Line tension controls wall-induced crystal nucleation in hard-sphere colloids

We report on a numerical study of the effect of a smooth, hard wall on the crystallization of hard-sphere colloids. We find that the presence of the wall drastically lowers the barrier for crystal nucleation, but it does not eliminate it. Crystal nucleation becomes noticeable at pressures that are some 5% above the coexistence value. The first particles to crystallize on the wall form a (111) plane. Initially, this crystallite grows laterally, rather than in the third dimension. The free energy of the critical crystal nucleus on the wall is about 2 orders of magnitudes lower than in the bulk. Analysis of the numerical data indicates that, at coexistence, the (111) plane is at the threshold of wetting the wall. The nucleation barrier is dominated by line tension.