Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis

Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids.