Covalent Functionalization of Black Phosphorus from First-Principles

The chemical functionalization is proven to be an effective and controllable approach to modify the properties of black phosphorus (BP), and improve the air-stability of BP and its nanoelectronic applications [Nat. Chem., 2016, 8, 597]. However, covalent functionalization of BP and related properties are poorly understood. Here we present a theoretical investigation on the electronic structure and transport property of chemically modified BP. Our calculations reveal that the molecule modification generates a rather flat energy band within the bandgap, which leads to a reduced hole mobility of BP. Alternatively, we propose to use polymers bonded to BP surface, aiming at a balance between functionality and carrier mobility. The polymer-BP composites preserve both electron and hole mobility of pristine BP. Meanwhile, the stability of polymer-BP composites in ambient condition is enhanced as well.