Oxygen chemisorption and oxide formation on Ni silicide surfaces at room temperature

Abstract

Auger spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) have been used in a comparative study of the room temperature oxidation of Ni silicides of increasing silicon content, from Ni3Si to NiSi2. The results were compared with those for the oxidation of pure Si and Ni. All suicide surfaces in the exposure range between 0.2 and 104 L follow two-step oxidation kinetics: the first step is characterized by an oxygen uptake rate higher than in the second one. Attention was focused on the oxygen induced modifications of metal and silicon AES and XPS spectra in silicides, which are indicative of changes in the local electronic structure and in the chemical bonding. In general oxygen bonds with silicon leaving the metal unaffected; however, at high exposures, characteristic feature of the Ni-oxygen bonds appear in the Ni(MVV) Auger line of the Ni-rich silicides. The presence of Ni atoms enhances considerably the Si oxidation process in silicides with respect to pure Si, in terms both of a higher Si oxidation state and a higher oxygen uptake; this enhancement is stronger in Ni-rich silicides than in Si-rich silicides. The oxygen induced contributions in the Si(LVV) Auger line show structures at 76 and 83 eV, and those in the Si 2p photoemission spectra show binding energy shifts between −1 and −3.8 eV; we conclude that the oxidation products are mainly silicon suboxides, like Si2O3 and SiO; only on Ni3 Si at 104 L, a significant contribution of SiO2 was found. The Ni catalytic effect on Si oxidation has been discussed in terms of the suicide heat of formation, of the breaking of the silicon sp3 configuration in silicides and of the metal atom dissociative effect on the O2 molecule.