A new phosphorene allotrope: the assembly of phosphorene nanoribbons and chains

Abstract

Phosphorene allotrope monolayers such as blue and red phosphorus are being designed and synthesized to be used in the optoelectronics field due to their tunable bandgap and high mobility. Using the organic molecule self-assembly method similar to the synthesis of graphene allotropes, a novel phosphorene allotrope, P₅₆₇ monolayer, with five-, six-, and seven-membered rings is designed through the assembly of black phosphorus chains and blue phosphorene nanoribbons. Ab initio molecular dynamics, phonon dispersion, and elastic constants demonstrate the dynamic, thermal, and mechanical stability of the P₅₆₇ monolayer. Additionally, the first-principles calculations show that the P₅₆₇ monolayer is an indirect bandgap semiconductor with moderate bandgap and high anisotropic mobility (4.47 × 10³ cm² V⁻¹ s⁻¹). Compared with black phosphorene, the suitable band edge position and higher optical absorption coefficient (10⁵ cm⁻¹) make the P₅₆₇ monolayer more likely to be used as a photocatalytic hydrolysis material. The P₅₆₇ monolayer is a viable candidate for use in innovative optoelectronic devices and the assembly method provides a rational approach to designing phosphorus allotropes with high photocatalytic efficiency.