Reactivity to sulphur of clean and pre-oxidised Cu(1 1 1) surfaces

The reactivity of clean and pre-oxidised Cu(1 1 1) surfaces exposed to sulphur (H2S) has been studied at room temperature by Auger electron spectroscopy, low energy electron diffraction and scanning tunneling microscopy. On the clean surface, the sulphur-saturated surface structure is dominated by the 4135 or so-called “zigzag” superstructure. It is shown that a single orientation domain is favoured by the slight misorientation (∼2°) of the surface with respect to the (1 1 1) plane. Scanning tunneling microscopy measurements also revealed two minority structures. Pre-oxidation 4138-O/Cu(111)structure was performed by exposure to 1.5 × 104 L of O2 at 300 °C. Under exposure to H2S (1 × 10−7 mbar) at room temperature, the oxygen is totally substituted by sulphur. Once initiated, sulphur adsorption seems to propagate to cover the whole surface on the O-covered surface faster than on the clean Cu(1 1 1). At saturation by adsorbed sulphur, the surface is completely covered by the (7×7)R19.1 superstructure of highest coverage. This enhanced uptake of sulphur is assigned to the surface reconstruction of the copper surface induced by the pre-oxidation, causing a stronger reactivity of the Cu atoms released by the decomposition of the oxide.