Anomalous Behaviors of Visible Luminescence from Graphene Quantum Dots: Interplay between Size and Shape

For the application of graphene quantum dots (GQDs) to optoelectronic nanodevices, it is of critical importance to understand the mechanisms which result in novel phenomena of their light absorption/emission. Here, we present size-dependent shape/edge-state variations of GQDs and visible photoluminescence (PL) showing anomalous size dependences. With varying the average size (<i>d</i>_a) of GQDs from 5 to 35 nm, the peak energy of the absorption spectra monotonically decreases, while that of the visible PL spectra unusually shows nonmonotonic behaviors having a minimum at <i>d</i>_a = ∼17 nm. The PL behaviors can be attributed to the novel feature of GQDs, that is, the circular-to-polygonal-shape and corresponding edge-state variations of GQDs at <i>d</i>_a = ∼17 nm as the GQD size increases, as demonstrated by high-resolution transmission electron microscopy