelectric polarization
journal, November 2003
- Kimura, T.; Goto, T.; Shintani, H.
- Nature, Vol. 426, Issue 6962
Probing oxygen vacancy concentration and homogeneity in solid-oxide fuel-cell cathode materials on the subunit-cell level
journal, August 2012
- Kim, Young-Min; He, Jun; Biegalski, Michael D.
- Nature Materials, Vol. 11, Issue 10
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
Complexity in Strongly Correlated Electronic Systems
journal, July 2005
- Dagotto, E.
- Science, Vol. 309, Issue 5732
Orbital Physics in Transition-Metal Oxides
journal, April 2000
- Tokura, Y.
- Science, Vol. 288, Issue 5465
Stair-like Metamagnetic Transition Induced by Controlled Introduction of Oxygen Deficiency in La 0.5 Ca 0.5 MnO 3−δ
journal, June 2012
- Cortés-Gil, R.; Ruiz-González, L.; Alonso, J. M.
- Chemistry of Materials, Vol. 24, Issue 13
Atomic-Resolution Imaging of Spin-State Superlattices in Nanopockets within Cobaltite Thin Films
journal, March 2011
- Gazquez, Jaume; Luo, Weidong; Oxley, Mark P.
- Nano Letters, Vol. 11, Issue 3, p. 973-976
Insulating Ferromagnetic Films: A Phase Induced by Ordering of Oxygen Vacancies
journal, February 2014
- Biškup, Neven; Salafranca, Juan; Mehta, Virat
- Physical Review Letters, Vol. 112, Issue 8
Functional Ion Defects in Transition Metal Oxides
journal, August 2013
- Kalinin, S. V.; Spaldin, N. A.
- Science, Vol. 341, Issue 6148
Reversible Chemical Switching of a Ferroelectric Film
journal, January 2009
- Wang, R. V.; Fong, D. D.; Jiang, F.
- Physical Review Letters, Vol. 102, Issue 4
Atomic-Scale Compensation Phenomena at Polar Interfaces
journal, November 2010
- Chisholm, Matthew F.; Luo, Weidong; Oxley, Mark P.
- Physical Review Letters, Vol. 105, Issue 19
The classification of tilted octahedra in perovskites
journal, November 1972
- Glazer, A. M.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 11
Octahedral Tilting in Perovskites. I. Geometrical Considerations
journal, February 1997
- Woodward, P. M.
- Acta Crystallographica Section B Structural Science, Vol. 53, Issue 1
Neutron-diffraction study of the magnetic properties of perovskite-like compounds LaBO3
journal, April 1957
- Koehler, W. C.; Wollan, E. O.
- Journal of Physics and Chemistry of Solids, Vol. 2, Issue 2
Electronic Conductivity, Seebeck Coefficient, and Defect Structure of La1-xSrxFeO3 (x=0.l, 0.25)
journal, April 1983
- Mizusaki, Junichiro; Sasamoto, Tadashi; Cannon, W. Roger
- Journal of the American Ceramic Society, Vol. 66, Issue 4
Thermochemistry of La 1 - x Sr x FeO 3 - δ Solid Solutions (0.0 ≤ x ≤ 1.0, 0.0 ≤ δ ≤ 0.5)
journal, April 2005
- Cheng, Jihong; Navrotsky, Alexandra; Zhou, Xiao-Dong
- Chemistry of Materials, Vol. 17, Issue 8
The Effect of Oxygen Stoichiometry on Phase Relations and Structure in the System La1-xSrxFeO3-δ (0 ≤ x ≤ 1, 0 ≤ δ ≤ 0.5)
journal, March 1994
- Dann, S. E.; Currie, D. B.; Weller, M. T.
- Journal of Solid State Chemistry, Vol. 109, Issue 1
Anisotropic and Nonlinear Thermal and Chemical Expansion of La 1– x Sr x FeO 3−δ ( x = 0.3, 0.4, 0.5) Perovskite Materials
journal, August 2013
- Chen, Xinzhi; Grande, Tor
- Chemistry of Materials, Vol. 25, Issue 16
Crystal Structure and Thermal Expansion of La1−xSrxFeO3−δ Materials
journal, October 2004
- Fossdal, Anita; Menon, Mohan; Waernhus, Ivar
- Journal of the American Ceramic Society, Vol. 87, Issue 10
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
The structural consequences of charge disproportionation in mixed-valence iron oxides. I. The crystal structure of Sr2LaFe3O8.94 at room temperature and 50 K
journal, February 1990
- Battle, P. D.; Gibb, T. C.; Lightfoot, P.
- Journal of Solid State Chemistry, Vol. 84, Issue 2
The crystal and magnetic structures of Sr2LaFe3O8
journal, February 1990
- Battle, P. D.; Gibb, T. C.; Lightfoot, P.
- Journal of Solid State Chemistry, Vol. 84, Issue 2
Suppression of Octahedral Tilts and Associated Changes in Electronic Properties at Epitaxial Oxide Heterostructure Interfaces
journal, August 2010
- Borisevich, A. Y.; Chang, H. J.; Huijben, M.
- Physical Review Letters, Vol. 105, Issue 8
Atomically Resolved Mapping of Polarization and Electric Fields Across Ferroelectric/Oxide Interfaces by Z-contrast Imaging
journal, April 2011
- Chang, Hye Jung; Kalinin, Sergei V.; Morozovska, Anna N.
- Advanced Materials, Vol. 23, Issue 21
Interplay of Octahedral Tilts and Polar Order in BiFeO 3 Films
journal, March 2013
- Kim, Young-Min; Kumar, Amit; Hatt, Alison
- Advanced Materials, Vol. 25, Issue 17
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Chemical Expansivity of Electrochemical Ceramics
journal, September 2001
- Adler, Stuart B.
- Journal of the American Ceramic Society, Vol. 84, Issue 9
Charge localization increases chemical expansion in cerium-based oxides
journal, January 2012
- Marrocchelli, Dario; Bishop, Sean R.; Tuller, Harry L.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 35
Surface effects on phase transitions in ferroelectrics and dipolar magnets
journal, August 1979
- Kretschmer, R.; Binder, K.
- Physical Review B, Vol. 20, Issue 3
Unit-cell scale mapping of ferroelectricity and tetragonality in epitaxial ultrathin ferroelectric films
journal, December 2006
- Jia, Chun-Lin; Nagarajan, Valanoor; He, Jia-Qing
- Nature Materials, Vol. 6, Issue 1
Structural Basis for the Conducting Interface between and
journal, October 2007
- Willmott, P. R.; Pauli, S. A.; Herger, R.
- Physical Review Letters, Vol. 99, Issue 15, Article No. 155502
Ionic Polarizability of Conductive Metal Oxides and Critical Thickness for Ferroelectricity in
journal, March 2006
- Gerra, G.; Tagantsev, A. K.; Setter, N.
- Physical Review Letters, Vol. 96, Issue 10
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
First-Principles Modeling of Electrostatically Doped Perovskite Systems
journal, March 2011
- Stengel, Massimiliano
- Physical Review Letters, Vol. 106, Issue 13
Quantification of the EELS near-edge structures to study Mn doping in oxides
journal, December 1995
- Botton, G. A.; Appel, C. C.; Horsewell, A.
- Journal of Microscopy, Vol. 180, Issue 3
Oxidation states of Mn and Fe in various compound oxide systems
journal, July 2006
- Schmid, H. K.; Mader, W.
- Micron, Vol. 37, Issue 5
A STEM/EELS method for mapping iron valence ratios in oxide minerals
journal, June 2006
- Cavé, Lisa; Al, Tom; Loomer, Diana
- Micron, Vol. 37, Issue 4
Cation ordering in perovskites
journal, January 2010
- King, Graham; Woodward, Patrick M.
- Journal of Materials Chemistry, Vol. 20, Issue 28
Structures and Electromagnetic Properties of New Metal-Ordered Manganites: R BaMn 2 O 6 ( R =Y and Rare-Earth Elements)
journal, December 2002
- Nakajima, Tomohiko; Kageyama, Hiroshi; Yoshizawa, Hideki
- Journal of the Physical Society of Japan, Vol. 71, Issue 12
Ferrodistortive Instability at the (001) Surface of Half-Metallic Manganites
journal, November 2007
- Pruneda, J. M.; Ferrari, V.; Rurali, R.
- Physical Review Letters, Vol. 99, Issue 22
Ferroelectric control of magnetization in La Sr MnO manganites: A first-principles study
journal, July 2012
- Chen, Hanghui; Ismail-Beigi, Sohrab
- Physical Review B, Vol. 86, Issue 2
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Strain-controlled oxygen vacancy formation and ordering in CaMnO
journal, August 2013
- Aschauer, Ulrich; Pfenninger, Reto; Selbach, Sverre M.
- Physical Review B, Vol. 88, Issue 5
Lattice mismatch accommodation via oxygen vacancy ordering in epitaxial La 0.5 Sr 0.5 CoO 3-δ thin films
journal, July 2013
- Gazquez, J.; Bose, Shameek; Sharma, M.
- APL Materials, Vol. 1, Issue 1
Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge
journal, August 2013
- Jeen, Hyoungjeen; Choi, Woo Seok; Biegalski, Michael D.
- Nature Materials, Vol. 12, Issue 11
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Correlation hole of the spin-polarized electron gas, with exact small-wave-vector and high-density scaling
journal, December 1991
- Wang, Yue; Perdew, John P.
- Physical Review B, Vol. 44, Issue 24
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
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
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
Spin-phonon coupling effects in transition-metal perovskites: A DFT + and hybrid-functional study
journal, February 2012
- Hong, Jiawang; Stroppa, Alessandro; Íñiguez, Jorge
- Physical Review B, Vol. 85, Issue 5
Works referencing / citing this record:
Nanoscale Topotactic Phase Transformation in SrFeO x Epitaxial Thin Films for High‐Density Resistive Switching Memory
journal, October 2019
- Tian, Junjiang; Wu, Haijun; Fan, Zhen
- Advanced Materials, Vol. 31, Issue 49
Electrochemistry Induced Giant and Reversible Deformation in Oxides
journal, February 2020
- Meng, Fanqi; Ji, Yiru; Chen, Sijing
- Advanced Functional Materials, Vol. 30, Issue 15
Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale
journal, June 2017
- Vasudevan, Rama K.; Balke, Nina; Maksymovych, Peter
- Applied Physics Reviews, Vol. 4, Issue 2
The effects of the oxygen content on the photoelectrochemical properties of LaFeO3 perovskite thin films obtained by pulsed laser deposition
journal, November 2019
- Andrei, F.; Boerasu, I.; Birjega, R.
- Applied Physics A, Vol. 125, Issue 11
Aberration-corrected scanning transmission electron microscopy for complex transition metal oxides
journal, June 2016
- Zhang, Qing-Hua; Xiao, Dong-Dong; Gu, Lin
- Chinese Physics B, Vol. 25, Issue 6
Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO2.5-σ
journal, July 2017
- Zhang, Qinghua; He, Xu; Shi, Jinan
- Nature Communications, Vol. 8, Issue 1
Atomic-resolution in-situ cooling study of oxygen vacancy ordering in La 0.5 Sr 0.5 CoO 3−δ thin films
journal, June 2019
- Rui, Xue; Klie, Robert F.
- Applied Physics Letters, Vol. 114, Issue 23
Emergent magnetic phase transitions in Fe-doped SrTiO 3−δ
journal, December 2019
- Pei, Yujuan; Zhang, Ruyi; Song, Yang
- AIP Advances, Vol. 9, Issue 12
Ferroelectric or non-ferroelectric: why so many materials exhibit ferroelectricity on the nanoscale
preprint, January 2017
- Vasudevan, Rama K.; Balke, Nina; Maksymovych, Peter
- arXiv