Local work function of Pt clusters vacuum-deposited on a TiO2 surface.

Surface topography and work function maps were simultaneously obtained for Pt-evaporated titanium dioxide (TiO(2)) surfaces by using a Kelvin probe force microscope (KPFM). Platinum clusters with diameters of 2-3 nm and heights of 0.2-0.4 nm were obtained on rutile TiO(2)(110)-(1 x 1) surfaces. The work function on the Pt clusters was smaller than that on the surrounding TiO(2) surface. With the assumption that the work function was perturbed by electric dipole moments created at the Pt-TiO(2) interface, the work function decrease indicates that dipole moments were created at the interface and directed toward the vacuum. Such dipole moments can be formed by electron transfer from the originally neutral Pt atoms to the Ti cations exposed on the (1 x 1) surface. A simple model is constructed by assuming a uniform dipole moment per unit interface area. Using this model, the size-dependent perturbation of the work function can be interpreted. The electrostatic potential is more perturbed above the Pt clusters with a larger interface area since the number density of dipole moments is equal to that of the Ti cations and is uniform. A similar correlation between the work function decrease and interface area was observed for the clusters formed on terraces and on step edges. The work function maps showed no peculiar contribution for Ti atoms exposed at the step edges. Vacuum annealing caused a considerable change in the work function on the clusters. The work function was decreased on some clusters relative to the TiO(2) substrate, while it increased on the other clusters. The atomistic structure of the interface may be modified upon annealing, thus perturbing the electron transfer across the interface.