Publication date: 15th December 2025
Continuous injection reactions are designed to allow for continuous nanocrystal growth as long as monomers are supplied. This strategy is commonly leveraged to synthesize large nanocrystals, of which nanocrystals with sizes larger than their Bohr radius, termed bulk-like nanocrystals (BNCs), have emerged a promising optical gain media for optically pumped lasers [1, 2]. Rationalizing the growth process in continuous injections is thus critical to achieving synthetic protocols to arbitrarily large nanocrystal sizes with narrow size distribution. Herein, we use in-situ small and wide angle X-ray scattering (SAXS/WAXS) to monitor the nucleation and growth of CdSe and CdS BNCs. Contrary to the common assumption of continuous growth we observe a size threshold and continuous nucleation of CdSe nanocrystals. We rationalize this behaviour by invoking a strongly size dependent growth rate—superfocusing—which caps the range of attainable sizes [3]. The reaction profile for CdS is more complex and involves a size-bifurcation convoluted with the presence of both zinc-blende and wurtzite polymorphs. Kinetic reactions simulations qualitatively reproduce this behaviour when weakening the size-dependency of growth to a fraction of the nucleated particles. In sum, our work highlights that continuous injection reaction are complex and motivates further structural and computational studies to evaluate how receptive nanocrystal surfaces are to growth.
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