Phonon bunching induced strong four-phonon scattering for low lattice thermal conductivity in layered Na2CoSe2O

Abstract

Layered oxyselenides are of interest as promising mid- to high-temperature thermoelectric applications due to their tunable electrical properties and intrinsically low lattice thermal conductivity (κ). Understanding microscopic phonon mechanisms driving low-κ in these materials is essential for rational design. Here, we report a layer-differentiated phonon transport in Na2CoSe2O via solving the Wigner transport equation based on first-principles calculations, where CoSe6 and Na6O octahedra dominate acoustic and low-energy optical phonons, respectively, together inducing acoustic-optical bunching (a typical feature in homo-layered structures such as bilayer graphene and MoS2). In addition, Na6O generates high-energy flat optical phonons, in contrast to oxide-typical dispersive modes. This phonon dispersion feature, constrained by three-phonon scattering channels, necessitates interpretation via four-phonon processes, which simultaneously enhance wavelike coherent tunneling effects. Consequently, by considering anharmonic phonon renormalization, strong scattering of heat-carrying bunched phonons reduces κ by ~28%, with ~13% compensatory contribution from phonon coherence, yielding a low lattice thermal conductivity of 1.52 W m−1 K−1 at 300 K in Na2CoSe2O. This work provides new insights into the specific vibrational mechanisms, phonon bunching induced strong four-phonon scattering, highlights the critical role of distinct structural layers in governing thermal transport, and enriches the fundamental thermal transport mechanism in layered oxyselenides.