Sulfur-induced corrosion of Au(111) studied by real-time STM

The interaction of sulfur with gold surfaces has attracted considerable interest due to numerous technological applications such as the formation of self-assembled monolayers (SAMs), use as a corrosion inhibitor, and as a chemical sensor. In this work, the interaction of sulfur with Au(111) at two different temperatures (300 K and 420 K) was studied by real-time scanning tunneling microscopy (STM), low energy electron diffraction (LEED) and Auger electron spectroscopy (AES). In the low coverage regime (< 0.1 monolayer), S modifies the surface stress leading to a lateral expansion of the Au surface layer. An ordered ({radical}3 x {radical}3)R30{sup o} sulfur adlayer develops as the coverage reaches {approx}0.3 ML. With further increasing S coverage the Au(111) surface undergoes a dynamic rearrangement while forming a two-dimensional AuS phase: gold surface atoms are removed from regular terrace sites and incorporated into the growing gold sulfide phase resulting in the appearance of pits and irregularly shaped AuS islands. Gold sulfide prepared at room temperature exhibits short-range order; an incommensurate, long-range ordered AuS phase develops upon annealing at 450-525 K. Higher temperatures lead to decomposition of the AuS corrosion film. Formation of an ordered AuS phase via rapid step retraction rather than etch pit formation is observed during S-interaction with Au(111) surfaces at 420 K. Our results shed new light on the S-Au(111) interaction