Half-Heusler materials are strong candidates for thermoelectric applications due to their high weighted mobilities and power factors, which is known to be correlated to valley degeneracy in the electronic band structure. However, there are over 50 known semiconducting half-Heusler phases, and it is not clear how the chemical composition affects the electronic structure. While all the n-type electronic structures have their conduction band minimum at either the Γ - or X -point, there is more diversity in the p-type electronic structures, and the valence band maximum can be at either the Γ -, L -, or W -point. Here, we use high throughput computation and machine learning to compare the valence bands of known half-Heusler compounds and discover new chemical guidelines for promoting the highly degenerate W -point to the valence band maximum. We do this by constructing an “orbital phase diagram” to cluster the variety of electronic structures expressed by these phases into groups, based on the atomic orbitals that contribute most to their valence bands. Then, with the aid of machine learning, we develop new chemical rules that predict the location of the valence band maximum in each of the phases. These rules can be used to engineer band structures with band convergence and high valley degeneracy.
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Tuning valley degeneracy with band inversion
Valley degeneracy is a key feature of the electronic structure that benefits the thermoelectric performance of a material. Despite recent studies which claim that high valley degeneracy can be achieved with inverted bands, our analysis of rock-salt IV–VI compounds using first-principles calculations and k · p perturbation theory demonstrates that mere band inversion is an insufficient condition for high valley degeneracy; rather, there is a critical degree to which the bands must be inverted to induce multiple carrier pockets. The so-called “band inversion parameter” is formalized as a chemically-tunable property, offering a design route to achieving high valley degeneracy in compounds with inverted bands. We predict that the valley degeneracy of rock-salt IV–VI compounds can be increased from N V = 4 to N V = 24, which could result in a corresponding increase in the thermoelectric figure of merit zT .
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- PAR ID:
- 10379008
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 10
- Issue:
- 3
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 1588 to 1595
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1TA08379A
