Komeda T

Electron energy-loss spectroscopy study of oxygen chemisorption and initial oxidation of Fe(110)

Abstract The initial stages of the interaction of oxygen with an Fe(110) surface have been studied at 300 K by electron energy-loss spectroscopy with in-situ combined low energy electron diffraction, Auger electron spectroscopy and work-function change measurement. From all the results, four different stages of the oxygen interaction are distinguished: (I) a first dissociative chemisorption up to 3 L, characterized by the c(2×2)-O structure, (II) a second dissociative chemisorption between 3 and 7 L, characterized by the c(3×1)-O structure, (III) incorporation of O adatoms into the selvage between 7 and 30 L, and (IV) oxidation above 30 L leading to the formation of FeO(111), characterized by the diffuse hexagonal diffraction pattern. The sticking probability was found to be initially near unity and fall off rapidly to a minimum value of ≈0.05 at ≈1 L. Particular emphasis was placed upon the investigation of the change in surface electronic properties from those characteristic of them metal to those of the oxide. In stage (I) an energy-loss peak, being attributed to the transition from the 2p orbital of the chemisorbed oxygen, was observed at 6.0 eV, while in stage (II) two additional peaks of the same origin appeared at 7.5 and 9.3 eV due to the formation of the O 2p band. The energy-loss spectrum in the oxide phase was characterized by the peaks at 4.8 and 7.5 eV due to the O2− 2p → Fe2+3d charge-transfer transitions and by a peak at 2.4 eV due to the ligand-field d → d transitions of an Fe2+ ion in FeO. It is shown that the Fe 3dyz,zx and 4sp electrons play a major role in the chemisorption bond (O adatoms located in the long-bridge site), and that for the incorporation process the Fe 3dy2 electrons are also involved in bonding by the symmetry breaking. The change in the Fe 3p-excitation spectrum during oxidation was also investigated. The differences between the experimental results on Fe(100) and (110) surfaces are summarized.

Angle-resolved photoemission of the c(2×2) and c(3×1) oxygen overlayers on Fe(110)

Abstract Angle-resolved photoemission spectroscopy utilizing synchrotron radiation has been used to study the band structure of the c(2×2) and (3×1) oxygen overlayers on Fe(110). The symmetries of the O-2p-derived states at the center of the surface Brillouin zone ( Γ ) were identified using polarized light. At Γ the p x p y - and p z -derived levels are at about 5.5 and 7.0 eV below the Fermi level, respectively, for both ordered overlayers. The p-states of the c(2×2)-O structure show very little dispersion (⪅0.1 eV) with k  . On the other hand, the c(3×1)-O overlayer exhibits considerable dispersion of ∼1.6 eV. The essential features of the measured dispersion are reproduced well by the dispersion predicted in a qualitative way for an isolated c(3×1) oxygen monolayer.