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Title: Acceptor doping in the proton conductor SrZrO 3

Abstract

Perovskite zirconates such as SrZrO 3 exhibit improved proton solubility and conductivity when doped with trivalent cations substituting at the Zr site. In this work, we present a detailed study of Sc and Y dopants in SrZrO 3 based on first-principles, hybrid density-functional calculations. When substituting at the Zr site (ScZr, YZr), both dopants give rise to a single, deep acceptor level, where the neutral impurity forms a localized hole polaron state. The ε(0/-) charge transition levels are 0.60 eV and 0.58 eV above the valence-band maximum for ScZr and YZr, respectively. Under certain growth conditions, Sc and Y will form self-compensating donor species by substituting at the Sr site (ScSr, YSr), and this is detrimental to proton conductivity. Due to its larger ionic radius, Y exhibits a greater tendency than Sc to self-compensate at the Sr site. We also investigated the proton–dopant association. The binding energy of a proton to a negatively charged acceptor impurity is 0.41 eV for Sc and 0.31 eV for Y, indicating that proton transport is limited by trapping at impurity sites.

Authors:
ORCiD logo [1];  [1];  [2];  [3];  [1]
  1. Materials Department; University of California; Santa Barbara; California 93106-5050; USA
  2. Australian Centre for Microscopy and Microanalysis; School of Aerospace; Mechanical and Mechatronic Engineering; The University of Sydney; Australia
  3. School of Physics; The University of Sydney; Sydney; Australia
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1492386
DOE Contract Number:  
FG02-07ER46434; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 19; Journal Issue: 18; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Weston, Leigh, Janotti, A., Cui, X. Y., Stampfl, C., and Van de Walle, C. G. Acceptor doping in the proton conductor SrZrO3. United States: N. p., 2017. Web. doi:10.1039/c7cp01471f.
Weston, Leigh, Janotti, A., Cui, X. Y., Stampfl, C., & Van de Walle, C. G. Acceptor doping in the proton conductor SrZrO3. United States. doi:10.1039/c7cp01471f.
Weston, Leigh, Janotti, A., Cui, X. Y., Stampfl, C., and Van de Walle, C. G. Sun . "Acceptor doping in the proton conductor SrZrO3". United States. doi:10.1039/c7cp01471f.
@article{osti_1492386,
title = {Acceptor doping in the proton conductor SrZrO3},
author = {Weston, Leigh and Janotti, A. and Cui, X. Y. and Stampfl, C. and Van de Walle, C. G.},
abstractNote = {Perovskite zirconates such as SrZrO3 exhibit improved proton solubility and conductivity when doped with trivalent cations substituting at the Zr site. In this work, we present a detailed study of Sc and Y dopants in SrZrO3 based on first-principles, hybrid density-functional calculations. When substituting at the Zr site (ScZr, YZr), both dopants give rise to a single, deep acceptor level, where the neutral impurity forms a localized hole polaron state. The ε(0/-) charge transition levels are 0.60 eV and 0.58 eV above the valence-band maximum for ScZr and YZr, respectively. Under certain growth conditions, Sc and Y will form self-compensating donor species by substituting at the Sr site (ScSr, YSr), and this is detrimental to proton conductivity. Due to its larger ionic radius, Y exhibits a greater tendency than Sc to self-compensate at the Sr site. We also investigated the proton–dopant association. The binding energy of a proton to a negatively charged acceptor impurity is 0.41 eV for Sc and 0.31 eV for Y, indicating that proton transport is limited by trapping at impurity sites.},
doi = {10.1039/c7cp01471f},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 18,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}

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