Towards 3D mapping of BO₆ octahedron rotations at perovskite heterointerfaces, unit cell by unit cell
Abstract
The rich functionalities in the ABO₃ perovskite oxides originate at least partly from the ability of the corner-connected BO₆ octahedral network to host a large variety of cations through distortions and rotations. Characterizing these rotations, which significantly affect both fundamental aspects of materials behavior and possible applications, remains a major challenge. In this work, we have developed a unique method of investigating BO₆ rotation patterns in complex oxides ABO₃ with unit cell resolution at heterointerfaces, where novel properties often emerge. Our method involves column shape analysis in annular bright field - scanning transmission electron microscope images of the ABO₃ heterointerfaces taken in specific orientations. The rotating phase of BO₆ octahedra can be identified for all three spatial dimensions without the need of case-by-case simulation. In several common rotation systems, it is now possible to quantitatively measure all three rotation angles. With this method, we examined interfaces between perovskites with distinct tilt systems as well as interfaces between tilted and untilted perovskites, identifying an unusual coupling behavior at the CaTiO₃/LSAT interface. We believe this unique method will significantly improve our knowledge of the complex oxide heterointerfaces.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); The Univ. of Tokyo, Tokyo (Japan)
- Drexel Univ., Philadelphia, PA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1213334
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 8; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
He, Qian, Ishikawa, Ryo, Lupini, Andrew R., Qiao, Liang, Moon, Eun Ju, Ovchinnikov, Oleg S., May, Steven J., Biegalski, Michael D., and Borisevich, Albina Y. Towards 3D mapping of BO₆ octahedron rotations at perovskite heterointerfaces, unit cell by unit cell. United States: N. p., 2015.
Web. doi:10.1021/acsnano.5b03232.
He, Qian, Ishikawa, Ryo, Lupini, Andrew R., Qiao, Liang, Moon, Eun Ju, Ovchinnikov, Oleg S., May, Steven J., Biegalski, Michael D., & Borisevich, Albina Y. Towards 3D mapping of BO₆ octahedron rotations at perovskite heterointerfaces, unit cell by unit cell. United States. https://doi.org/10.1021/acsnano.5b03232
He, Qian, Ishikawa, Ryo, Lupini, Andrew R., Qiao, Liang, Moon, Eun Ju, Ovchinnikov, Oleg S., May, Steven J., Biegalski, Michael D., and Borisevich, Albina Y. Wed .
"Towards 3D mapping of BO₆ octahedron rotations at perovskite heterointerfaces, unit cell by unit cell". United States. https://doi.org/10.1021/acsnano.5b03232. https://www.osti.gov/servlets/purl/1213334.
@article{osti_1213334,
title = {Towards 3D mapping of BO₆ octahedron rotations at perovskite heterointerfaces, unit cell by unit cell},
author = {He, Qian and Ishikawa, Ryo and Lupini, Andrew R. and Qiao, Liang and Moon, Eun Ju and Ovchinnikov, Oleg S. and May, Steven J. and Biegalski, Michael D. and Borisevich, Albina Y.},
abstractNote = {The rich functionalities in the ABO₃ perovskite oxides originate at least partly from the ability of the corner-connected BO₆ octahedral network to host a large variety of cations through distortions and rotations. Characterizing these rotations, which significantly affect both fundamental aspects of materials behavior and possible applications, remains a major challenge. In this work, we have developed a unique method of investigating BO₆ rotation patterns in complex oxides ABO₃ with unit cell resolution at heterointerfaces, where novel properties often emerge. Our method involves column shape analysis in annular bright field - scanning transmission electron microscope images of the ABO₃ heterointerfaces taken in specific orientations. The rotating phase of BO₆ octahedra can be identified for all three spatial dimensions without the need of case-by-case simulation. In several common rotation systems, it is now possible to quantitatively measure all three rotation angles. With this method, we examined interfaces between perovskites with distinct tilt systems as well as interfaces between tilted and untilted perovskites, identifying an unusual coupling behavior at the CaTiO₃/LSAT interface. We believe this unique method will significantly improve our knowledge of the complex oxide heterointerfaces.},
doi = {10.1021/acsnano.5b03232},
journal = {ACS Nano},
number = 8,
volume = 9,
place = {United States},
year = {Wed Jul 15 00:00:00 EDT 2015},
month = {Wed Jul 15 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 62 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:
Octahedral Tilting in Perovskites. I. Geometrical Considerations
journal, February 1997
- Woodward, P. M.
- Acta Crystallographica Section B Structural Science, Vol. 53, Issue 1
Octahedral Tilting in Perovskites. II. Structure Stabilizing Forces
journal, February 1997
- Woodward, P. M.
- Acta Crystallographica Section B Structural Science, Vol. 53, Issue 1
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
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
Emergent phenomena at oxide interfaces
journal, January 2012
- Hwang, H. Y.; Iwasa, Y.; Kawasaki, M.
- Nature Materials, Vol. 11, Issue 2
Magnetic Oxide Heterostructures
journal, July 2014
- Bhattacharya, Anand; May, Steven J.
- Annual Review of Materials Research, Vol. 44, Issue 1
Oxide Interfaces--An Opportunity for Electronics
journal, March 2010
- Mannhart, J.; Schlom, D. G.
- Science, Vol. 327, Issue 5973, p. 1607-1611
Emerging physics of oxide heterostructures
journal, June 2011
- Demkov, A. A.; Posadas, A.; Seo, H.
- physica status solidi (b)
Interface Physics in Complex Oxide Heterostructures
journal, March 2011
- Zubko, Pavlo; Gariglio, Stefano; Gabay, Marc
- Annual Review of Condensed Matter Physics, Vol. 2, Issue 1
Substrate coherency driven octahedral rotations in perovskite oxide films
journal, September 2010
- Rondinelli, James M.; Spaldin, Nicola A.
- Physical Review B, Vol. 82, Issue 11
Control of octahedral connectivity in perovskite oxide heterostructures: An emerging route to multifunctional materials discovery
journal, March 2012
- Rondinelli, James M.; May, Steven J.; Freeland, John W.
- MRS Bulletin, Vol. 37, Issue 3
Polar octahedral rotations: A path to new multifunctional materials
journal, November 2012
- Benedek, Nicole A.; Mulder, Andrew T.; Fennie, Craig J.
- Journal of Solid State Chemistry, Vol. 195
Octahedral Rotation-Induced Ferroelectricity in Cation Ordered Perovskites
journal, April 2012
- Rondinelli, James M.; Fennie, Craig J.
- Advanced Materials, Vol. 24, Issue 15
Hybrid Improper Ferroelectricity: A Mechanism for Controllable Polarization-Magnetization Coupling
journal, March 2011
- Benedek, Nicole A.; Fennie, Craig J.
- Physical Review Letters, Vol. 106, Issue 10
Improper ferroelectricity in perovskite oxide artificial superlattices
journal, April 2008
- Bousquet, Eric; Dawber, Matthew; Stucki, Nicolas
- Nature, Vol. 452, Issue 7188
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
Spatial control of functional properties via octahedral modulations in complex oxide superlattices
journal, December 2014
- Moon, E. J.; Colby, R.; Wang, Q.
- Nature Communications, Vol. 5, Issue 1
Effect of Interfacial Octahedral Behavior in Ultrathin Manganite Films
journal, April 2014
- Moon, E. J.; Balachandran, P. V.; Kirby, B. J.
- Nano Letters, Vol. 14, Issue 5
Interrelation between Structure - Magnetic Properties in La 0.5 Sr 0.5 CoO 3
journal, July 2014
- Biegalski, Michael. D.; Takamura, Yayoi; Mehta, Apurva
- Advanced Materials Interfaces, Vol. 1, Issue 8
Tilt engineering of spontaneous polarization and magnetization above 300 K in a bulk layered perovskite
journal, January 2015
- Pitcher, M. J.; Mandal, P.; Dyer, M. S.
- Science, Vol. 347, Issue 6220
Oxygen octahedron reconstruction in the heterointerfaces investigated using aberration-corrected ultrahigh-resolution transmission electron microscopy
journal, February 2009
- Jia, C. L.; Mi, S. B.; Faley, M.
- Physical Review B, Vol. 79, Issue 8
Control of octahedral rotations in (LaNiO ) /(SrMnO ) superlattices
journal, April 2011
- May, S. J.; Smith, C. R.; Kim, J. -W.
- Physical Review B, Vol. 83, Issue 15
Octahedral Tilt Propagation Controlled by A-Site Cation Size at Perovskite Oxide Heterointerfaces
journal, April 2014
- Aso, Ryotaro; Kan, Daisuke; Shimakawa, Yuichi
- Crystal Growth & Design, Vol. 14, Issue 5
Atomic level observation of octahedral distortions at the perovskite oxide heterointerface
journal, July 2013
- Aso, Ryotaro; Kan, Daisuke; Shimakawa, Yuichi
- Scientific Reports, Vol. 3, Issue 1
Octahedral rotations in strained LaAlO 3 /SrTiO 3 (001) heterostructures
journal, February 2014
- Fister, T. T.; Zhou, H.; Luo, Z.
- APL Materials, Vol. 2, Issue 2
Quantifying octahedral rotations in strained perovskite oxide films
journal, July 2010
- May, S. J.; Kim, J. -W.; Rondinelli, J. M.
- Physical Review B, Vol. 82, Issue 1
Electron diffraction of tilted perovskites
journal, July 2005
- Woodward, David I.; Reaney, Ian M.
- Acta Crystallographica Section B Structural Science, Vol. 61, Issue 4
Nano- and Mesoscale Structure of Na$_{1 \over 2}$Bi$_{1 \over 2}$TiO3: A TEM Perspective
journal, May 2012
- Levin, Igor; Reaney, Ian M.
- Advanced Functional Materials, Vol. 22, Issue 16
Oxygen Octahedral Distortions in LaMO 3 /SrTiO 3 Superlattices
journal, April 2014
- Sanchez-Santolino, Gabriel; Cabero, Mariona; Varela, Maria
- Microscopy and Microanalysis, Vol. 20, Issue 3
Nanoscale quantification of octahedral tilts in perovskite films
journal, May 2012
- Hwang, Jinwoo; Zhang, Jack Y.; Son, Junwoo
- Applied Physics Letters, Vol. 100, Issue 19
Direct determination of epitaxial interface structure in Gd2O3 passivation of GaAs
journal, October 2002
- Yacoby, Yizhak; Sowwan, Mukhles; Stern, Edward
- Nature Materials, Vol. 1, Issue 2
Position averaged convergent beam electron diffraction: Theory and applications
journal, January 2010
- LeBeau, James M.; Findlay, Scott D.; Allen, Leslie J.
- Ultramicroscopy, Vol. 110, Issue 2
Mapping Octahedral Tilts and Polarization Across a Domain Wall in BiFeO 3 from Z-Contrast Scanning Transmission Electron Microscopy Image Atomic Column Shape Analysis
journal, October 2010
- Borisevich, AlbinaY.; Ovchinnikov, Oleg S.; Chang, Hye Jung
- ACS Nano, Vol. 4, Issue 10
POTATO – a program for generating perovskite structures distorted by tilting of rigid octahedra
journal, April 1997
- Woodward, P. M.
- Journal of Applied Crystallography, Vol. 30, Issue 2
Control of Octahedral Tilts and Magnetic Properties of Perovskite Oxide Heterostructures by Substrate Symmetry
journal, November 2010
- He, Jun; Borisevich, Albina; Kalinin, Sergei V.
- Physical Review Letters, Vol. 105, Issue 22
Quantitative transmission electron microscopy at atomic resolution
journal, July 2012
- Allen, L. J.; D'Alfonso, A. J.; Forbes, B. D.
- Journal of Physics: Conference Series, Vol. 371
Quantitative STEM: Experimental Methods and Applications
journal, July 2012
- LeBeau, J. M.; Findlay, S. D.; Allen, L. J.
- Journal of Physics: Conference Series, Vol. 371
Direct Observation of Dopant Atom Diffusion in a Bulk Semiconductor Crystal Enhanced by a Large Size Mismatch
journal, October 2014
- Ishikawa, Ryo; Mishra, Rohan; Lupini, Andrew R.
- Physical Review Letters, Vol. 113, Issue 15
Assembly of a Pentagonal Polyoxomolybdate Building Block, [Mo 6 O 21 ] 6- , into Crystalline MoV Oxides
journal, December 2012
- Sadakane, Masahiro; Endo, Keisuke; Kodato, Katsunori
- European Journal of Inorganic Chemistry, Vol. 2013, Issue 10-11
Quantitative Annular Dark Field Electron Microscopy Using Single Electron Signals
journal, October 2013
- Ishikawa, Ryo; Lupini, Andrew R.; Findlay, Scott D.
- Microscopy and Microanalysis, Vol. 20, Issue 1
Counting lithium ions in the diffusion channel of an LiV 2 O 4 crystal
journal, June 2011
- Lee, Soyeon; Oshima, Yoshifumi; Sawada, Hidetaka
- Journal of Applied Physics, Vol. 109, Issue 11
Quantitative evaluation of annular bright-field phase images in STEM
journal, January 2015
- Ishida, Takafumi; Kawasaki, Tadahiro; Tanji, Takayoshi
- Microscopy, Vol. 64, Issue 2
Large-angle illumination STEM: Toward three-dimensional atom-by-atom imaging
journal, April 2015
- Ishikawa, Ryo; Lupini, Andrew R.; Hinuma, Yoyo
- Ultramicroscopy, Vol. 151
Strain Effects in Narrow-Bandwidth Manganites: The Case of Epitaxial Thin Films
journal, June 2014
- Moon, Eun Ju; Keavney, David J.; May, Steven J.
- Physical Review Applied, Vol. 1, Issue 5
Works referencing / citing this record:
Atomic-scale measurement of polar entropy
journal, September 2019
- Mukherjee, Debangshu; Prokhorenko, Sergei; Miao, Leixin
- Physical Review B, Vol. 100, Issue 10
Feature extraction via similarity search: application to atom finding and denoising in electron and scanning probe microscopy imaging
journal, March 2018
- Somnath, Suhas; Smith, Christopher R.; Kalinin, Sergei V.
- Advanced Structural and Chemical Imaging, Vol. 4, Issue 1
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
Atomap: a new software tool for the automated analysis of atomic resolution images using two-dimensional Gaussian fitting
journal, February 2017
- Nord, Magnus; Vullum, Per Erik; MacLaren, Ian
- Advanced Structural and Chemical Imaging, Vol. 3, Issue 1
Control of octahedral rotations via octahedral connectivity in an epitaxially strained [1 u.c.//4 u.c.] LaNiO3/LaGaO3 superlattice
journal, June 2016
- Qi, H. Y.; Kinyanjui, M. K.; Chen, X. D.
- Journal of Materials Science, Vol. 51, Issue 17
Three-dimensional bright-field scanning transmission electron microscopy elucidate novel nanostructure in microbial biofilms: THREE-DIMENSIONAL BRIGHT-FIELD SCANNING TRANSMISSION
journal, August 2016
- Hickey, William J.; Shetty, Ameesha R.; Massey, Randall J.
- Journal of Microscopy, Vol. 265, Issue 1
Material structure, properties, and dynamics through scanning transmission electron microscopy
journal, April 2018
- Pennycook, Stephen J.; Li, Changjian; Li, Mengsha
- Journal of Analytical Science and Technology, Vol. 9, Issue 1
Impact of interfacial coupling of oxygen octahedra on ferromagnetic order in La0.7Sr0.3MnO3/SrTiO3 heterostructures
journal, January 2017
- Li, Xiaoyan; Lindfors-Vrejoiu, Ionela; Ziese, Michael
- Scientific Reports, Vol. 7, Issue 1
Surface-screening mechanisms in ferroelectric thin films and their effect on polarization dynamics and domain structures
journal, January 2018
- Kalinin, Sergei V.; Kim, Yunseok; Fong, Dillon D.
- Reports on Progress in Physics, Vol. 81, Issue 3
Structure of epitaxial SrIrO 3 perovskite studied by interference between X-ray waves diffracted by the substrate and the thin film
journal, February 2017
- Horák, Lukáš; Kriegner, Dominik; Liu, Jian
- Journal of Applied Crystallography, Vol. 50, Issue 2
Quantifying Jahn-Teller distortion at the nanoscale with picometer accuracy using position averaged convergent beam electron diffraction
journal, December 2019
- Wang, Binbin; Esser, Bryan D.; Bagués, Núria
- Physical Review Research, Vol. 1, Issue 3
Structural “ Doping” to Control Local Magnetization in Isovalent Oxide Heterostructures
journal, November 2017
- Moon, E. J.; He, Q.; Ghosh, S.
- Physical Review Letters, Vol. 119, Issue 19
Correlation between Geometrically Induced Oxygen Octahedral Tilts and Multiferroic Behaviors in BiFeO 3 Films
journal, March 2018
- Lee, Sung Su; Kim, Young‐Min; Lee, Hyun‐Jae
- Advanced Functional Materials, Vol. 28, Issue 19
Low-field switching of noncollinear spin texture at interfaces
journal, January 2019
- Das, S.; Rata, A. D.; Maznichenko, I. V.
- Physical Review B, Vol. 99, Issue 2
Identifying local structural states in atomic imaging by computer vision
journal, November 2016
- Laanait, Nouamane; Ziatdinov, Maxim; He, Qian
- Advanced Structural and Chemical Imaging, Vol. 2, Issue 1
Thickness‐Dependent Ru Exchange Spring at La 0.7 Sr 0.3 MnO 3 –SrRuO 3 Interface
journal, February 2020
- Koch, Martin M.; Bergmann, Lukas; Agrestini, Stefano
- physica status solidi (b), Vol. 257, Issue 7
Materials Structure, Properties and Dynamics through Scanning Transmission Electron Microscopy
text, January 2019
- Pennycook, Stephen J.; Li, Changjian; Li, Mengsha
- arXiv
Identifying local structural states in atomic imaging by computer vision
journal, November 2016
- Laanait, Nouamane; Ziatdinov, Maxim; He, Qian
- Advanced Structural and Chemical Imaging, Vol. 2, Issue 1
Atomap: a new software tool for the automated analysis of atomic resolution images using two-dimensional Gaussian fitting
journal, February 2017
- Nord, Magnus; Vullum, Per Erik; MacLaren, Ian
- Advanced Structural and Chemical Imaging, Vol. 3, Issue 1
Feature extraction via similarity search: application to atom finding and denoising in electron and scanning probe microscopy imaging
journal, March 2018
- Somnath, Suhas; Smith, Christopher R.; Kalinin, Sergei V.
- Advanced Structural and Chemical Imaging, Vol. 4, Issue 1