We present in situ STM studies on Sn electrodeposition on Au(100) surfaces
at underpotentials. The Sn under potential deposition (UPD) on Au(100) proc
eeds in three stages: the reversible submonolayer UPD; surface alloying; an
d alloying that extends to the bulk. The formation of the reversible submon
olayer UPD proceeds in the form of clusters of similar to2 nm. at potential
s as early as 0.04 V. The surface alloying takes place at -0.04 V, which is
evidenced by sudden immersion of the Sn clusters as well as significant ch
anges of steps on the surface. The bulk alloying sets in at -0.3 V, which l
eads to rapid change of the surface morphology. The earlier set in of the s
urface and bulk alloying process is considered the result of enhanced inter
diffusion of Sn and Au atoms upon decreasing the potential. It has been sho
wn that Sn UPD on Au(100) is much more complex than that of other metal UPD
systems studied previously by electrochemical scanning tunnelling microsco
py, but it serves as a good system for all-sided studies of the UPD process
es. Copyright (C) 2001 John Wiley & Sons, Ltd.