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Revealing the structure and oxygen transport at interface in complex oxide heterostructures via 17O NMR spectroscopy

Michael A. Hope1, Bowen Zhang2, Bonan Zhu2, David M. Halat1, Judith L. MacManus-Driscoll2, Clare P. Gray1*

1 Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom

2 Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS, United Kingdom

* Corresponding authors emails: cpg27@cam.ac.uk
DOI10.24435/materialscloud:4v-04 [version v1]

Publication date: Sep 04, 2020

How to cite this record

Michael A. Hope, Bowen Zhang, Bonan Zhu, David M. Halat, Judith L. MacManus-Driscoll, Clare P. Gray, Revealing the structure and oxygen transport at interface in complex oxide heterostructures via 17O NMR spectroscopy, Materials Cloud Archive 2020.104 (2020), doi: 10.24435/materialscloud:4v-04.

Description

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 lift-off 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. The dataset contains the Experimental data, first-principles calculations and random structures searching results.

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Files

File name Size Description
CeO2-STO_17O_NMR.zip
MD5md5:cc5c3103d4e815922a474c239e91cbfe
3.8 MiB Archive of experimental 17O NMR data
magres-0.12.aiida
MD5md5:73119e7f11365cc719708b425ecfa19a
87.2 MiB NMR calculations of the 0/90 degree interfaces
magres-1.0.aiida
MD5md5:3af6cb8f7ca50e52c4315ee3b4410ef9
7.2 MiB NMR calculations of the 45 degree interfaces
rss.tar.gz
MD5md5:40f35673b6f5ad8c413be5e49ad37be0
44.3 MiB Random structure searching results for the 45 degree interfaces
README.md
MD5md5:4f8e4de6a6a379c3740485775f8d1bb7
1.6 KiB Longer descriptions for the files uploaded

License

Files and data are licensed under the terms of the following license: Creative Commons Attribution 4.0 International.
Metadata, except for email addresses, are licensed under the Creative Commons Attribution Share-Alike 4.0 International license.

Keywords

solid-state NMR Interface thin films oxide ERC

Version history:

2020.104 (version v1) [This version] Sep 04, 2020 DOI10.24435/materialscloud:4v-04