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

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

Abstract

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.

Authors:
 [1];  [2];  [3];  [2];  [4];  [5]; ORCiD logo [6];  [7];  [1];  [1]
  1. Pennsylvania State Univ., University Park, PA (United States). Dept. of Material Sciences and Engineering
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  3. Univ. of Minnesota, Minneapolis, MN (United States)
  4. 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
  5. Pennsylvania State Univ., University Park, PA (United States)
  6. Cornell Univ., Ithaca, NY (United States)
  7. Cornell Univ., Ithaca, NY (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1377432
Grant/Contract Number:
AC02-05CH11231; DMR-1420620; DMR-1210588; DMR-1056441
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; ferroelectrics and multiferroics; transmission electron microscopy

Citation Formats

Stone, Greg, Ophus, Colin, Birol, Turan, Ciston, Jim, Lee, Che-Hui, Wang, Ke, Fennie, Craig J., Schlom, Darrell G., Alem, Nasim, and Gopalan, Venkatraman. Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide. United States: N. p., 2016. Web. doi:10.1038/ncomms12572.
Stone, Greg, Ophus, Colin, Birol, Turan, Ciston, Jim, Lee, Che-Hui, Wang, Ke, Fennie, Craig J., Schlom, Darrell G., Alem, Nasim, & Gopalan, Venkatraman. Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide. United States. doi:10.1038/ncomms12572.
Stone, Greg, Ophus, Colin, Birol, Turan, Ciston, Jim, Lee, Che-Hui, Wang, Ke, Fennie, Craig J., Schlom, Darrell G., Alem, Nasim, and Gopalan, Venkatraman. 2016. "Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide". United States. doi:10.1038/ncomms12572. https://www.osti.gov/servlets/purl/1377432.
@article{osti_1377432,
title = {Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide},
author = {Stone, Greg and Ophus, Colin and Birol, Turan and Ciston, Jim and Lee, Che-Hui and Wang, Ke and Fennie, Craig J. and Schlom, Darrell G. and Alem, Nasim and Gopalan, Venkatraman},
abstractNote = {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.},
doi = {10.1038/ncomms12572},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = 2016,
month = 8
}

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

Save / Share:
  • We report the discovery of noncentrosymmetry in the family of HRTiO 4 (R = Eu, Gd, Dy) layered oxides possessing a Ruddlesden-Popper derivative structure, by second harmonic generation and synchrotron x-ray diffraction with the support of density functional theory calculations. These oxides were previously thought to possess inversion symmetry. Here, inversion symmetry is broken by oxygen octahedral rotations, a mechanism that is not active in simple perovskites. We discover a competition between oxygen octahedral rotations and sliding of the octahedral perovskite blocks at the OH layers. For the smaller rare earth ions, R = Eu, Gd, Dy, which favor themore » octahedral rotations, noncentrosymmetry is present but the sliding at the OH layer is absent. For the larger rare earth ions, R = Nd and Sm, the octahe-dral rotations are absent, but sliding of the octahedral blocks at the OH layer is present, likely to optimize the hydrogen bond length arising from the directional nature of these bonds in the crystal structure. The study reveals a new mechanism for inducing noncentrosymmetry in layered oxides, and chemical-structural effects related to rare earth ion size and hydrogen bonding that can turn this mechanism on and off. In conclusion, we construct a complete phase diagram of temperature versus rare earth ionic radius for the HRTiO 4 family.« less
  • Pillaring studies on four layered oxides, KCa{sub 2}Nb{sub 3}O{sub 10}, KCa{sub 3}Nb{sub 3} TiO{sub 13}, KCa{sub 4}Nb{sub 3}Ti{sub 2}O{sub 16}, and KCa{sub 2}Sr{sub 0.5}Nb{sub 3}Ti{sub 0.5}O{sub 11.5}, possessing Ruddlesden-Popper related structures have been carried out. The aluminum keggin ion, [Al{sub 13}O{sub 4}(OH){sub 24}(H{sub 2}O){sub 12}]{sup 7+}, was used as the polymeric cation for the pillar. These samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, neutron activation analysis, and sorption studies. X-ray diffraction and other structural studies suggest that the polymeric cations were incorporated into the interlayer and upon calcination the layer thicknesses observed correspond to that expected formore » the formation of the dehydrated polymers in between the layers as a composite. BET surface area measurements and sorption experiments indicate that these products are nonporous oxides suggesting that the interlayer regions are stuffed rather than pillared.« less
  • This paper describes the synthesis and crystal structures of Ruddlesden-Popper phases of manganese oxides. The crystal structure is goverened by the size of the lanthanide cation.
  • The crystal structure of the Ruddlesden-Popper layered perovskite Li{sub 2}SrTa{sub 2}O{sub 7} has been characterized at various temperatures between -185 and 300 deg. C by several techniques: X-ray and neutron powder diffraction, single crystal diffraction, transmission electron microscopy and Raman spectroscopy. The low temperature structure has been confirmed to be orthorhombic Cmcm with a small octahedra antiphase tilting ({phi}{phi}0) ({phi}{phi}0) inside the perovskite blocks. With temperature, the tilting progressively vanishes leading around 230 deg. C to a tetragonal symmetry (S.G. I4/mmm). This reversible phase transition, followed by X-ray and neutron thermodiffraction and thermal Raman measurements, is considered as of secondmore » order. An attribution of the Raman bands based on normal mode analysis is proposed. - Graphical abstract: Thermal evolution of Li{sub 2}SrTa{sub 2}O{sub 7} X-ray powder diffraction patterns showing the structural transformation from orthorhombic to tetragonal cell.« less