Halide-Assisted Synthesis of Cadmium Chalcogenide Nanoplatelets

Atomically flat colloidal semiconductor CdSe nanoplatelets (NPLs) with precisely controlled thickness possess a range of unique optoelectronic properties. Here, we study the growth of CdSe, CdTe, and CdS NPLs with the aim of synthesizing thicker NPLs in order to extend their optical activity further into the lower energy/larger wavelength range. We employ cadmium halides, which lead to faster reaction kinetics as confirmed by control experiments with cadmium hydroxide as a Cd-precursor. Addition of halides in all cases led to the formation of thicker NPL species, as compared with the corresponding syntheses without these additives. Analysis of a recent theoretical model of the platelet growth mechanism confirms an earlier suggestion that reducing both the reaction enthalpy and the surface energy of CdSe, by replacing acetate ligands with chloride ions, should indeed lead to thicker NPLs as observed. We noticed a formation of Cd-0-metal nanoparticles in the first stage of the synthesis by preparing the Cd-precursor, which is another key finding of our work. We assume that these particles can serve as an active cadmium source facilitating the growth of the NPLs. The resulting 6 ML CdSe NPLs exhibited bright photoluminescence with quantum yield of up to 50%, exceptionally narrow spectrum centered at 582 nm with full width at half-maximum of approx. 11 nm, and small Stokes shift of 2 nm. Moreover, we demonstrated the synthesis of heterostructured core/shell CdSe/CdS NPLs based on 6 ML CdSe platelets, which also exhibited bright fluorescence. This work shows the possibility to overcome energetic barrier limiting the size (thickness) control by using appropriate promoters of the growth of CdSe, CdTe, and CdS 2D structures.