Crystallization of a molecular liquid from solution often initiates at solid–liquid interfaces1,2,3, and nucleation rates are generally believed to be enhanced by surface roughness4,5. Here we show that, on a rough surface, the shape of surface nanopores can also alter nucleation kinetics. Using lithographic methods, we patterned polymer films with nanopores of various shapes and found that spherical nanopores 15–120 nm in diameter hindered nucleation of aspirin crystals, whereas angular nanopores of the same size promoted it. We also show that favourable surface–solute interactions are required for angular nanopores to promote nucleation, and propose that pore shape affects nucleation kinetics through the alteration of the orientational order of the crystallizing molecule near the angles of the pores. Our findings have clear technological implications, for instance in the control of pharmaceutical polymorphism and in the design of ‘seed’ particles for the regulation of crystallization of fine chemicals.
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We acknowledge the Novartis-MIT Center for Continuous Manufacturing for funding. We are grateful to T. Savas at MIT Research Laboratory of Electronics for fabricating the imprint mould with Si square nanopillars and to K. Gleason for use of her equipment for plasma treatment and glass silanization.
The authors declare no competing financial interests.
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Diao, Y., Harada, T., Myerson, A. et al. The role of nanopore shape in surface-induced crystallization. Nature Mater 10, 867–871 (2011). https://doi.org/10.1038/nmat3117
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