Rapid growth of large, defect-free colloidal crystals

We demonstrate controlled growth of face-centered cubic (FCC), monodisperse hard-sphere colloidal crystals by centrifugation at up to 3000g onto FCC (100) templates. Such rapid deposition rates often result in an amorphous sediment. Surprisingly, however, growth onto (100) templates results only in single crystals with few or no extended defects. By contrast, deposition onto flat, (111), or (110) templates causes rapid disordering to an amorphous sediment if the dimensionless flux (particle volume fraction x Peclet number) exceeds a critical value. This crystalline-to-amorphous crossover results from the degeneracy of possible stacking positions for these orientations. No such degeneracy exists for growth onto (100). After growth, extended defects can nucleate and grow only if the crystal exceeds a critical thickness that depends on the lattice misfit with the template spacing. The experimental observations of the density of misfit dislocations are accounted for by the Frank-van der Merwe theory, adapted for the depth-dependent variation of lattice spacing and elastic constants that results from the gravitational pressure.