Deep vs shallow nature of oxygen vacancies and consequent n-type carrier concentrations in transparent conducting oxides
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Published version
Author(s)
Type
Journal Article
Abstract
The source of n-type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In2O3,SnO2, and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In2O3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO2, the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n-type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In2O3, but also in SnO2 and ZnO.
Date Issued
2018-05-25
Date Acceptance
2018-05-01
Citation
Physical Review Materials, 2018, 2 (5)
ISSN
2475-9953
Publisher
American Physical Society
Journal / Book Title
Physical Review Materials
Volume
2
Issue
5
Copyright Statement
Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license (https://creativecommons.org/licenses/by/4.0/). Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.
Sponsor
The Royal Society
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000433074900003&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Grant Number
UF150657
Subjects
Science & Technology
Technology
Materials Science, Multidisciplinary
Materials Science
LEVEL TRANSIENT SPECTROSCOPY
INITIO MOLECULAR-DYNAMICS
TOTAL-ENERGY CALCULATIONS
NATIVE POINT-DEFECTS
P-TYPE SEMICONDUCTOR
ZNO SINGLE-CRYSTALS
WAVE BASIS-SET
ELECTRICAL-PROPERTIES
ZINC-OXIDE
THIN-FILMS
Publication Status
Published
Article Number
054604
Date Publish Online
2018-05-25