Studies of the fundamental physics and chemistry of colloidal semiconductor nanocrystal quantum dots (QDs) have been central to the field for over 30 years. Although the photophysics of QDs has been intensely studied, much less is understood about the underlying chemical reaction mechanism leading to monomer formation and subsequent QD growth. Here we investigate the reaction mechanism behind CdSe QD synthesis, the most widely studied QD system. Remarkably, we find that it is not necessary for chemical precursors used in the most common synthetic methods to directly react to form QD monomers, but rather they can generate in situ the same highly reactive Cd and Se precursors that were used in some of the original II-VI QD syntheses decades ago, i.e., hydrogen chalcogenide gas and alkyl cadmium. Appreciating this surprising finding may allow for directed manipulation of these reactive intermediates, leading to more controlled syntheses with improved reproducibility.
Little is understood about the chemical evolution of precursors to quantum dots. Here, the authors find that under the high temperature conditions typical of CdSe quantum dot synthesis, precursors decompose into highly reactive species in a critical first step before forming monomers and finally nanocrystals.