STM and XPS investigation of the oxidation of the Al4(Cr,Fe) quasicrystal approximant

•Comprehensive investigation of all three primary surfaces of an orthorhombic complex metallic alloy.•Localised oxidation tracked by scanning tunneling microscopy.•Oxidation resistance found using X-ray photoelectron spectroscopy. The oxidation of the Al4(Cr, Fe) quasicrystal approximant has been studied using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). STM data indicate that the initial oxidation on the (100) surface proceeds in a highly ordered fashion. Oxygen preferentially adsorbs onto the surface of terraces, and step edges remain intact. The STM images show ordered stripes after initial oxidation. XPS data indicate that only Al is oxidised, with at least two oxidation states present. The Cr and Fe peaks remain unchanged. The oxidation of Al, rather than Cr or Fe, is consistent with the enthalpies of formation for each oxide. The stripes visible on the STM images are therefore identified to be the initial stages of aluminium oxide formation. XPS performed after higher O2 exposure indicates that the (100) termination shows hindered Al oxide film thickness growth rates compared to the (010) and (001) surfaces.