Entropy-Driven Unconventional Crystallization of Spherical Colloidal Nanocrystals Confined in Wide Cylinders

The densest packings of identical spherical colloidal nanocrystals in a thin cylinder generally give rise to confinement-induced chiral ordering. Here, we demonstrate that entropy can invalidate Pauling's packing rules for the nanocrystals confined in wide cylinders and novel ordered phases, where chiral ordering is broken, emerge. The nucleation and growth of spherical colloidal nanocrystals in the wide cylinders exhibit unique mechanisms which are distinctly different from that of thin ones. Furthermore, theoretical models which capture the essential physics of the ordering transitions are developed to reproduce the achiral ordering and reveal that the ordered phases are thermodynamically stable and stabilized through confinement-mediated entropic effect. These findings demonstrate that entropy arising from thermal motion can invalidate Pauling's packing rules of spherical colloidal nanocrystals confined in cylinders, which provides new insights into confinement physics of colloidal particles and might inspire nonintuitive design rules for the fabrication of novel ordered phases through confinement.