Self‐Assembly Pathways of Triblock Janus Particles into 3D Open Lattices

Abstract The self‐assembly of triblock Janus particles is simulated from a fluid to 3D open lattices: pyrochlore, perovskite, and diamond. The coarse‐grained model explicitly takes into account the chemical details of the Janus particles (attractive patches at the poles and repulsion around the equator) and it contains explicit solvent particles. Hydrodynamic interactions are accounted for by dissipative particle dynamics. The relative stability of the crystals depends on the patch width. Narrow, intermediate, and wide patches stabilize the pyrochlore‐, the perovskite‐, and the diamond‐lattice, respectively. The nucleation of all three lattices follows a two‐step mechanism: the particles first agglomerate into a compact and disordered liquid cluster, which does not crystallize until it has grown to a threshold size. Second, the particles reorient inside this cluster to form crystalline nuclei. The free‐energy barriers for the nucleation of pyrochlore and perovskite are ≈10 k B T , which are close to the nucleation barriers of previously studied 2D kagome lattices. The barrier height for the nucleation of diamond, however, is much larger (>20 k B T ), as the symmetry of the triblock Janus particles is not perfect for a diamond structure. The large barrier is associated with the reorientation of particles, i.e., the second step of the nucleation mechanism.