Strong excitonic effects in the optical properties of graphitic carbon nitrideg-C3N4from first principles

Abstract

Graphitic carbon nitride ($g$-C${}_{3}$N${}_{4}$) has recently triggered extensive investigations due to its potential applications, such as in direct photochemical water splitting, CO${}_{2}$ activation, and transition-metal-free spintronics. However, electronic, and particularly the optical properties of $g$-C${}_{3}$N${}_{4}$ still have not been well established. Based on one of the state-of-the-art approaches---many-body Green's function theory (i.e., $GW$ $+$ BSE)---absorption of ultraviolet light by $g$-C${}_{3}$N${}_{4}$ is found to be determined by strong excitonic effects with a significantly large binding energy assigned to the bound excitons. Dark states have also been found in $g$-C${}_{3}$N${}_{4}$, which can affect the photoluminescence yield of $g$-C${}_{3}$N${}_{4}$. We find that the band gap of $g$-C${}_{3}$N${}_{4}$ probably can be tuned by adjusting the condensation (dimensionality) to initiate excitonic absorption in the visible light region, which might help improve the solar energy conversion efficiency.