Void-Based Assembly of Colloidal Crystals: Using Structure-Directing Agents to Direct the Assembly of Open Colloidal...

We have used computer simulations to reveal how colloidal crystals may be assembled by engineering the shape and charge of polymeric additives, which act as structure-directing agents (SDAs). Using these agents, only a single desired polymorph may be obtained from a crystallizing mixture of colloids and polymers, which would otherwise result in a defective crystal in the absence of these agents. Building on previous work, which demonstrated this principle in the limiting case of high-density, close-packed crystals, we have now achieved this control over low-density, open crystals, which have broad utility especially in optical applications. These results reveal the general utility of the SDA paradigm in assembling tailored colloidal crystals, which represents a new design method that does not rely on any modification of the colloids themselves.