Tuning the coalescence degree in the growth of Pt–Pd nanoalloys

Abstract

Coalescence is a phenomenon in which two or more nanoparticles merge to form a single larger aggregate. By means of gas-phase magnetron-sputtering aggregation experiments on Pt–Pd nanoalloys, it is shown that the degree of coalescence can be tuned from a growth regime in which coalescence is negligible to a regime where the growth outcome is dominated by coalescence events. This transition is achieved by varying both the length of the aggregation zone and the pressure difference between the aggregation and the deposition chamber. In the coalescence-dominated regime, a wide variety of coalescing aggregates is produced and analyzed by TEM. The experimental results are interpreted with the aid of molecular-dynamics simulations. This allows to distinguish four different steps through which coalescence proceeds towards equilibrium. These steps, occurring on a hierarchy of well-separated time scales, consist in: (i) alignment of atomic columns; (ii) alignment of close-packed atomic planes; (iii) equilibration of shape; (iv) equilibration of chemical ordering.