Ultralow thermal conductivity via weak interactions in PbSe/PbTe monolayer heterostructure for thermoelectric design

Abstract: In this study, we systematically investigate the thermal and electronic transport properties of two-dimensional PbSe/PbTe monolayer heterostructure by combining first-principles calculations, Boltzmann transport theory, and machine learning methods. The heterostructure exhibits a unique honeycomb-like corrugated and asymmetric configuration, which significantly enhances phonon scattering. Moreover, the relatively weak interatomic interactions in PbSe/PbTe lead to the formation of anti-bonding states, resulting in strong anharmonicity and ultimately yielding ultralow lattice thermal conductivity (${\kappa_{\rm L}}$). In the four-phonon scattering model, the ${\kappa_{\rm L}}$~values along the $x$ and $y$ directions are as low as 0.37 and 0.31 W/mK, respectively. Contrary to the conventional view that long mean free path acoustic phonons dominate heat transport, we find that optical phonons contribute approximately 59\% of the lattice thermal conductivity in this heterostructure. These optical phonons exhibit large Gr\"uneisen parameters, strong anharmonic scattering, and relatively high group velocities, thereby playing a crucial role in the low ${\kappa_{\rm L}}$ regime. Further analysis of thermoelectric performance shows that at a high temperature of 800 K, the heterostructure achieves an exceptional dimensionless figure of merit ($ZT$) of 5.3 along the $y$ direction, indicating outstanding thermoelectric conversion efficiency. These findings not only provide theoretical insights into the transport mechanisms of PbSe/PbTe monolayer heterostructure but also offer a practical design strategy for developing high-performance two-dimensional layered thermoelectric materials.