A Study of Halide Ion Exchange-Induced Phase Transition in CsPbBr3 Perovskite Quantum Dots for Detecting Chlorinated Volatile Compounds

Abstract

The unique optical properties of perovskite quantum dots (PQDs), particularly the tunable photoluminescence (PL) across the visible spectrum, make them a promising tool for chlorinated detection. However, the correlation between the fluorescence emission shift behavior and the interface of phase transformation in PQDs has not been thoroughly explored. In this study, we synthesized CsPbBr₃ PQDs via the hot-injection method and demonstrated their ability to detect chlorinated volatile compounds such as HCl and NaOCl through a halide exchange process between the PQDs’ solid thin film and the chlorinated vapor phase. This exchange process, which occurs alongside chloride (Cl) and bromine (Br) ion exchange and halide atom rearrangement, leads to sequential structural changes: the initial CsPbBr₃ cubic Pm3̅m phase transitions to the CsPb₂Br_xCl_5–x tetragonal I4/mcm phase, which subsequently transforms into the CsPbBr_xCl_3–x orthorhombic Pnma phase. The detailed exploration of this proposed mechanism during chlorinated vapor detection with CsPbBr₃ PQDs thin films, supported by X-ray diffraction (XRD) analysis and PL spectrum over time, revealed high sensitivity to HCl vapor. The limit of detection (LOD) for HCl vapor was determined to be 0.02 ppm in visual recognition and 0.005 ppm via PL spectra. Additionally, the LOD for NaOCl was established at 0.50 ppm, facilitated by the photolysis reaction accelerating the conversion of NaOCl to HCl vapor under UV light irradiation. These insights have enriched our understanding of the mechanisms involved and broadened the potential use of CsPbBr₃ PQDs as PL detection probes for chloride ions.