Aqueously synthesized color-tunable quaternary Cu-In-Zn-S quantum dots for Cu(II) detection via mild and rapid cation exchange

Abstract

Non-cadimum photoluminescent I−III−VI semiconductor nanocrystals have attracted increasing attention due to their low toxicity, extraordinary optical and electronic properties. Herein, water-soluble quaternary Cu-In-Zn-S quantum dots (CIZS QDs) with tunable emission from 535 nm to 645 nm were successfully synthesized via ecofriendly one-pot aqueous method. The full width at half-maximum (FWHM) of the emissions are about 68 nm–88 nm, which are rather narrow among Cu-based semiconductors and preferred to facilitate improving color purity. The photoluminescence of water-soluble QDs was enhanced by ZnS coating with the absolute quantum yield (QY) up to 30.8%. Further, a novel fluorescent sensor for Cu2+ detection was developed based on the alteration of intrinsic optical properties of the CIZS/ZnS QDs after cation exchange at room temperature within 10 min, presenting a linear range of 0.020–20 μM and a detection limit down to 6.7 nM. Mechanism studies revealed that the QDs served as the template for cation exchange, through UV–vis absorption and fluorescence spectra in combination with the chemical composition and time-resolved photoluminescence decay analysis. Ions interference experiments demonstrated the good selectivity of the QDs towards Cu2+ and the sensor showed comparable accuracy to ICP-AES method as well as good performance in real sample detection, manifesting the reliability of the current strategy for sensing Cu2+ mildly and rapidly.