Precursor Compound-Assisted Formation of CdS Magic-Size Clusters in Aqueous Solutions

Investigations of the formation pathway of semiconductor magic-size clusters (MSCs) in aqueous solutions are quite limited. Here, we present our understanding about a precursor compound (PC)-assisted formation pathway of aqueous-phase CdS MSCs exhibiting a characteristic absorption peak at about 360 nm (MSC-360). The reaction uses CdCl₂ as the Cd source and thioglycolic acid (TGA) as both the S source and ligand in alkaline aqueous solutions. The mixture remains absorption featureless upon incubation at room temperature but with MSC-360 absorption observed upon adding butylamine. The longer the incubation period of the aqueous solution, the more MSC-360 forms after adding butylamine. We propose that Cd-TGA complexes form first, in which the TGA moieties then decompose partially to form PC of MSC-360 (PC-360) that cannot be observed in the optical absorption spectrum. The resulting PC-360 transforms to MSC-360 via quasi-isomerization in the presence of butylamine. The present study provides an in-depth understanding about the formation of aqueous-phase MSCs.