Alloying, de-alloying and reentrant alloying in (sub-)monolayer growth of Ag on Pt(111)

An in-situ nanoscopic investigation of the prototypical surface alloying system Ag/Pt(111) is reported. The morphology and the structure of the ultrathin Ag-Pt film is studied using Low Energy Electron Microscopy during growth at about 800 K. An amazingly rich dynamic behaviour is uncovered in which stress relieve plays a governing role. Initial growth leads to surface alloying with prolonged and retarded nucleation of ad-islands. Beyond 50% coverage de-alloying proceeds, joined by partial segregation of Pt towards the centre of large islands in violent processes. Upon coalescence the irregularly shaped vacancy clusters are filled by segregating Pt, which then take a compact shape (black spots). As a result at around 85% coverage the strain of the initially pseudo-morphological film is almost completely relieved and Pt-segregation is at its maximum. Further deposition of Ag leads to transient re-entrant alloying and recovery of the pseudo-morphological layer. The black spots persist even in/on several layers thick films. Ex-situ atomic force microscopy data confirm that these are constituted by probably amorphous Pt(-rich) structures. The (sub-)monolayer films are very much heterogeneous.