Perovskite quantum dots (PQDs) exhibit exceptional fluorescence property and are potential candidates for fluorescent metal-ion sensors. The present work shows the presence of inner filter effect (IFE) in perovskite sensing systems and its significance in enhancing the detection limits. Two different sensing systems (with a different extent of IFE), one with simple long-chain monodentate ligand-capped PQDs and the other with short-chain bidentate ligand capped PQDs, were developed toward sensing Co2+. The fluorescence quenching mechanism is elucidated and is observed to be a combination of Forster resonance energy transfer (FRET) and IFE. The electrostatic interaction of donor (D) with acceptor (A) and its distance for energy transfer was appropriate and was well within the requirement for a good energy transfer from PQDs (donor) to Co2+ ions (acceptor) facilitating partial FRET. Also, the spectral overlap of absorption of excited and emitted radiation (of PQDs) with that of Co2+ allows a significant amount of IFE. PQDs were successfully modified for lesser spectral overlap with reduced IFE. The reduction in IFE adversely drops the detection levels from 0.733 × 10-7 to 0.7970 × 10-6 on modification. This work provides insights into the design and development of high sensing perovskite probes with manipulation of IFE and also shows the importance of IFE to be considered during the study of such sensing systems, which has been neglected so far in perovskite systems.
Keywords: cobalt; fluorescence; ligand exchange; perovskite quantum dots; quenching; sensing.