PNNL

Abstract

Ordered tungsten oxide ultra-thin films were prepared on a Pt(111) substrate at 700 K via direct sublimation of monodispersed cyclic (WO3)3 trimers. The surface composition, structure and morphology were determined using a combination of atomically resolved imaging, ensemble-averaged surface-sensitive spectroscopies, and density functional theory (DFT). We find that half of the (WO3)3 tungsten atoms get partially reduced to the (5+) oxidation state in the first layer at the Pt(111) interface. The opening of the (WO3)3 ring leads to the formation of a tungsten oxide layer with a zig-zag chain structure with a c(4×2) periodicity. In the second layer, the (WO3)3 clusters remain intact and form an ordered (3×3) array of molecularly-bound (WO3)3. DFT calculations provide a detailed understanding of the structure, oxidation states, and the vibrational frequencies for both the c(4×2) and (3×3) overlayers.