Carrier Dynamics and Recombination Pathways in Ag-In-Zn-S Quantum Dots

Strong tolerance to off-stoichiometry of group I-III-VI semiconductors in their nanocrystal form allows fabrication of multinary, alloyed structures of desired properties. In particular, alloyed Cu-In-Zn-S and Ag-In-Zn-S quantum dots (QDs) have recently emerged as efficient fluorophors, in which tailoring the composition allows tuning the optical properties, and achieving photoluminescence (PL) quantum yields approaching unity. However, poor understanding of the carrier recombination mechanism in these materials limits their further development. In this work, by studying transient absorption and temperature dependent PL on bare QDs and QDs conjugated with electron scavenger molecules, we obtain a detailed picture of carrier dynamics. Our results challenge the prevailing assumption that the PL is due to a donor-acceptor-pair transition. We show that the PL occurs as a result of a recombination of a delocalized electron with a localized hole.