X-ray photoelectron studies of clean and oxidized α-GeTe(111) surfaces

Clean and oxidized (10(4)-10(15) L of O(2)) surfaces of alpha-GeTe have been investigated with x-ray photoelectron spectroscopy by using the synchrotron radiation facility BESSY II as well as an Al K alpha source. To understand the first steps of oxidation, complementary quantum chemical calculations were performed. The cleaved surfaces of alpha-GeTe were found to be rumpled with (111) domains that can be related to the domain (twin) structure of the bulk. Both the Ge 3d and the Te 4d spectra of freshly cleaved surfaces exhibit at least three components, which are explained by a Ge or Te termination of the surface domains with possible contributions of a surface reconstruction. The surface oxidation starts at exposures of 10(4) L and proceeds via several steps. At low exposures, only changes in the Ge spectra are observed. Consequently, the first step of the reaction is associated with the formation of intermediate peroxidelike structures, wherein both oxygen atoms are bonded to germanium atoms. In the range of exposures between 10(10) and 10(15) L, a layer of a relatively stable oxidation product with the approximate stoichiometry Ge(1+delta)(+4)Te(1-delta)(0)O(2(1+delta))(2-) is formed, which shows growth kinetics that obey a time-logarithmic law. At this stage, the peroxidelike structures are still present at the oxide/crystal interface. Once the oxidized layer exceeds a thickness of approximate to 2.5 nm at similar to 10(13) L, a transformation of the Te(0) state into the Te(+4) state is observed at the surface of the oxide layer. The final oxidation product can be described as mGeO(2) x nTeO(2). (C) 2008 American Institute of Physics.