Non-equilibrium anisotropic colloidal single crystal growth with DNA

Anisotropic colloidal crystals are materials with novel optical and electronic properties. However, experimental observations of colloidal single crystals have been limited to relatively isotropic habits. Here, we show DNA-mediated crystallization of two types of nanoparticles with different hydrodynamic radii that form highly anisotropic, hexagonal prism microcrystals with AB₂ crystallographic symmetry. The DNA directs the nanoparticles to assemble into a non-equilibrium crystal shape that is enclosed by the highest surface energy facets (AB₂(10 $$\overline 1$$1 ¯ 0) and AB₂(0001)). Simulations and theoretical arguments show that this observation is a consequence of large energy barriers between different terminations of the AB₂(10 $$\overline 1$$1 ¯ 0) facet, which results in a significant deceleration of the (10 $$\overline 1$$1 ¯ 0) facet growth rate. In addition to reporting a hexagonal colloidal crystal habit, this work introduces a potentially general plane multiplicity mechanism for growing non-equilibrium crystal shapes, an advance that will be useful for designing colloidal crystal habits with important applications in both optics and photocatalysis.