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Highly ordered titanium oxide films grown on a Pt 3 Ti(111) alloy surface were utilized for the controlled immobilization and tip-induced electric field-triggered electronic manipulation of nanoscopic W 3 O 9 clusters. Depending on the operating conditions, two different stable oxide phases, z'-TiO  x  and w'-TiO  x  , were produced. These phases show a strong effect on the adsorption characteristics and reactivity of W 3 O 9 clusters, which are formed as a result of thermal evaporation of WO 3 powder on the complex TiO  x  /Pt 3 Ti(111) surfaces under ultra-high vacuum conditions. The physisorbed tritungsten nano-oxides were found as isolated single units located on the metallic attraction points or as supramolecular self-assemblies with a W 3 O 9 -capped hexagonal scaffold of W 3 O 9 units. By applying scanning tunneling microscopy to the W 3 O 9 -(W 3 O 9 ) 6 structures, individual units underwent a tip-induced reduction to W 3 O 8 . At elevated temperatures, agglomeration and growth of large WO 3 islands, which thickness is strongly limited to a maximum of two unit cells, were observed. The findings boost progress toward template-directed nucleation, growth, networking, and charge state manipulation of functional molecular nanostructures on surfaces using operando techniques.

beilstein journal of nanotechnology

TiOx/Pt3Ti(111) surface-directed formation of electronically responsive supramolecular assemblies of tungsten oxide clusters