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Title: Transition state redox during dynamical processes in semiconductors and insulators

Abstract

Activation barriers associated with ion diffusion and chemical reactions are vital to understand and predict a wide range of phenomena, such as material growth, ion transport, and catalysis. In the calculation of activation barriers for non-redox processes in semiconductors and insulators, it has been widely assumed that the charge state remains fixed to that of the initial electronic ground state throughout a dynamical process. In this work, we demonstrate that this assumption is generally inaccurate and that a rate-limiting transition state can have a different charge state from the initial ground state. This phenomenon can significantly lower the activation barrier of a dynamical process that depends strongly on charge state, such as carbon vacancy diffusion in 4H-SiC. With inclusion of such transition state redox, the activation barrier varies continuously with Fermi level, in contrast to the step-line feature predicted by the traditional fixed-charge assumption. In this study, a straightforward approach to include the transition state redox effect is provided, the typical situations where the effect plays a significant role are identified, and the relevant electron dynamics are discussed.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543740
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
NPG Asia Materials
Additional Journal Information:
Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 1884-4049
Publisher:
Nature Publishing Group Asia
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Materials Science

Citation Formats

Luo, Guangfu, Kuech, Thomas F., and Morgan, Dane. Transition state redox during dynamical processes in semiconductors and insulators. United States: N. p., 2018. Web. doi:10.1038/s41427-018-0010-0.
Luo, Guangfu, Kuech, Thomas F., & Morgan, Dane. Transition state redox during dynamical processes in semiconductors and insulators. United States. doi:10.1038/s41427-018-0010-0.
Luo, Guangfu, Kuech, Thomas F., and Morgan, Dane. Wed . "Transition state redox during dynamical processes in semiconductors and insulators". United States. doi:10.1038/s41427-018-0010-0. https://www.osti.gov/servlets/purl/1543740.
@article{osti_1543740,
title = {Transition state redox during dynamical processes in semiconductors and insulators},
author = {Luo, Guangfu and Kuech, Thomas F. and Morgan, Dane},
abstractNote = {Activation barriers associated with ion diffusion and chemical reactions are vital to understand and predict a wide range of phenomena, such as material growth, ion transport, and catalysis. In the calculation of activation barriers for non-redox processes in semiconductors and insulators, it has been widely assumed that the charge state remains fixed to that of the initial electronic ground state throughout a dynamical process. In this work, we demonstrate that this assumption is generally inaccurate and that a rate-limiting transition state can have a different charge state from the initial ground state. This phenomenon can significantly lower the activation barrier of a dynamical process that depends strongly on charge state, such as carbon vacancy diffusion in 4H-SiC. With inclusion of such transition state redox, the activation barrier varies continuously with Fermi level, in contrast to the step-line feature predicted by the traditional fixed-charge assumption. In this study, a straightforward approach to include the transition state redox effect is provided, the typical situations where the effect plays a significant role are identified, and the relevant electron dynamics are discussed.},
doi = {10.1038/s41427-018-0010-0},
journal = {NPG Asia Materials},
number = 4,
volume = 10,
place = {United States},
year = {2018},
month = {4}
}

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