Resonant bonding driven giant phonon anharmonicity and low thermal conductivity of phosphorene

Abstract

Two-dimensional (2D) phosphorene, which possesses fascinating physical and chemical properties distinctively different from other 2D materials, calls for a fundamental understanding of thermal transport properties for its rapidly growing applications in nano- and optoelectronics and thermoelectrics. However, even the basic phonon property, for example, the exact value of the lattice thermal conductivity ($\ensuremath{\kappa}$) of phosphorene reported in the literature, can differ unacceptably by one order of magnitude. More importantly, the fundamental physics underlying its unique properties such as strong phonon anharmonicity and unusual anisotropy remains largely unknown. In this paper, based on the analysis of electronic structure and lattice dynamics from first principles, we report that the giant phonon anharmonicity in phosphorene is associated with the soft transverse optical (TO) phonon modes and arises from the long-range interactions driven by the orbital governed resonant bonding. We also provide a microscopic picture connecting the anisotropic and low $\ensuremath{\kappa}$ of phosphorene to the giant directional phonon anharmonicity and long-range interactions, which are further traced back to the asymmetric resonant orbital occupations of electrons and characteristics of the hinge-like structure. The unambiguously low $\ensuremath{\kappa}$ of phosphorene obtained consistently by three independent ab initio methods confirms the phonon anharmonicity to a large extent and is expected to end the confusing huge deviations in previous studies. This work further pinpoints the necessity of including van der Waals interactions to accurately describe the interatomic interactions in phosphorene. We propose in 2D material that resonant bonding leads to low thermal conductivity, despite that it is originally found in three-dimensional (3D) thermoelectric and phase-change materials. Our study offers insights into phonon transport from the view of orbital states, which would be of great significance to the design of emerging phosphorene-based nanodevices.