Thermodynamics of void nucleation in nanoparticles

The nucleation of voids at the initial stage of hollow nanoshell formation is described in terms of the thermodynamics of nucleation in systems of finite size (or small systems) pumped with vacancies by interdiffusion-driven vacancy influx. Crossovers from suppressed nucleation to metastable nucleus formation and then to stable nucleus formation are analysed, describing, in particular, the possibility of significant supersaturations with vacancies of the metallic core. It is shown that at higher temperatures it becomes more favourable to nucleate at once a large single void instead of multiple tiny voids.