Vanadium on TiO2(1 1 0): adsorption site and sub-surface migration

The initial stages of the growth of vanadium overlayers on TiO2(1 1 0) at room temperature have been investigated with scanning tunneling microscopy. At very low coverages both individual vanadium adatoms and small vanadium clusters have been imaged with good resolution. The V adatoms adsorb preferentially on the so-called “upper threefold hollow” sites, as revealed by atomically resolved STM images: they are thus bonded to two bridging oxygen atoms and one threefold coordinated basal oxygen atom. At higher coverages the vanadium adlayers grow in form of poorly ordered three-dimensional islands. The number of V clusters at low coverages decreases by gentle annealing or with time even at room temperature. This kinetic effect has been interpreted in terms of sub-surface migration of V adatoms.