Phosphorene, the single layer counterpart of black phosphorus, is a novel two-dimensional semiconductor with high carrier mobility and a large fundamental direct band gap, which has attracted tremendous interest recently. Its potential applications in nano-electronics and thermoelectrics call for fundamental study of the phonon transport. Here, we calculate the intrinsic lattice thermal conductivity of phosphorene by solving the phonon Boltzmann transport equation (BTE) based on first-principles calculations. The thermal conductivity of phosphorene at 300 K is 30.15 W m⁻¹ K⁻¹ (zigzag) and 13.65 W m⁻¹ K⁻¹ (armchair), showing an obvious anisotropy along different directions. The calculated thermal conductivity fits perfectly to the inverse relationship with temperature when the temperature is higher than Debye temperature (Θ_D = 278.66 K). In comparison to graphene, the minor contribution around 5% of the ZA mode is responsible for the low thermal conductivity of phosphorene. In addition, the representative mean free path (MFP), a critical size for phonon transport, is also obtained.

New classes of two-dimensional (2D) materials beyond graphene, including layered and non-layered, and their heterostructures, are currently attracting increasing interest due to their promising applications in nanoelectronics, optoelectronics and clean energy, where thermal transport is a fundamental physical parameter. In this paper, we systematically investigated the phonon transport properties of the 2D orthorhombic group IV–VI compounds of GeS, GeSe, SnS and SnSe by solving the Boltzmann transport equation (BTE) based on first-principles calculations. Despite their similar puckered (hinge-like) structure along the armchair direction as phosphorene, the four monolayer compounds possess diverse anisotropic properties in many aspects, such as phonon group velocity, Young's modulus and lattice thermal conductivity (κ), etc. Especially, the κ along the zigzag and armchair directions of monolayer GeS shows the strongest anisotropy while monolayer SnS and SnSe show almost isotropy in phonon transport. The origin of the diverse anisotropy is fully studied and the underlying mechanism is discussed in details. With limited size, the κ could be effectively lowered, and the anisotropy could be effectively modulated by nanostructuring, which would extend the applications to nanoscale thermoelectrics and thermal management. Our study offers fundamental understanding of the anisotropic phonon transport properties of 2D materials, and would be of significance for further study, modulation and applications in emerging technologies.

Silicene, the silicon-based counterpart of graphene with a two-dimensional honeycomb lattice, has attracted tremendous interest both theoretically and experimentally due to its significant potential industrial applications. From the aspect of theoretical study, the widely used classical molecular dynamics simulation is an appropriate way to investigate the transport phenomena and mechanisms in nanostructures such as silicene. Unfortunately, no available interatomic potential can precisely characterize the unique features of silicene. Here, we optimized the Stillinger-Weber potential parameters specifically for a single-layer Si sheet, which can accurately reproduce the low buckling structure of silicene and the full phonon dispersion curves obtained from ab initio calculations. By performing equilibrium and nonequilibrium molecular dynamics simulations and anharmonic lattice dynamics calculations with the new potential, we reveal that the three methods consistently yield an extremely low thermal conductivity of silicene and a short phonon mean-free path, suggesting silicene as a potential candidate for high-efficiency thermoelectric materials. Moreover, by qualifying the relative contributions of lattice vibrations in different directions, we found that the longitudinal phonon modes dominate the thermal transport in silicene, which is fundamentally different from graphene, despite the similarity of their two-dimensional honeycomb lattices.

We systematically investigated the geometric, electronic and thermoelectric (TE) properties of bulk black phosphorus (BP) under strain. The hinge-like structure of BP brings unusual mechanical responses such as anisotropic Young's modulus and negative Poisson's ratio. A sensitive electronic structure of BP makes it transform among metal, direct and indirect semiconductors under strain. The maximal figure of merit ZT of BP is found to be 0.72 at 800[emsp14]K that could be enhanced to 0.87 by exerting an appropriate strain, revealing BP could be a potential medium-high temperature TE material. Such strain-induced enhancements of TE performance are often observed to occur at the boundary of the direct-indirect band gap transition, which can be attributed to the increase of degeneracy of energy valleys at the transition point. By comparing the structure of BP with SnSe, a family of potential TE materials with hinge-like structure are suggested. This study not only exposes various novel properties of BP under strain, but also proposes effective strategies to seek for better TE materials.

Strain engineering is one of the most promising and effective routes toward continuously tuning the electronic and optic properties of materials, while thermal properties are generally believed to be insensitive to mechanical strain. In this paper, the strain-dependent thermal conductivity of monolayer silicene under uniform biaxial tension is computed by solving the phonon Boltzmann transport equation with interatomic force constants extracted from first-principles calculations. Unlike the commonly believed understanding that thermal conductivity only slightly decreases with increased tensile strain for bulk materials, it is found that the thermal conductivity of silicene can increase dramatically with strain. Depending on the size, the maximum thermal conductivity of strained silicene can be a few times higher than that of the unstrained case. Such an unusual strain dependence is mainly attributed to the dramatic enhancement in the acoustic phonon lifetime. Such enhancement plausibly originates from the flattening of the buckling of the silicene structure upon stretching, which is unique for silicene as compared with other common two-dimensional materials. Our findings offer perspectives on modulating the thermal properties of low-dimensional structures for applications such as thermoelectrics, thermal circuits, and nanoelectronics.