Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Revealing the Structure and Oxygen Transport at Interfaces in Complex Oxide Heterostructures via 17 O NMR Spectroscopy

Abstract

Vertically aligned nanocomposite (VAN) films, comprising nanopillars of one phase embedded in a matrix of another, have shown great promise for a range of applications due to their high interfacial areas oriented perpendicular to the substrate. In particular, oxide VANs show enhanced oxide-ion conductivity in directions that are orthogonal to those found in more conventional thin-film heterostructures; however, the structure of the interfaces and its influence on conductivity remain unclear. In this work, 17O NMR spectroscopy is used to study CeO2–SrTiO3 VAN thin films: selective isotopic enrichment is combined with a liftoff technique to remove the substrate, facilitating detection of the 17O NMR signal from single atomic layer interfaces. By performing the isotopic enrichment at variable temperatures, the superior oxide-ion conductivity of the VAN films compared to the bulk materials is shown to arise from enhanced oxygen mobility at this interface; oxygen motion at the interface is further identified from 17O relaxometry experiments. The structure of this interface is solved by calculating the NMR parameters using density functional theory combined with random structure searching, allowing the chemistry underpinning the enhanced oxide-ion transport to be proposed. Finally, a comparison is made with 1% Gd-doped CeO2–SrTiO3 VAN films, for which greater NMRmore » signal can be obtained due to paramagnetic relaxation enhancement, while the relative oxide-ion conductivities of the phases remain similar. These results highlight the information that can be obtained on interfacial structure and dynamics with solid-state NMR spectroscopy, in this and other nanostructured systems, our methodology being generally applicable to overcome sensitivity limitations in thin-film studies.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [1];  [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom
  2. Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United Kingdom
Publication Date:
Research Org.:
Univ. of Cambridge (United Kingdom)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1659357
Alternate Identifier(s):
OSTI ID: 1663147
Grant/Contract Number:  
SC0012583
Resource Type:
Published Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Name: Chemistry of Materials Journal Volume: 32 Journal Issue: 18; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Thin films; Interfaces; Layers; Ions; Interfacial structure

Citation Formats

Hope, Michael A., Zhang, Bowen, Zhu, Bonan, Halat, David M., MacManus-Driscoll, Judith L., and Grey, Clare P. Revealing the Structure and Oxygen Transport at Interfaces in Complex Oxide Heterostructures via 17 O NMR Spectroscopy. United States: N. p., 2020. Web. doi:10.1021/acs.chemmater.0c02698.
Copy to clipboard
Hope, Michael A., Zhang, Bowen, Zhu, Bonan, Halat, David M., MacManus-Driscoll, Judith L., & Grey, Clare P. Revealing the Structure and Oxygen Transport at Interfaces in Complex Oxide Heterostructures via 17 O NMR Spectroscopy. United States. https://doi.org/10.1021/acs.chemmater.0c02698
Copy to clipboard
Hope, Michael A., Zhang, Bowen, Zhu, Bonan, Halat, David M., MacManus-Driscoll, Judith L., and Grey, Clare P. Wed . "Revealing the Structure and Oxygen Transport at Interfaces in Complex Oxide Heterostructures via 17 O NMR Spectroscopy". United States. https://doi.org/10.1021/acs.chemmater.0c02698.
Copy to clipboard
@article{osti_1659357,
title = {Revealing the Structure and Oxygen Transport at Interfaces in Complex Oxide Heterostructures via 17 O NMR Spectroscopy},
author = {Hope, Michael A. and Zhang, Bowen and Zhu, Bonan and Halat, David M. and MacManus-Driscoll, Judith L. and Grey, Clare P.},
abstractNote = {Vertically aligned nanocomposite (VAN) films, comprising nanopillars of one phase embedded in a matrix of another, have shown great promise for a range of applications due to their high interfacial areas oriented perpendicular to the substrate. In particular, oxide VANs show enhanced oxide-ion conductivity in directions that are orthogonal to those found in more conventional thin-film heterostructures; however, the structure of the interfaces and its influence on conductivity remain unclear. In this work, 17O NMR spectroscopy is used to study CeO2–SrTiO3 VAN thin films: selective isotopic enrichment is combined with a liftoff technique to remove the substrate, facilitating detection of the 17O NMR signal from single atomic layer interfaces. By performing the isotopic enrichment at variable temperatures, the superior oxide-ion conductivity of the VAN films compared to the bulk materials is shown to arise from enhanced oxygen mobility at this interface; oxygen motion at the interface is further identified from 17O relaxometry experiments. The structure of this interface is solved by calculating the NMR parameters using density functional theory combined with random structure searching, allowing the chemistry underpinning the enhanced oxide-ion transport to be proposed. Finally, a comparison is made with 1% Gd-doped CeO2–SrTiO3 VAN films, for which greater NMR signal can be obtained due to paramagnetic relaxation enhancement, while the relative oxide-ion conductivities of the phases remain similar. These results highlight the information that can be obtained on interfacial structure and dynamics with solid-state NMR spectroscopy, in this and other nanostructured systems, our methodology being generally applicable to overcome sensitivity limitations in thin-film studies.},
doi = {10.1021/acs.chemmater.0c02698},
journal = {Chemistry of Materials},
number = 18,
volume = 32,
place = {United States},
year = {Wed Aug 19 00:00:00 EDT 2020},
month = {Wed Aug 19 00:00:00 EDT 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.chemmater.0c02698
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
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:

Temperature Dependence of 207 Pb MAS Spectra of Solid Lead Nitrate. An Accurate, Sensitive Thermometer for Variable-Temperature MAS
journal, October 1995

  • Bielecki, Anthony; Burum, Douglas P.
  • Journal of Magnetic Resonance, Series A, Vol. 116, Issue 2
  • DOI: 10.1006/jmra.1995.0010

Strongly enhanced current densities in superconducting coated conductors of YBa2Cu3O7–x + BaZrO3
journal, May 2004

  • MacManus-Driscoll, J. L.; Foltyn, S. R.; Jia, Q. X.
  • Nature Materials, Vol. 3, Issue 7, p. 439-443
  • DOI: 10.1038/nmat1156

Thermal motion in SrTiO 3 at room temperature: Anharmonic or disordered?
journal, January 1978

Strongly enhanced oxygen ion transport through samarium-doped CeO2 nanopillars in nanocomposite films
journal, October 2015

  • Yang, Sang Mo; Lee, Shinbuhm; Jian, Jie
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9588

Tunable Low-Field Magnetoresistance in (La0.7Sr0.3MnO3)0.5:(ZnO)0.5 Self-Assembled Vertically Aligned Nanocomposite Thin Films
journal, April 2011

  • Chen, Aiping; Bi, Zhenxing; Tsai, Chen-Fong
  • Advanced Functional Materials, Vol. 21, Issue 13
  • DOI: 10.1002/adfm.201002746

NMR crystallography: the use of chemical shifts
journal, October 2004

Modelling one- and two-dimensional solid-state NMR spectra: Modelling 1D and 2D solid-state NMR spectra
journal, December 2001

  • Massiot, Dominique; Fayon, Franck; Capron, Mickael
  • Magnetic Resonance in Chemistry, Vol. 40, Issue 1
  • DOI: 10.1002/mrc.984

Synthesis of freestanding single-crystal perovskite films and heterostructures by etching of sacrificial water-soluble layers
journal, September 2016

  • Lu, Di; Baek, David J.; Hong, Seung Sae
  • Nature Materials, Vol. 15, Issue 12
  • DOI: 10.1038/nmat4749

Thick lead-free ferroelectric films with high Curie temperatures through nanocomposite-induced strain
journal, July 2011

  • Harrington, Sophie A.; Zhai, Junyi; Denev, Sava
  • Nature Nanotechnology, Vol. 6, Issue 8
  • DOI: 10.1038/nnano.2011.98

Multiferroic BaTiO3-CoFe2O4 Nanostructures
journal, January 2004

Oxygen Speciation in Nanophase MgO from Solid-State 17O NMR
journal, February 1998

  • Chadwick, Alan V.; Poplett, Iain J. F.; Maitland, David T. S.
  • Chemistry of Materials, Vol. 10, Issue 3
  • DOI: 10.1021/cm970629+

Ab initio random structure searching
journal, January 2011

Probing Dynamic Processes in Lithium-Ion Batteries by In Situ NMR Spectroscopy: Application to Li 1.08 Mn 1.92 O 4 Electrodes
journal, October 2015

  • Zhou, Lina; Leskes, Michal; Liu, Tao
  • Angewandte Chemie International Edition, Vol. 54, Issue 49
  • DOI: 10.1002/anie.201507632

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

AiiDA: automated interactive infrastructure and database for computational science
journal, January 2016

Identification of different oxygen species in oxide nanostructures with 17 O solid-state NMR spectroscopy
journal, February 2015

Dynamic Monte Carlo simulation of spin‐lattice relaxation of quadrupolar nuclei in solids. Oxygen‐17 in yttria‐doped ceria
journal, May 1993

  • Adler, Stuart B.; Smith, Jacob W.; Reimer, Jeffrey A.
  • The Journal of Chemical Physics, Vol. 98, Issue 9
  • DOI: 10.1063/1.464701

Probing Oxide-Ion Mobility in the Mixed Ionic–Electronic Conductor La 2 NiO 4+δ by Solid-State 17 O MAS NMR Spectroscopy
journal, September 2016

  • Halat, David M.; Dervişoğlu, Rıza; Kim, Gunwoo
  • Journal of the American Chemical Society, Vol. 138, Issue 36
  • DOI: 10.1021/jacs.6b07348

Nanoscale strain-induced pair suppression as a vortex-pinning mechanism in high-temperature superconductors
journal, February 2012

  • Llordés, A.; Palau, A.; Gázquez, J.
  • Nature Materials, Vol. 11, Issue 4
  • DOI: 10.1038/nmat3247

Oxygen ion dynamics in yttria-stabilized zirconia as evaluated by solid-state 17O NMR spectroscopy
journal, November 2006

All-electron magnetic response with pseudopotentials: NMR chemical shifts
journal, May 2001

3D strain-induced superconductivity in La 2 CuO 4+δ using a simple vertically aligned nanocomposite approach
journal, April 2019

93Nb NMR and DFT investigation of the polymorphs of NaNbO3
journal, January 2011

  • Johnston, Karen E.; Griffin, John M.; Walton, Richard I.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 16
  • DOI: 10.1039/c1cp20258h

Oxygen Defects and Novel Transport Mechanisms in Apatite Ionic Conductors: Combined 17O NMR and Modeling Studies
journal, August 2011

  • Panchmatia, Pooja M.; Orera, Alodia; Rees, Gregory J.
  • Angewandte Chemie International Edition, Vol. 50, Issue 40
  • DOI: 10.1002/anie.201102064

17 O quadrupole coupling and the origin of ferroelectricity in isotopically enriched BaTiO 3 and SrTiO 3
journal, February 2008

Electric-Field Control of Ferromagnetism in a Nanocomposite via a ZnO Phase
journal, November 2013

  • Fix, Thomas; Choi, Eun-Mi; Robinson, Jason W. A.
  • Nano Letters, Vol. 13, Issue 12
  • DOI: 10.1021/nl402775h

Strong room temperature exchange bias in self-assembled BiFeO 3 –Fe 3 O 4 nanocomposite heteroepitaxial films
journal, January 2013

  • Choi, Eun-Mi; Weal, Emily; Bi, Zhenxing
  • Applied Physics Letters, Vol. 102, Issue 1
  • DOI: 10.1063/1.4773567

Surface-selective direct 17 O DNP NMR of CeO 2 nanoparticles
journal, January 2017

  • Hope, Michael A.; Halat, David M.; Magusin, Pieter C. M. M.
  • Chemical Communications, Vol. 53, Issue 13
  • DOI: 10.1039/C6CC10145C

Transition Metal Dopant Cation Distributions in MgO and CaO: New Inferences from Paramagnetically Shifted Resonances in 17 O, 25 Mg, and 43 Ca NMR Spectra
journal, May 2016

  • McCarty, Ryan J.; Stebbins, Jonathan F.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 20
  • DOI: 10.1021/acs.jpcc.6b02710

Metal Oxide Nanocomposites: A Perspective from Strain, Defect, and Interface
journal, October 2018

Strong isotropic flux pinning in solution-derived YBa2Cu3O7−x nanocomposite superconductor films
journal, April 2007

  • Gutiérrez, J.; Llordés, A.; Gázquez, J.
  • Nature Materials, Vol. 6, Issue 5
  • DOI: 10.1038/nmat1893

Distinguishing faceted oxide nanocrystals with 17O solid-state NMR spectroscopy
journal, September 2017

Rapid Structure Determination of Molecular Solids Using Chemical Shifts Directed by Unambiguous Prior Constraints
journal, May 2019

  • Hofstetter, Albert; Balodis, Martins; Paruzzo, Federico M.
  • Journal of the American Chemical Society, Vol. 141, Issue 42
  • DOI: 10.1021/jacs.9b03908

Mixed Electrical Conduction in the Fluorite-Type Ce[sub 1−x]Gd[sub x]O[sub 2−x∕2]
journal, January 1976

  • Kudo, T.
  • Journal of The Electrochemical Society, Vol. 123, Issue 3
  • DOI: 10.1149/1.2132840

Calculation of NMR chemical shifts for extended systems using ultrasoft pseudopotentials
journal, July 2007

Ferroelectric Properties of Vertically Aligned Nanostructured BaTiO 3 –CeO 2 Thin Films and Their Integration on Silicon
journal, November 2013

  • Khatkhatay, Fauzia; Chen, Aiping; Lee, Joon Hwan
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 23
  • DOI: 10.1021/am403834k

Self-assembled oxide films with tailored nanoscale ionic and electronic channels for controlled resistive switching
journal, August 2016

  • Cho, Seungho; Yun, Chao; Tappertzhofen, Stefan
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12373

Observation of polar vortices in oxide superlattices
journal, January 2016

  • Yadav, A. K.; Nelson, C. T.; Hsu, S. L.
  • Nature, Vol. 530, Issue 7589
  • DOI: 10.1038/nature16463

Energy dispersive x-ray spectroscopy for nanostructured thin film density evaluation
journal, April 2015

  • Prencipe, Irene; Dellasega, David; Zani, Alessandro
  • Science and Technology of Advanced Materials, Vol. 16, Issue 2
  • DOI: 10.1088/1468-6996/16/2/025007

Toward Clean and Crackless Transfer of Graphene
journal, October 2011

  • Liang, Xuelei; Sperling, Brent A.; Calizo, Irene
  • ACS Nano, Vol. 5, Issue 11
  • DOI: 10.1021/nn203377t

O 17 nuclear-magnetic-resonance spectroscopic study of high- T c superconductors
journal, October 1989

  • Oldfield, Eric; Coretsopoulos, Chris; Yang, Shengtian
  • Physical Review B, Vol. 40, Issue 10
  • DOI: 10.1103/PhysRevB.40.6832

Integration of Self-Assembled Vertically Aligned Nanocomposite (La 0.7 Sr 0.3 MnO 3 ) 1– x :(ZnO) x Thin Films on Silicon Substrates
journal, May 2013

  • Zhang, Wenrui; Chen, Aiping; Khatkhatay, Fauzia
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 10
  • DOI: 10.1021/am400068h

Strain Tuning and Strong Enhancement of Ionic Conductivity in SrZrO 3 -RE 2 O 3 (RE = Sm, Eu, Gd, Dy, and Er) Nanocomposite Films
journal, June 2015

  • Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia
  • Advanced Functional Materials, Vol. 25, Issue 27
  • DOI: 10.1002/adfm.201404420

Microstructure characterization of BaSnO3 thin films on LaAlO3 and PrScO3 substrates from transmission electron microscopy
journal, July 2018

Ionic Conductivity Increased by Two Orders of Magnitude in Micrometer-Thick Vertical Yttria-Stabilized ZrO 2 Nanocomposite Films
journal, September 2015

Multiscale modeling of the ionic conductivity of acceptor doped ceria
journal, June 2020

17O NMR in simple oxides
journal, June 1990

Study on vacancy motion in Y2O3-doped CeO2 by 17O NMR technique
journal, January 1985

  • Fuda, Kiyoshi; Kishio, Kohji; Yamauchi, Shigeru
  • Journal of Physics and Chemistry of Solids, Vol. 46, Issue 10
  • DOI: 10.1016/0022-3697(85)90142-8

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

Solid oxide fuel cells (SOFCs): a review of an environmentally clean and efficient source of energy
journal, October 2002

Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via 17 O NMR and DFT Calculations
journal, July 2016

  • Seymour, Ieuan D.; Middlemiss, Derek S.; Halat, David M.
  • Journal of the American Chemical Society, Vol. 138, Issue 30
  • DOI: 10.1021/jacs.6b05747

Factors Controlling the 17 O NMR Chemical Shift in Ionic Mixed Metal Oxides
journal, January 1996

  • Bastow, Timothy J.; Dirken, Peter J.; Smith, Mark E.
  • The Journal of Physical Chemistry, Vol. 100, Issue 47
  • DOI: 10.1021/jp9622694

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

A 17O paramagnetic NMR study of Sm2O3, Eu2O3, and Sm/Eu-substituted CeO2
journal, October 2019

A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface
journal, January 2004

Gaussian-approximation formalism for evaluating decay of NMR spin echoes
journal, August 1996

First principles methods using CASTEP
journal, January 2005

  • Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J.
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6
  • DOI: 10.1524/zkri.220.5.567.65075

Bi0.9Ho0.1FeO3/TiO2 Composite Thin Films: Synthesis and Study of Optical, Electrical and Magnetic Properties
journal, March 2019

Electric-field control of tri-state phase transformation with a selective dual-ion switch
journal, May 2017

  • Lu, Nianpeng; Zhang, Pengfei; Zhang, Qinghua
  • Nature, Vol. 546, Issue 7656
  • DOI: 10.1038/nature22389

Complex oxides on fire
journal, September 2008

  • Tokura, Yoshinori; Hwang, Harold Y.
  • Nature Materials, Vol. 7, Issue 9
  • DOI: 10.1038/nmat2264

Determining interface structures in vertically aligned nanocomposite films
journal, June 2019

  • Zhu, Bonan; Schusteritsch, Georg; Lu, Ping
  • APL Materials, Vol. 7, Issue 6
  • DOI: 10.1063/1.5099204
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: