Electron and Hole Mobilities in Bulk Hematite from Spin-Constrained Density Functional Theory
Abstract
We report transition metal oxide materials have attracted much attention for photoelectrochemical water splitting, but problems remain, e.g. the sluggish transport of excess charge carriers in these materials, which is not well understood. Here we use periodic, spin-constrained and gap-optimised hybrid density functional theory to uncover the nature and transport mechanism of holes and excess electrons in a widely used water splitting material, bulk-hematite (α-Fe2O3). We find that upon ionisation the hole relaxes from a delocalized band state to a polaron localised on a single iron atom with localisation induced by tetragonal distortion of the 6 surrounding iron-oxygen bonds. This distortion is responsible for sluggish hopping transport in the Fe-bilayer, characterised by an activation energy of 70 meV and a hole mobility of 0.031 cm2/Vs. By contrast, the excess electron induces a smaller distortion of the iron-oxygen bonds resulting in delocalisation over two neighbouring Fe units. We find that 2-site delocalisation is advantageous for charge transport due to the larger spatial displacements per transfer step. As a result, the electron mobility is predicted to be a factor of 3 higher than the hole mobility, 0.098 cm2/Vs, in qualitative agreement with experimental observations. Our study demonstrates that constrained DFT is amore »
- Authors:
-
[1];
[2];
[1]
- Department of Physics and Astronomy, University College London, London WC1E 6BT, U.K.
- Pacific Northwest National Laboratory, Richland, Washington 99354, United States
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Engineering and Physical Sciences Research Council
- OSTI Identifier:
- 1867321
- Alternate Identifier(s):
- OSTI ID: 1860248
- Report Number(s):
- PNNL-SA-170645
Journal ID: ISSN 0002-7863
- Grant/Contract Number:
- AC05-76RL01830; EP/L000202; EP/R029431; EP/P020194
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 144 Journal Issue: 10; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; iron; polarons; hematite; quantum mechanics; charge transfer
Citation Formats
Ahart, Christian S., Rosso, Kevin M., and Blumberger, Jochen. Electron and Hole Mobilities in Bulk Hematite from Spin-Constrained Density Functional Theory. United States: N. p., 2022.
Web. doi:10.1021/jacs.1c13507.
Ahart, Christian S., Rosso, Kevin M., & Blumberger, Jochen. Electron and Hole Mobilities in Bulk Hematite from Spin-Constrained Density Functional Theory. United States. https://doi.org/10.1021/jacs.1c13507
Ahart, Christian S., Rosso, Kevin M., and Blumberger, Jochen. Thu .
"Electron and Hole Mobilities in Bulk Hematite from Spin-Constrained Density Functional Theory". United States. https://doi.org/10.1021/jacs.1c13507.
@article{osti_1867321,
title = {Electron and Hole Mobilities in Bulk Hematite from Spin-Constrained Density Functional Theory},
author = {Ahart, Christian S. and Rosso, Kevin M. and Blumberger, Jochen},
abstractNote = {We report transition metal oxide materials have attracted much attention for photoelectrochemical water splitting, but problems remain, e.g. the sluggish transport of excess charge carriers in these materials, which is not well understood. Here we use periodic, spin-constrained and gap-optimised hybrid density functional theory to uncover the nature and transport mechanism of holes and excess electrons in a widely used water splitting material, bulk-hematite (α-Fe2O3). We find that upon ionisation the hole relaxes from a delocalized band state to a polaron localised on a single iron atom with localisation induced by tetragonal distortion of the 6 surrounding iron-oxygen bonds. This distortion is responsible for sluggish hopping transport in the Fe-bilayer, characterised by an activation energy of 70 meV and a hole mobility of 0.031 cm2/Vs. By contrast, the excess electron induces a smaller distortion of the iron-oxygen bonds resulting in delocalisation over two neighbouring Fe units. We find that 2-site delocalisation is advantageous for charge transport due to the larger spatial displacements per transfer step. As a result, the electron mobility is predicted to be a factor of 3 higher than the hole mobility, 0.098 cm2/Vs, in qualitative agreement with experimental observations. Our study demonstrates that constrained DFT is a very powerful tool for the prediction of charge transfer rates and mobilities in application-relevant oxide materials.},
doi = {10.1021/jacs.1c13507},
journal = {Journal of the American Chemical Society},
number = 10,
volume = 144,
place = {United States},
year = {Thu Mar 03 00:00:00 EST 2022},
month = {Thu Mar 03 00:00:00 EST 2022}
}
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