Investigation on Fluorescence Origin and Spectral Heterogeneity in Carbon Dots: A Dynamic Perspective

Abstract

Heterogeneity in the fluorescence of carbon dots (CDs) has been hard to figure out so far. This could potentially be related to structural factors, size or intermediate fluorophores, especially when employing the bottom‐up synthesis. Herein, we unveil the origin of fluorescence and spectral heterogeneity of CDs using a simple dynamic method. This work reports the room light‐excited green fluorescence and dual‐emissive N‐doped CDs synthesized using a hydrothermal method. Studies were carried out considering the factors of fluorescence phenomena, such as excitation‐independent emission, fluorescent impurities, aggregation and solvation dynamics. The new steady‐state, Excitation‐resolved area‐normalized emission spectroscopy (ERANES) and ensemble measurements, including time‐resolved studies reveal that a heterogeneous environment exists in the ground state. Eventually, the results show the existence of core, edge and surface states in the CDs. Additionally, the fluorescence characteristics depend on the structural functionalization that occurs in both the intrinsic and extrinsic states of the CDs and it is proven that this does not violate the Kasha‐Vavilov rule. Although a highly purified material could still exhibit heterogeneity due to the ensemble emissive states and structural variations. Our results provide insights into the enduring debates about fluorescence and a deeper understanding of the structure‐ property relationship of CDs.

Solvent-Assisted Structural Modifications of Sulfur Dots Followed by Time-Dependent Emergence of a New Emissive State and Long-Lived Afterglow

“…The formation of a new emissive domain upon solvent variation remains entirely unresolved. For a better understanding of these two different emissive domains and their interdomain interactions depending on the solvent medium/extent of aggregation, we tried to unveil the excited-state dynamics of the S dots during the solvent-directed growth process. , It is very obvious that any ground state interaction upon changing the solvent should affect the absorption spectra . However, from the absorption spectra (Figure S6), we noticed that the absorption of aggregation-induced structural modifications remains unaltered.…”