Solvent Effects: A Signature of J- and H-Aggregate of Carbon Nanodots in Polar Solvents

The secret behind excitation-dependent/-independent photoluminescence of carbon nanodots (CDs) is not yet revealed completely. To address this issue, a detailed investigation on solvent polarity-dependent optical properties of citric acid-urea co-derived nitrogen-doped carbon nanodots (NCDs) was carried out. The interpretation on UV-visible spectral data reveals the presence of H-aggregates formed through hydrogen bonding. In addition, dipole-dipole interaction-mediated J-aggregates are clearly evident. The broad and intense excitation band of NCDs is mostly contributed by highly emissive J-like self-assembly of H-aggregates in polar solvents. Time-resolved fluorescence spectra of NCDs show triexponential decay kinetics. The three lifetime components correspond to long-lived H-aggregates, short-lived J-aggregates, and JH-aggregates of intermediate lifetime. Moreover, fluorescence of NCD is influenced by concentration and storage time. Accordingly, mismatch in spectral shapes of excitation and absorption spectra of NCD can be successfully correlated to aggregate species of NCDs that exist even in very dilute solutions.