Synergistic Effect of Alloying on Thermoelectric Properties of Two-Dimensional Pdpq (Q = S, Se).

Published In

Physical Chemistry Chemical Physics : PCCP

Document Type

Post-Print

Publication Date

3-21-2023

Abstract

Hosts of 2D materials exist, yet few allow compositional and structural tailoring as the MQ (M = Mo, W; Q = S, Se) family does, for which various structural superlattices have been synthesized. Using thorough first-principles calculations, we show how bonding hierarchy contributes to the structural resilience of 2D PdPQ and allows for full-range alloying of sulfur and selenium. Within the structural unit of PdPQ, the covalently-bonded [PQ] polyanions hold the structure together with their molecular-like P-P bonds while ionically bonded Pd-Qs allow the S/Se substitution. Here, the bonding hierarchy imparts superior electronic and structural features to the PdPQ monolayers. As such, the flat-and-dispersive valence band and the eight degenerate valleys of the conduction band benefit the p-type and n-type thermoelectricity of pristine PdPQ, which can be further enhanced by alloying. The high-entropy alloying synergistically suppresses the lattice heat transport from 75 to 30 W m K and increases the band degeneracy of PdPQ monolayers, resulting in an overall improvement in . Combining these features, in a naïve approach, results in a large approaching two for both p-type and n-type doping. However, accurate fully-fledged electron-phonon calculations rebut this promise, showing that at high temperatures, the increased electron scattering results in a stagnant power factor in the flat-and-dispersive valence band. Using a realistic first-principles scattering, we finally calculate the thermoelectric efficiency of PdPQ (Q = S, Se) and highlight the importance of an accurate estimation of electron relaxation time for thermoelectric predictions.

Rights

Copyright the Owner Societies 2023

Description

This is the author’s version of a work that was accepted for publication in Physical Chemistry Chemical Physics. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Physical Chemistry Chemical Physics.

DOI

10.1039/d2cp05979g

Persistent Identifier

https://archives.pdx.edu/ds/psu/39691

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