Intrinsic Self-Trapped Excitons in Graphitic Carbon Nitride

Graphitic carbon nitrides (g-C₃N₄) as low-cost, chemically stable, and ecofriendly layered semiconductors have attracted rapidly growing interest in optoelectronics and photocatalysis. However, the nature of photoexcited carriers in g-C₃N₄ is still controversial, and an independent charge-carrier picture based on the band theory is commonly adopted. Here, by performing transient spectroscopy studies, we show characteristics of self-trapped excitons (STEs) in g-C₃N₄ nanosheets including broad trapped exciton-induced absorption, picosecond exciton trapping without saturation at high photoexcitation density, and transient STE-induced stimulated emissions. These features, together with the ultrafast exciton trapping polarization memory, strongly suggest that STEs intrinsically define the nature of the photoexcited states in g-C₃N₄. These observations provide new insights into the fundamental photophysics of carbon nitrides, which may enlighten novel designs to boost energy conversion efficiency.