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A well ordered Fe(001) ultra thin film epitaxially grown on MgO(001) has beenoxidized by post deposition annealing in oxygen atmosphere. LEED patternsindicate the formation of magnetite (Fe$_3$O$_4$) after one hour of oxygenexposure. The LEED pattern remains stable despite annealing the sample forfurther four hours. In contrast X-ray Photoelectron Spectroscopy (XPS) of theFe $2p$ core levels suggests the formation of an iron oxide comprising mostlyof merely trivalent iron. This discrepancy is analyzed and discussed employingcharge transfer multiplet calculations for the Fe $2p$ XPS spectra. We findthat Mg ion segregation from the substrate into the magnetite thin filmreplacing octahedrally coordinated Fe$^{2+}$ ions and the excess occupation ofoctahedral sites which are unoccupied in the ideal inverse spinel structure aredriving forces for the altered shape of the Fe $2p$ XPS spectra. Differentpotential models which might explain the nature of the Mg ion segregation intothe magnetite films are discussed.

Link between local iron coordination, Fe 2p XPS core level line shape and Mg segregation into thin magnetite films grown on MgO(001)