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Little is known about the induction period before the nucleation and growth of colloidal semiconductor quantum dots. Here, we introduce an approach that allows us to probe intermediates present in the induction period. We show that this induction period itself exhibits distinct stages with the evolution of the intermediates, first without and then with the formation of covalent bonds between metal cations and chalcogenide anions. The intermediates are optically invisible in toluene, while the covalent-bonded intermediates become visible as magic-size clusters when a primary amine is added. Such evolution of magic-size clusters provides indirect but compelling evidence for the presence of the intermediates in the induction period and supports the multi-step nucleation model. Our study reveals that magic-size clusters could be readily engineered in a single-size form, and suggests that the existence of the intermediates during the growth of conventional quantum dots results in low product yield.

Probing intermediates of the induction period prior to nucleation and growth of semiconductor quantum dots