Modeling Strain Distribution at the Atomic Level in Doped Ceria Films with Extended X-ray Absorption Fine Structure Spectroscopy

Olga Kraynis, Janis Timoshenko, Jiahao Huang, Harishchandra Singh, Ellen Wachtel, Anatoly I. Frenkel, Igor Lubomirsky

Research output: Contribution to journalArticle

Abstract

Ceria doped with trivalent dopants exhibits nonclassical electrostriction, strong anelasticity, and room-temperature (RT) mechanical creep. These phenomena, unexpected for a ceramic material with a large Young's modulus, have been attributed to the generation of local strain in the vicinity of the host Ce cations due to symmetry-breaking point defects, including oxygen vacancies. However, understanding why strain is generated at the host rather than at the dopant site, as well as predicting these effects as a function of dopant size and concentration, remains a challenge. We have used the evolutionary-algorithm-based reverse Monte Carlo modeling to reconcile the experimental data of extended X-ray absorption fine structure and X-ray diffraction in a combined model structure. By extracting the details of the radial distribution function (RDF) around the host (Ce) and trivalent dopants (Sm or Y), we find that RDF of the first-nearest neighbor (1NN) of host and dopant cations as well as the second-nearest neighbor (2NN) of the dopant are each best modeled with two separate populations corresponding to short and long interatomic distances. This heterogeneity indicates that fluorite symmetry is not preserved locally, especially for the dopant first-and second-NN sites, appearing at surprisingly low doping fractions (5 mol % Sm and 10 mol % Y). Given that Ce rather than dopant sites act as the source of local strain for electrostriction and RT creep, we conclude that the environment around the dopant does not respond to electrical and mechanical excitations, likely because of its similarity to the double fluorite structure which has poor electrostrictive and anelastic properties. The trends we observe in the RDFs around the Ce sites as a function of dopant size and concentration suggest that the response of these sites can be controlled by the extent of doping: Increasing dopant size to increase strain magnitude at the 1NN shell of Ce and decreasing dopant fraction to decrease strain propagation to the 2NN shell of Ce should produce stronger electrostrictive response and RT creep.

Original languageEnglish
Pages (from-to)7527-7536
Number of pages10
JournalInorganic Chemistry
Volume58
Issue number11
DOIs
Publication statusPublished - Jun 3 2019

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Extended X ray absorption fine structure spectroscopy
strain distribution
Cerium compounds
electrostriction
fine structure
Doping (additives)
fluorite
radial distribution
room temperature
distribution functions
anelasticity
spectroscopy
cations
x rays
point defects
broken symmetry
modulus of elasticity
ceramics
trends
Electrostriction

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Modeling Strain Distribution at the Atomic Level in Doped Ceria Films with Extended X-ray Absorption Fine Structure Spectroscopy. / Kraynis, Olga; Timoshenko, Janis; Huang, Jiahao; Singh, Harishchandra; Wachtel, Ellen; Frenkel, Anatoly I.; Lubomirsky, Igor.

In: Inorganic Chemistry, Vol. 58, No. 11, 03.06.2019, p. 7527-7536.

Research output: Contribution to journalArticle

Kraynis, Olga ; Timoshenko, Janis ; Huang, Jiahao ; Singh, Harishchandra ; Wachtel, Ellen ; Frenkel, Anatoly I. ; Lubomirsky, Igor. / Modeling Strain Distribution at the Atomic Level in Doped Ceria Films with Extended X-ray Absorption Fine Structure Spectroscopy. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 11. pp. 7527-7536.
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