Ultrathin TiOx Films on Pt(111):  A LEED, XPS, and STM Investigation

Ultrathin ordered titanium oxide films on Pt(111) surface are prepared by reactive evaporation of Ti in oxygen. By varying the Ti dose and the annealing conditions (i.e., temperature and oxygen pressure), six different long-range ordered phases are obtained. They are characterized by means of low-energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). By careful optimization of the preparative parameters, we find conditions where predominantly single phases of TiO(x), revealing distinct LEED pattern and STM images, are produced. XPS binding energy and photoelectron diffraction (XPD) data indicate that all the phases, except one (the stoichiometric rect-TiO2), are one monolayer thick and composed of a Ti-O bilayer with interfacial Ti. Atomically resolved STM images confirm that these TiO(x) phases wet the Pt surface, in contrast to rect-TiO2. This indicates their interface stabilization. At a low Ti dose (0.4 monolayer equivalents, MLE), an incommensurate kagomé-like low-density phase (k-TiO(x) phase) is observed where hexagons are sharing their vertexes. At a higher Ti dose (0.8 MLE), two denser phases are found, both characterized by a zigzag motif (z- and z'-TiO(x) phases), but with distinct rectangular unit cells. Among them, z'-TiO(x), which is obtained by annealing in ultrahigh vacuum (UHV), shows a larger unit cell. When the postannealing of the 0.8 MLE deposit is carried out at high temperatures and high oxygen partial pressures, the incommensurate nonwetting, fully oxidized rect-TiO2 is found The symmetry and lattice dimensions are almost identical with rect-VO2, observed in the system VO(x)/Pd(111). At a higher coverage (1.2 MLE), two commensurate hexagonal phases are formed, namely the w- [(square root(43) x square root(43)) R 7.6 degrees] and w'-TiO(x) phase [(7 x 7) R 21.8 degrees]. They show wagon-wheel-like structures and have slightly different lattice dimensions. Larger Ti deposits produce TiO2 nanoclusters on top of the different monolayer films, as supported both by XPS and STM data. Besides the formation of TiO(x) surfaces phases, wormlike features are found on the bare parts of the substrate by STM. We suggest that these structures, probably multilayer disordered TiO2, represent growth precursors of the ordered phases. Our results on the different nanostructures are compared with literature data on similar systems, e.g., VO(x)/Pd(111), VO(x)/Rh(111), TiO(x)/Pd(111), TiO(x)/Pt(111), and TiO(x)/Ru(0001). Similar and distinct features are observed in the TiO(x)/Pt(111) case, which may be related to the different chemical natures of the overlayer and of the substrate.