Transition metal oxides: extra thermodynamic stability as thin films.
The oxides of many transition metals wet their own metal surface. The adhesion energy at this interface (E(adh,ox/m)) provides extra stabilization, which lowers the O2 pressure required for oxide stability as a thin film below that required for bulk-oxide stability by the factor exp[(2gamma(g/ox) - E(adh,ox/m))/(tN(ox)RT)], where gamma(g/ox) is the surface energy of the oxide, t is the oxide film thickness, and N(ox) is the oxygen concentration in the bulk oxide (moles O2 per volume). For oxide films only approximately 1 nm thick, this correction can be many orders of magnitude. This may extend to other compounds.
Campbell
Charles T
CT
Chemistry Department, University of Washington, Seattle, Washington 98195-1700, USA.