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Title: Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy and enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.
Authors:
 [1] ;  [2] ;  [3] ; ORCiD logo [3] ;  [4] ; ORCiD logo [5] ;  [6] ;  [3] ;  [3] ;  [5] ; ORCiD logo [3]
  1. ShanghaiTech Univ, Shanghai (China)
  2. Univ. of Salerno (Italy); TASC National Lab, Trieste (Italy)
  3. Univ. of Rome Tor Vergata (Italy)
  4. TASC National Lab, Trieste (Italy)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. Univ. of Milano (Italy)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 16; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1376532

Yang, Nan, Orgiani, Pasquale, Di Bartolomeo, Elisabetta, Foglietti, Vittorio, Torelli, Piero, Ievlev, Anton V., Rossi, Giorgio, Licoccia, Silvia, Balestrino, Giuseppe, Kalinin, Sergei V., and Aruta, Carmela. Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films. United States: N. p., Web. doi:10.1021/acs.jpcc.7b00386.
Yang, Nan, Orgiani, Pasquale, Di Bartolomeo, Elisabetta, Foglietti, Vittorio, Torelli, Piero, Ievlev, Anton V., Rossi, Giorgio, Licoccia, Silvia, Balestrino, Giuseppe, Kalinin, Sergei V., & Aruta, Carmela. Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films. United States. doi:10.1021/acs.jpcc.7b00386.
Yang, Nan, Orgiani, Pasquale, Di Bartolomeo, Elisabetta, Foglietti, Vittorio, Torelli, Piero, Ievlev, Anton V., Rossi, Giorgio, Licoccia, Silvia, Balestrino, Giuseppe, Kalinin, Sergei V., and Aruta, Carmela. 2017. "Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films". United States. doi:10.1021/acs.jpcc.7b00386. https://www.osti.gov/servlets/purl/1376532.
@article{osti_1376532,
title = {Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films},
author = {Yang, Nan and Orgiani, Pasquale and Di Bartolomeo, Elisabetta and Foglietti, Vittorio and Torelli, Piero and Ievlev, Anton V. and Rossi, Giorgio and Licoccia, Silvia and Balestrino, Giuseppe and Kalinin, Sergei V. and Aruta, Carmela},
abstractNote = {The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce3+ concentration while decreasing the dopant ionic radius from La3+ to Yb3+ was observed, thus explaining the measured increased activation energy and enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce3+ ionic radius allows promoting the formation of oxygen vacancies and Ce3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.},
doi = {10.1021/acs.jpcc.7b00386},
journal = {Journal of Physical Chemistry. C},
number = 16,
volume = 121,
place = {United States},
year = {2017},
month = {4}
}