A Two‐Pathway Model for the Evolution of Colloidal Compound Semiconductor Quantum Dots and Magic‐Size Clusters

Abstract A fundamental understanding of formation pathways is critical to the controlled synthesis of colloidal semiconductor nanocrystals. As ultrasmall‐size quantum dots (QDs) sometimes emerge in reactions along with magic‐size clusters (MSCs), distinguishing their individual pathway of evolution is important, but has proven difficult. To decouple the evolution of QDs and MSCs, an unconventional, selective approach has been developed, along with a two‐pathway model that provides a fundamental understanding of production selectivity. For on‐demand production of either ultrasmall QDs or MSCs, the key enabler is in how to allow a reaction to proceed in the time prior to nucleation and growth of QDs. In this prenucleation stage, an intermediate compound forms, which is the precursor compound (PC) to the MSC. Here, the two‐pathway model and the manipulation of such PCs to synthesize either ultrasmall QDs or binary and ternary MSCs are highlighted. The two‐pathway model will assist the development of nucleation theory as well as provide a basis for a mechanism‐enabled design and predictive synthesis of functional nanomaterials.