Understanding the effect of heteroatom doping is crucial for the design of carbon nanodots (CNDs) with enhanced luminescent properties for fluorescence imaging and light-emitting devices. Here, we study the effect and mechanisms of luminescence enhancement through nitrogen doping in nanodots synthesized by the bottom-up route in an intense femtosecond laser field using the comparative analysis of CNDs obtained from benzene and pyridine. We demonstrate that laser irradiation of aromatic compounds produces hybrid nanoparticles consisting of a nanocrystalline core with a shell of surface-bonded aromatic rings. These nanoparticles exhibit excitation-dependent visible photoluminescence typical for CNDs. Incorporation of nitrogen into pyridine-derived CNDs enhances their luminescence characteristics through the formation of small pyridine-based fluorophores peripherally bonded to the nanoparticles. We identify oxidation of surface pyridine rings as a mechanism of formation of several distinct blue- and green-emitting fluorophores in nanodots, containing pyridine moieties. These findings shed additional light on the nature and formation mechanism of effective fluorophores in nitrogen-doped carbon nanodots produced by the bottom-up route.
© 2022 The Authors. Published by American Chemical Society.