Excitation Energy Induced S-shaped PL behavior in Graphene Quantum Dots

Graphene quantum dots (GQDs) have attracted much attention because of various advantages such as cost-effectiveness of synthesis, low toxicity, and photostability. The origins of photoluminescence (PL) in GQDs were suggested as the intrinsic states for localized sp2 carbon domains and the extrinsic states formed by oxygen-functional groups.[1,2] Nevertheless, it is still unclear to understand the information of electric band structure in GQD. Here, we observed excitation energy induced S-shaped PL behavior. The PL peak energy position shows an S-shaped shift (redshift-blueshift-redshift) as function of the excitation wavelengths. From various samples, we only observed S-shaped PL shift in the GQDs with both luminescent origins of intrinsic and extrinsic states. Therefore, this S-shaped PL shift is related to different weight of intrinsic and extrinsic states in PL spectrum depending on the excitation wavelengths. This would be the key result to understand the electric band structure of the GQDs and its derivatives.