Covalent Functionalized Black Phosphorus Greatly Inhibits Nonradiative Charge Recombination: A Time Domain Ab Initio Study.

Mono- or few-layer black phosphorus (BP) has emerged as a promising photovoltaic and optoelectronic material with realistic applications subjected to instability and short charge carrier lifetime. Experiments show that covalent functionalization can improve the stability, but the underlying mechanism for the prolonged lifetime remains elusive. By performing spin-polarized time domain density functional theory combined with nonadiabatic (NA) molecular dynamics simulations, we demonstrate that BP passivated with both phenyl and nitrophenyl can suppress the nonradiative electron-hole recombination by a factor of 2 and 3, respectively, relative to the pristine system. The slow recombination is due to the interplay between energy gap, NA coupling, and decoherence time, which happens either through a hole-trap-assisted process or in a direct way between a free electron and hole in the spin-up channel. The observations hold in the spin-down channel. The study suggests that the passivating strategy should work for BP and other two-dimensional materials.