Clean and oxidized (104–1015 L of O2) surfaces of α-GeTe have been investigated with x-ray photoelectron spectroscopy by using the synchrotron radiation facility BESSY II as well as an Al Kα source. To understand the first steps of oxidation, complementary quantum chemical calculations were performed. The cleaved surfaces of α-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 104 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 1010 and 1015 L, a layer of a relatively stable oxidation product with the approximate stoichiometry Ge1+δ+4Te1−δ0O2(1+δ)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 ≈2.5 nm at ∼1013 L, a transformation of the Te0 state into the Te+4 state is observed at the surface of the oxide layer. The final oxidation product can be described as mGeO2×nTeO2.

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The adsorption of molecular oxygen on PbTe(001) surfaces has been investigated using synchrotron radiation induced photoelectron spectroscopy (BESSY II, Berlin). The behavior of adsorbate system O 2 /PbTe(001) was also modeled in complementary DFT-B3LYP studies using a large-cluster approach. For several possible adsorption structures, the adsorption enthalpies, the changes of the effective charges, and the core-level shifts induced by adsorption were calculated. For the energetically most favorable adsorption structures, the calculated chemical shifts are in good agreement with the experimental observations. Oxidation was observed at exposures above ∼10 5 L of O 2 . In total, three steps of oxidation were observed. The first step of the reaction is associated with the formation of Te-O-Pb bonds resulting in Te 0 states. The subsequent second step is characterized by a Te 0 fTe 4+ transformation with three O atoms attaching to each surface Te atom. As a result, -TeO 3 2species are formed. The third step is associated with the growth of the planar layer of PbTeO 3 . In the range of exposures from 10 11 to 10 15 L, the kinetics of this layer growth can be described with the time-logarithmic law. The oxide growth rate does not depend on the presence of water vapor.

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