Robert Sinclair1

1, Stanford University, Stanford, California, United States

We have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilised zirconia (YSZ) substrates [1]. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Particular attention is paid to the transition from fully to partially coherent interfacial structures, and this is correlated to x-ray diffraction measurements [2]. Under high electron beam dose rate (above about 6,000 e-/Å2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower lose rates (ca. 2,600 e-/Å2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce3+ versus Ce4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains, which can be analyzed by the classical Avrami approach, as well as atomic migration along the ceria thin film (001) surface. The influence of thin film strain, by using different substrates, will also be considered [3].

[1] R. Sinclair, S. C. Lee, Y. Shi, W. C. Chueh, Ultramicroscopy, 2017, 176, 200.
[2] Y. Shi, S. C. Lee, M. Monti, C. Wang, Z. A. Feng, W. D. Nix, M. F. Toney, R. Sinclair, W. C. Chueh, ACS Nano, 2016, 10, 9938
[3] C. B. Gopal, M. Garcia-Melchor, S. C. Lee, Y. Shi, A. Shavorsky, M. Monti, Z. Guan, R. Sinclair, H. Bluhm, A. Vojvodic, W. C. Chueh, Nature Comm., 2017, 8, 15360.