Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis.

Prins, P Tim; Montanarella, Federico; Dümbgen, Kim; Justo, Yolanda; van der Bok, Johanna C; Hinterding, Stijn O M; Geuchies, Jaco J; Maes, Jorick et al. · Nano Lett · 2021

basic_science · Level V

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Abstract

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 <i>in</i>-<i>situ</i> 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.