Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

doi:10.1038/ncomms12572

Title: Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

Journal Article · Wed Aug 31 00:00:00 EDT 2016 · Nature Communications

DOI:https://doi.org/10.1038/ncomms12572· OSTI ID:1377432

Stone, Greg ^[1]; Ophus, Colin ^[2]; Birol, Turan ^[3]; Ciston, Jim ^[2]; Lee, Che-Hui ^[4]; Wang, Ke ^[5];

^[6]; Schlom, Darrell G. ^[7]; Alem, Nasim ^[1]; Gopalan, Venkatraman ^[1]

Pennsylvania State Univ., University Park, PA (United States). Dept. of Material Sciences and Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Univ. of Minnesota, Minneapolis, MN (United States)
Pennsylvania State Univ., University Park, PA (United States). Dept. of Material Sciences and Engineering; Cornell Univ., Ithaca, NY (United States). Dept. of Materials Science and Engineering
Pennsylvania State Univ., University Park, PA (United States)
Cornell Univ., Ithaca, NY (United States)
Cornell Univ., Ithaca, NY (United States). Dept. of Materials Science and Engineering

Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), A _n+1 B _n O _3n+1 , thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Sr _n+1 Ti _n O _3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; DMR-1420620; DMR-1210588; DMR-1056441

OSTI ID:: 1377432

Journal Information:: Nature Communications, Vol. 7; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 27 works

Citation information provided by
Web of Science

References (54)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Ferroelectricity in the Compound Ba 2 Bi 4 Ti 5 O 18 Aurivillius, Bengt; Fang, P. H. Physical Review, Vol. 126, Issue 3 https://doi.org/10.1103/PhysRev.126.893	journal	May 1962
Correcting nonlinear drift distortion of scanning probe and scanning transmission electron microscopies from image pairs with orthogonal scan directions Ophus, Colin; Ciston, Jim; Nelson, Chris T. Ultramicroscopy, Vol. 162 https://doi.org/10.1016/j.ultramic.2015.12.002	journal	March 2016
Dimensionality Control of Electronic Phase Transitions in Nickel-Oxide Superlattices Boris, A. V.; Matiks, Y.; Benckiser, E. Science, Vol. 332, Issue 6032 https://doi.org/10.1126/science.1202647	journal	May 2011
Nouvelles familles de phases MIMII2Nb3O10 a feuillets “perovskites” Dion, Michel; Ganne, Marcel; Tournoux, Michel Materials Research Bulletin, Vol. 16, Issue 11 https://doi.org/10.1016/0025-5408(81)90063-5	journal	November 1981
A Thin Film Approach to Engineering Functionality into Oxides Schlom, Darrell G.; Chen, Long-Qing; Pan, Xiaoqing Journal of the American Ceramic Society, Vol. 91, Issue 8 https://doi.org/10.1111/j.1551-2916.2008.02556.x	journal	August 2008
Giant magnetoresistance of manganese oxides with a layered perovskite structure Moritomo, Y.; Asamitsu, A.; Kuwahara, H. Nature, Vol. 380, Issue 6570 https://doi.org/10.1038/380141a0	journal	March 1996
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
The compound Sr ₃ Ti ₂ O ₇ and its structure Ruddlesden, S. N.; Popper, P. Acta Crystallographica, Vol. 11, Issue 1 https://doi.org/10.1107/S0365110X58000128	journal	January 1958
New Layered Oxide-Fluoride Perovskites: KNaNbOF5 and KNaMO2F4 (M = Mo6+, W6+) Pinlac, Rachelle Ann F.; Stern, Charlotte L.; Poeppelmeier, Kenneth R. Crystals, Vol. 1, Issue 1 https://doi.org/10.3390/cryst1010003	journal	March 2011
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
New compounds of the K ₂ NIF ₄ type Ruddlesden, S. N.; Popper, P. Acta Crystallographica, Vol. 10, Issue 8 https://doi.org/10.1107/S0365110X57001929	journal	August 1957
Exploiting dimensionality and defect mitigation to create tunable microwave dielectrics Lee, Che-Hui; Orloff, Nathan D.; Birol, Turan Nature, Vol. 502, Issue 7472 https://doi.org/10.1038/nature12582	journal	October 2013
Super-crystals in composite ferroelectrics Pierangeli, D.; Ferraro, M.; Di Mei, F. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10674	journal	February 2016
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
VESTA : a three-dimensional visualization system for electronic and structural analysis Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 41, Issue 3 https://doi.org/10.1107/S0021889808012016	journal	May 2008
Interface Physics in Complex Oxide Heterostructures Zubko, Pavlo; Gariglio, Stefano; Gabay, Marc Annual Review of Condensed Matter Physics, Vol. 2, Issue 1 https://doi.org/10.1146/annurev-conmatphys-062910-140445	journal	March 2011
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
Theory of Half-Metallic Ferrimagnetism in Double Perovskites Erten, Onur; Meetei, O. Nganba; Mukherjee, Anamitra Physical Review Letters, Vol. 107, Issue 25 https://doi.org/10.1103/PhysRevLett.107.257201	journal	December 2011
Atomically precise interfaces from non-stoichiometric deposition Nie, Y. F.; Zhu, Y.; Lee, C. -H. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5530	journal	August 2014
A Rapid Flux-Assisted Synthetic Approach Towards the Bandgap Engineering of Layered Perovskites Porob, Digamber G.; Maggard, Paul A. Chemistry of Materials, Vol. 19, Issue 5 https://doi.org/10.1021/cm062743a	journal	March 2007
Suppression of Octahedral Tilts and Associated Changes in Electronic Properties at Epitaxial Oxide Heterostructure Interfaces Borisevich, A. Y.; Chang, H. J.; Huijben, M. Physical Review Letters, Vol. 105, Issue 8 https://doi.org/10.1103/PhysRevLett.105.087204	journal	August 2010
Misfit-layered cobaltite with an anisotropic giant magnetoresistance: ${Ca}_{3} {Co}_{4} O_{9}$ Masset, A. C.; Michel, C.; Maignan, A. Physical Review B, Vol. 62, Issue 1 https://doi.org/10.1103/PhysRevB.62.166	journal	July 2000
Dynamics and Control in Complex Transition Metal Oxides Zhang, J.; Averitt, R. D. Annual Review of Materials Research, Vol. 44, Issue 1 https://doi.org/10.1146/annurev-matsci-070813-113258	journal	July 2014
Interface Control of Emergent Ferroic Order in Ruddlesden-Popper ${Sr}_{n + 1} {Ti}_{n} O_{3 n + 1}$ Birol, Turan; Benedek, Nicole A.; Fennie, Craig J. Physical Review Letters, Vol. 107, Issue 25 https://doi.org/10.1103/PhysRevLett.107.257602	journal	December 2011
The Crystal Chemistry of High-Temperature Oxide Superconductors and Materials with Related Structures Müller-Buschbaum, Hanskarl Angewandte Chemie International Edition in English, Vol. 28, Issue 11 https://doi.org/10.1002/anie.198914721	journal	November 1989
Next-generation electrocaloric and pyroelectric materials for solid-state electrothermal energy interconversion Alpay, S. Pamir; Mantese, Joseph; Trolier-McKinstry, Susan MRS Bulletin, Vol. 39, Issue 12 https://doi.org/10.1557/mrs.2014.256	journal	December 2014
Colossal Ionic Conductivity at Interfaces of Epitaxial ZrO2:Y2O3/SrTiO3 Heterostructures Garcia-Barriocanal, J.; Rivera-Calzada, A.; Varela, M. Science, Vol. 321, Issue 5889 https://doi.org/10.1126/science.1156393	journal	August 2008
Emergent phenomena at oxide interfaces Hwang, H. Y.; Iwasa, Y.; Kawasaki, M. Nature Materials, Vol. 11, Issue 2 https://doi.org/10.1038/nmat3223	journal	January 2012
Oxide pyrochlores — A review Subramanian, M. A.; Aravamudan, G.; Subba Rao, G. V. Progress in Solid State Chemistry, Vol. 15, Issue 2 https://doi.org/10.1016/0079-6786(83)90001-8	journal	January 1983
Dynamic layer rearrangement during growth of layered oxide films by molecular beam epitaxy Lee, J. H.; Luo, G.; Tung, I. C. Nature Materials, Vol. 13, Issue 9 https://doi.org/10.1038/nmat4039	journal	August 2014
Structure, Magnetism, and Properties of Ruddlesden−Popper Calcium Manganates Prepared from Citrate Gels Fawcett, Ian D.; Greenblatt, Martha Chemistry of Materials, Vol. 10, Issue 11 https://doi.org/10.1021/cm980380b	journal	November 1998
Epitaxial Growth and Properties of Doped Transition Metal and Complex Oxide Films Chambers, Scott A. Advanced Materials, Vol. 22, Issue 2 https://doi.org/10.1002/adma.200901867	journal	January 2010
Atomically resolved EELS mapping of the interfacial structure of epitaxially strained ${LaNiO}_{3} / {LaAlO}_{3}$ superlattices Gauquelin, N.; Benckiser, E.; Kinyanjui, M. K. Physical Review B, Vol. 90, Issue 19 https://doi.org/10.1103/PhysRevB.90.195140	journal	November 2014
Perovskites by Design: A Toolbox of Solid-State Reactions Schaak, Raymond E.; Mallouk, Thomas E. Chemistry of Materials, Vol. 14, Issue 4, p. 1455-1471 https://doi.org/10.1021/cm010689m	journal	April 2002
Interlayer chemistry between thick transition-metal oxide layers: synthesis and intercalation reactions of K[Ca2Nan-3NbnO3n+1] (3 .ltoreq. n .ltoreq. 7) Jacobson, A. J.; Johnson, Jack W.; Lewandowski, J. T. Inorganic Chemistry, Vol. 24, Issue 23 https://doi.org/10.1021/ic00217a006	journal	November 1985
Tilt engineering of spontaneous polarization and magnetization above 300 K in a bulk layered perovskite Pitcher, M. J.; Mandal, P.; Dyer, M. S. Science, Vol. 347, Issue 6220 https://doi.org/10.1126/science.1262118	journal	January 2015
An introduction to the tools hosted in the Bilbao Crystallographic Server Tasci, E. S.; de la Flor, G.; Orobengoa, D. EPJ Web of Conferences, Vol. 22 https://doi.org/10.1051/epjconf/20122200009	journal	January 2012
Complex oxides on fire Tokura, Yoshinori; Hwang, Harold Y. Nature Materials, Vol. 7, Issue 9 https://doi.org/10.1038/nmat2264	journal	September 2008
Recent Developments in Oxide Ion Conductors: Aurivillius Phases Kendall, Kurt R.; Navas, Carlos; Thomas, Julie K. Chemistry of Materials, Vol. 8, Issue 3 https://doi.org/10.1021/cm9503083	journal	January 1996
Magnetic Interactions in Ternary Ruthenium Oxides Callaghan, Alan; Moeller, Carl W.; Ward, Roland Inorganic Chemistry, Vol. 5, Issue 9 https://doi.org/10.1021/ic50043a023	journal	September 1966
Engineered spatial inversion symmetry breaking in an oxide heterostructure built from isosymmetric room-temperature magnetically ordered components Alaria, J.; Borisov, P.; Dyer, M. S. Chem. Sci., Vol. 5, Issue 4 https://doi.org/10.1039/c3sc53248h	journal	January 2014
Strain Tuning of Ferroelectric Thin Films Schlom, Darrell G.; Chen, Long-Qing; Eom, Chang-Beom Annual Review of Materials Research, Vol. 37, Issue 1 https://doi.org/10.1146/annurev.matsci.37.061206.113016	journal	August 2007
Solid state chemistry of Ruddlesden-Popper type complex oxides Sharma, Indu Bhushan; Singh, Devinder Bulletin of Materials Science, Vol. 21, Issue 5 https://doi.org/10.1007/BF02744920	journal	October 1998
Advanced Computing in Electron Microscopy Kirkland, Earl J. https://doi.org/10.1007/978-1-4419-6533-2	book	January 2010
Advanced Computing in Electron Microscopy Kirkland, Earl J. https://doi.org/10.1007/978-1-4757-4406-4	book	January 1998
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
High-resolution X-ray luminescence extension imaging Ou, Xiangyu; Qin, Xian; Huang, Bolong Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-021-03251-6	journal	February 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020
Advanced Computing in Electron Microscopy Kirkland, Earl J. Springer Cham https://doi.org/10.1007/978-3-030-33260-0	book	January 2020
A Rapid Flux-Assisted Synthetic Approach Towards the Bandgap Engineering of Layered Perovskites. Porob, Digamber G.; Maggard, Paul A. ChemInform, Vol. 38, Issue 22 https://doi.org/10.1002/chin.200722026	journal	May 2007
Theory of Half-metallic Ferrimagnetism in Double Perovskites Erten, Onur; Meetei, O. Nganba; Mukherjee, Anamitra arXiv https://doi.org/10.48550/arxiv.1107.0983	text	January 2011
Dimensionality Control of Electronic Phase Transitions in Nickel-Oxide Superlattices Boris, A. V.; Matiks, Y.; Benckiser, E. arXiv https://doi.org/10.48550/arxiv.1111.3819	text	January 2011
Engineered spatial inversion symmetry breaking in an oxide heterostructure built from isosymmetric room-temperature magnetically ordered components Alaria, J.; Borisov, P.; Dyer, M. S. arXiv https://doi.org/10.48550/arxiv.1311.7032	text	January 2013

Cited By (3)

A streaming multi-GPU implementation of image simulation algorithms for scanning transmission electron microscopy Pryor, Alan; Ophus, Colin; Miao, Jianwei Advanced Structural and Chemical Imaging, Vol. 3, Issue 1 https://doi.org/10.1186/s40679-017-0048-z	journal	October 2017
mpfit: a robust method for fitting atomic resolution images with multiple Gaussian peaks Mukherjee, Debangshu; Miao, Leixin; Stone, Greg Advanced Structural and Chemical Imaging, Vol. 6, Issue 1 https://doi.org/10.1186/s40679-020-0068-y	journal	January 2020
A Streaming Multi-GPU Implementation of Image Simulation Algorithms for Scanning Transmission Electron Microscopy Pryor, Alan; Ophus, Colin; Miao, Jianwei arXiv https://doi.org/10.48550/arxiv.1706.08563	preprint	January 2017

Similar Records

Spectroscopic Evidence of a Dimensionality-Induced Metal-to-Insulator Transition in the Ruddlesden–Popper La_n+1Ni_nO_3n+1 Series

Journal Article · Tue Jan 26 00:00:00 EST 2021 · ACS Applied Materials and Interfaces · OSTI ID:1377432

Di Pietro, Paola; Golalikhani, Maryam; Wijesekara, Kanishka; +5 more

Signatures of Coherent Phonon Transport in Ultralow Thermal Conductivity Two-Dimensional Ruddlesden–Popper Phase Perovskites

Journal Article · Thu Mar 04 00:00:00 EST 2021 · ACS Nano · OSTI ID:1377432

Christodoulides, Alexander D.; Guo, Peijun; Dai, Lingyun; +8 more

High Layer Number (n = 1–6) 2D Ruddlesden–Popper Lead Bromide Perovskites: Nanosheets, Crystal Structure, and Optoelectronic Properties

Journal Article · Thu Sep 28 00:00:00 EDT 2023 · ACS Materials Letters · OSTI ID:1377432

Forlano, Kristel M.; Roy, Chris R.; Mihalyi-Koch, Willa; +6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
ferroelectrics and multiferroics
transmission electron microscopy

Title: Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

Citation Formats

References (54)

Cited By (3)

Similar Records

Related Subjects