Transmutable Colloidal Crystals and Active Phase Separation <i>via</i> Dynamic, Directed Self-Assembly with Toggled External Fields

A diverse set of functional materials can be fabricated by assembling dispersions of colloids and nanoparticles. Two principal engineering challenges prevent efficient production of these materials: first, scalable synthesis of particles with carefully tailored interactions required to generate complex structures, and second, the propensity of such materials to arrest in undesirable metastable states. Active assembly processes, such as dynamic, directed self-assembly in which the interactions among particles are externally controlled and vary over time, offer a promising method to address these challenges. For dispersions of polarizable dielectric or paramagnetic nanoparticles, an effective mode of active assembly can be achieved by toggling an external electric or magnetic field, which induces attractive particle interactions, on and off cyclically over time. Here, we develop computational and theoretical models for such active assembly processes and find that cyclically toggling the external field leads to growth of colloidal crystals at significantly faster rates and with many fewer defects than for assembly in a steady field. The active process stabilizes phases that are only metastable in steady fields, including a dense fluid phase and body-centered orthorhombic crystals. The growth mechanism and terminal structure of the dispersion are easily controlled by the toggling protocol, and the toggle parameters can be used to continuously transmute between crystal structures with different lattice parameters. Finally, we show how results from linear irreversible thermodynamics can be used to predict the dissipative terminal states of the active assembly process in terms of parameters of the toggling protocol