Reversible oxidation-reduction of epitaxial iron oxide films on Pt(111): Magnetite-hematite interconversion

We studied magnetite-hematite-magnetite transformations in an ultrathin epitaxial film on Pt(111) using surface sensitive and bulk sensitive methods. At initial oxidation stages at elevated temperature (810 K), a 5-nm thick magnetite Fe₃O₄(111) film became non-stoichiometric toward maghemite and then showed the first signs of hematite phase formation under an oxygen exposure of 3 × 10³ L. Finally, under 2 × 10⁴ L, the film fully transformed to hematite α-Fe₂O₃(0001), maintaining a high single-crystal quality. A comparison of the conversion electron Mössbauer spectra and low energy electron diffraction pattern showed that at intermediate oxidation stages, hematite dominated at the surface, whereas a spinel phase was still observed in the deeper layers. The magnetite-hematite conversion was fully reversed by annealing under ultra-high vacuum at temperatures exceeding 600 K, and despite a change in morphology, the magnetite film preserved the original crystal structure and orientation.