Two-dimensional iron oxide bi-and trilayer structures on Pd(100)

The growth morphology and structure of iron oxide films, prepared by postoxidation of Fe monolayers on a Pd(100) surface, have been investigated in a multitechnique study, using scanning tunneling microscopy (STM), low energy electron diffraction (LEED), high-resolution x-ray photoelectron spectroscopy (HR-XPS) and x-ray absorption spectroscopy (XAS), both using synchrotron radiation, and comprehensive density functional theory (DFT) analysis. A two-dimensional (2-D) hexagonal O-Fe-O trilayer phase has been generated at submonolayer Fe coverages, which converges into two different 2-D hexagonal Fe-O bilayer structures at one monolayer. One phase exhibits a c(8 x 2) coincidence structure and is associated with a stoichiometric FeO(111) bilayer. The second phase displays a superstructure of triangular loops, which is understood from DFT modeling as excess O ad-atoms in the terminating oxygen layer, thus corresponding to a FeO bilayer with a formal FeO1.125 stoichiometry. Annealing the latter in ultrahigh vacuum to 770 K results in the pure c(8 x 2) wetting layer. The thermodynamic stability of the O-Fe-O trilayer and FeO bilayer phases is analyzed in the DFT framework and is found to be in good agreement with the experiment. The absence of a c(4 x 2)-Fe3O4 phase in the experimental phase diagram, which is found to be stable by DFT and is experimentally encountered for other transition metal oxide films, such as Ni-, Co-, and Mn-oxide on Pd(100), is ascribed to kinetic reasons. (C) 2015 Elsevier B.V. All rights reserved.