Multistep Heterogeneous Nucleation in Binary Mixtures of Charged Colloidal Spheres

Nucleation plays a decisive role in determining the crystal structure and size distribution; however, understanding of the fundamentals of nucleation is quite limited. In particular, it is unclear whether a nucleus forms spontaneously from solution via a single- or multiple-step process. Here we show how a binary mixture of charged colloidal spheres nucleates heterogeneously on a flat substrate by means of Bragg microscopy, laser diffraction, and laser microscopy. In contrast with the conventional one-step and two-step nucleation mechanisms, a novel pathway of multistep heterogeneous nucleation under certain experimental conditions is highlighted by four steps: initial homogeneous fluid → prenucleation clusters → preordered prenucleation clusters → intermediate ordered phase → final crystal. It is expected that the obtained results would be helpful in rationalizing the rich phase behavior exhibited by the binary mixture systems and in developing better and broadly applicable nucleation models as well as i...