Degenerate crystals from colloidal dimers under confinement

Abstract

Colloidal aperiodic phases (i.e., entropy stabilized degenerate crystals, DCs) are realized via self-assembly of hollow fluorescent silica dimers under wedge-cell confinement. The dimer building blocks approximate two tangent spheres and their arrangements are studied via laser scanning confocal microscopy. In the DCs, the individual lobes tile a lattice and five distinct DC arrangements with square, triangular or rectangular layer symmetry are determined as a function of confinement height. Moreover, Monte Carlo simulations are used to construct the phase diagram for DCs up to two layer confinements and to analyze structural order in detail. Just as for spheres, the DC structural transitions under confinement are attributed to the ability or frustration to accommodate an integral number of particle layers between hard walls. Unlike spheres, dimers can also experience transitions involving changes in orientation. DCs are among the unconventional structures (e.g., semi-regular tilings, quasicrystals, plastic crystals) expected to enhance the properties of photonic solids.