Spontaneous Alloying of Ultrasmall Non-Stoichiometric Ag–In–S and Cu–In–S Quantum Dots in Aqueous Colloidal Solutions

The effect of spontaneous alloying of non-stoichiometric aqueous Ag-In-S (AIS) and Cu-In-S (CIS) quantum dots (QDs) stabilized by surface glutathione (GSH) complexes was observed spectroscopically due to the phenomenon of band bowing typical for the solid-solution Cu(Ag)-In-S (CAIS) QDs. The alloying was found to occur even at room temperature and can be accelerated by a thermal treatment of colloidal mixtures at around 90 °C with no appreciable differences in the average size observed between alloyed and original individual QDs. An equilibrium between QDs and molecular and clustered metal-GSH complexes, which can serve as "building material" for the new mixed CAIS QDs, during the spontaneous alloying is assumed to be responsible for this behavior of GSH-capped ternary QDs. The alloying effect is expected to be of a general character for different In-based ternary chalcogenides.