Controlled creation of point defects in three-dimensional colloidal crystals.

Crystal defects crucially influence the properties of crystalline materials and have been extensively studied. Even for the simplest type of defect-the point defect-however, basic properties such as their diffusive behavior, and their interactions, remain elusive on the atomic scale. Here, we demonstrate in situ control over the creation of isolated point defects in a three-dimensional (3D) colloidal crystal allowing insight on a single-particle level. Our system consists of thermoresponsive microgel particles embedded in a crystal of nonresponsive colloids. Heating this mixed-particle system triggers the shrinking of the embedded microgels, which then vacate their lattice positions, creating vacancy-interstitial pairs. We use temperature-controlled confocal laser scanning microscopy to verify and visualize the formation of the point defects. In addition, by reswelling the microgels we quantify the local lattice distortion around an interstitial defect. Our experimental model system provides a unique opportunity to shed light on the interplay between point defects, on the mechanisms of their diffusion, on their interactions, and on collective dynamics.

Repulsive and attractive depletion forces mediated by nonadsorbing polyelectrolytes in the Donnan limit.

In mixtures of colloids and nonadsorbing polyelectrolytes, a Donnan potential arises across the region between surfaces that are depleted of the polyelectrolyte and the rest of the system. This Donnan potential tends to shift the polyelectrolyte density profile toward the colloidal surface and leads to the local accumulation of polyelectrolytes. We derive a zero-field theory for the disjoining pressure between two parallel flat plates. The polyelectrolyte is allowed to enter the confined interplate region at the cost of a conformational free energy penalty. The resulting disjoining pressure shows a crossover to a repulsive regime when the interplate separation gets smaller than the size of the polyelectrolyte chain, followed by an attractive part. We find a quantitative match between the model and self-consistent field computations that take into account the full Poisson-Boltzmann electrostatics.