Monitoring super and subsurface oxygen on Ag(210) by high resolution XPS: subsurface diffusion and segregation

We report on a high energy resolution X-ray photoelectron spectroscopy plus supersonic molecular beam investigation of O/Ag(210). Two components are detected in the O1s spectra upon O-2 adsorption, at binding energies E-B =527.7 and 529.6 eV. The former peak persists up to 470 K, while the latter one decreases abruptly above 280 K. Comparison with a previous vibrational spectroscopy investigation on the same system (L. Vattuone, et al. Phys. Rev. Lett. 2003, 90, 228302) allows to assign both features to atomic oxygen. The low-energy peak is identified with adatoms, while the other is correlated to O atoms in subsurface sites. A minor contribution at the same binding energy, due to carbonates, is quantified by inspection of the C1s region and shows a different temperature behavior with respect to oxygen. Oxygen segregation into the subsurface region is observed when heating the crystal in the presence of supersurface oxygen.