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:
-
- Univ. of Wisconsin-Madison, Madison, WI (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (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. https://doi.org/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. https://doi.org/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 = {Wed Apr 04 00:00:00 EDT 2018},
month = {Wed Apr 04 00:00:00 EDT 2018}
}
Web of Science
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