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The oxygen stoichiometry has a large influence on the physical and chemicalproperties of complex oxides. Most of the functionality in e.g. catalysis andelectrochemistry depends in particular on control of the oxygen stoichiometry.In order to understand the fundamental properties of intrinsic surfaces ofoxygen-deficient complex oxides, we report on in situ temperature dependentscanning tunnelling spectroscopy experiments on pristine oxygen deficient,epitaxial manganite films. Although these films are insulating in subsequent exsitu in-plane electronic transport experiments at all temperatures, in situscanning tunnelling spectroscopic data reveal that the surface of these filmsexhibits a metal-insulator transition (MIT) at 120 K, coincident with the onsetof ferromagnetic ordering of small clusters in the bulk of the oxygen-deficientfilm. The surprising proximity of the surface MIT transition temperature ofnonstoichiometric films with that of the fully oxygenated bulk suggests thatthe electronic properties in the surface region are not significantly affectedby oxygen deficiency in the bulk. This carries important implications for theunderstanding and functional design of complex oxides and their interfaces withspecific electronic properties for catalysis, oxide electronics andelectrochemistry.

Persistent metal-insulator transition at the surface of an oxygen-deficient, epitaxial manganite film