InP quantum dots: Stoichiometry regulates carrier dynamics

The optical properties of non-toxic indium phosphide (InP) quantum dots (QDs) are impinged by the existence of characteristic deep trap states. Several surface engineering strategies have been adopted to improve their optical quality, which has promoted the use of InP QDs for various technological applications. An antithetical approach involves the effective utilization of the deep trap states in InP QDs to modulate back electron transfer rates. Here, we explore the influence of the core-size of InP on their In-to-P stoichiometry and charge transfer dynamics when bound to an acceptor molecule, decyl viologen (DV2+). The mechanism of interaction of InP and DV2+ based on the quenching sphere model established the presence of (i) a 1:1 complex of DV2+ bound on InP and (ii) immobile quenchers in the quenching sphere, depending on the concentration of DV2+. While the forward electron transfer rates from photoexcited InP to bound DV2+ does not substantially vary with an increase in core size, the back electron transfer rates are found to be retarded. Findings from inductively coupled plasma-optical emission spectroscopy (ICP-OES) and X-ray photoelectron spectroscopy (XPS) reveal that the In to P ratio is higher for QDs with larger core size, which further brings about increased carrier trapping and a decreased rate of charge recombination. Furthermore, long-lived charge-separated states in DV2+ bound to InP, extending to hundreds of milliseconds, are obtained by varying the number of DV2+ in the quenching sphere of the QDs.