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Title: Oxygen Point Defect Chemistry in Ruddlesden–Popper Oxides (La 1-xSr x) 2MO 4±δ (M = Co, Ni, Cu)

Here, stability of oxygen point defects in Ruddlesden–Popper oxides (La 1-xSr x) 2MO 4±δ (M = Co, Ni, Cu) is studied with density functional theory calculations to determine their stable sites, charge states, and energetics as functions of Sr content ( x), transition metal (M), and defect concentration (δ). We demonstrate that the dominant O point defects can change between oxide interstitials, peroxide interstitials, and vacancies. In general, increasing x and atomic number of M stabilizes peroxide over oxide interstitials as well as vacancies over both peroxide and oxide interstitials; increasing δ destabilizes both oxide interstitials and vacancies but barely affects peroxide interstitials. We also demonstrate that the O 2p-band center is a powerful descriptor for these materials and correlates linearly with the formation energy of all defects. The trends of formation energy versus x, M, and δ and the correlation with O 2p-band center are explained in terms of oxidation chemistry and electronic structure.
Authors:
 [1] ;  [2] ;  [3] ;  [1]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States)
  2. Univ. of Wisconsin-Madison, Madison, WI (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Grant/Contract Number:
ACI-1053575; 1148011; FE0009435
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 7; Journal Issue: 10; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Research Org:
National Energy Technology Lab. (NETL), Morgantown, WV (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1481165

Xie, Wei, Lee, Yueh -Lin, Shao-Horn, Yang, and Morgan, Dane. Oxygen Point Defect Chemistry in Ruddlesden–Popper Oxides (La1-xSrx)2MO4±δ (M = Co, Ni, Cu). United States: N. p., Web. doi:10.1021/acs.jpclett.6b00739.
Xie, Wei, Lee, Yueh -Lin, Shao-Horn, Yang, & Morgan, Dane. Oxygen Point Defect Chemistry in Ruddlesden–Popper Oxides (La1-xSrx)2MO4±δ (M = Co, Ni, Cu). United States. doi:10.1021/acs.jpclett.6b00739.
Xie, Wei, Lee, Yueh -Lin, Shao-Horn, Yang, and Morgan, Dane. 2016. "Oxygen Point Defect Chemistry in Ruddlesden–Popper Oxides (La1-xSrx)2MO4±δ (M = Co, Ni, Cu)". United States. doi:10.1021/acs.jpclett.6b00739. https://www.osti.gov/servlets/purl/1481165.
@article{osti_1481165,
title = {Oxygen Point Defect Chemistry in Ruddlesden–Popper Oxides (La1-xSrx)2MO4±δ (M = Co, Ni, Cu)},
author = {Xie, Wei and Lee, Yueh -Lin and Shao-Horn, Yang and Morgan, Dane},
abstractNote = {Here, stability of oxygen point defects in Ruddlesden–Popper oxides (La1-xSrx)2MO4±δ (M = Co, Ni, Cu) is studied with density functional theory calculations to determine their stable sites, charge states, and energetics as functions of Sr content (x), transition metal (M), and defect concentration (δ). We demonstrate that the dominant O point defects can change between oxide interstitials, peroxide interstitials, and vacancies. In general, increasing x and atomic number of M stabilizes peroxide over oxide interstitials as well as vacancies over both peroxide and oxide interstitials; increasing δ destabilizes both oxide interstitials and vacancies but barely affects peroxide interstitials. We also demonstrate that the O 2p-band center is a powerful descriptor for these materials and correlates linearly with the formation energy of all defects. The trends of formation energy versus x, M, and δ and the correlation with O 2p-band center are explained in terms of oxidation chemistry and electronic structure.},
doi = {10.1021/acs.jpclett.6b00739},
journal = {Journal of Physical Chemistry Letters},
number = 10,
volume = 7,
place = {United States},
year = {2016},
month = {5}
}