  Zn nanoclusters (NCs) are deposited by Low-energy cluster beam deposition
technique. The mechanism of oxidation is studied by analysing their
compositional and morphological evolution over a long span of time (three
years) due to exposure to ambient atmosphere. It is concluded that the
mechanism proceeds in two steps. In the first step, the shell of ZnO forms over
Zn NCs rapidly up to certain limiting thickness: with in few days -- depending
upon the size -- Zn NCs are converted to Zn-ZnO (core-shell), Zn-void-ZnO, or
hollow ZnO type NCs. Bigger than ~15 nm become Zn-ZnO (core-shell) type: among
them, NCs above ~25 nm could able to retain their initial geometrical shapes
(namely triangular, hexagonal, rectangular and rhombohedral), but ~25 to 15 nm
size NCs become irregular or distorted geometrical shapes. NCs between ~15 to 5
nm become Zn-void-ZnO type, and smaller than ~5 nm become ZnO hollow sphere
type i.e. ZnO hollow NCs. In the second step, all Zn-void-ZnO and Zn-ZnO
(core-shell) structures are converted to hollow ZnO NCs in a slow and gradual
process, and the mechanism of conversion proceeds through expansion in size by
incorporating ZnO monomers inside the shell. The observed oxidation behaviour
of NCs is compared with theory of Cabrera - Mott on low-temperature oxidation
of metal.
