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Significance The transformation from a fluid to a crystal can be complicated and involve one or more precursors. Such multistep crystallization pathways occur in many chemical and physical systems, and the driving force for the appearance of the precursors has been explained by unique characteristics of the interactions among the system’s building blocks. Here we report 2-step crystallization pathways in hard particles, where interaction is dictated solely by building-block shape and thus entropy. We categorize our 2-step crystallization pathways based on the dimension of the prenucleation motifs, and discuss possible comparisons to other crystallization processes.

Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs