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

Highly ordered titanium oxide films grown on a Pt₃Ti(111) alloy surface were utilized for the controlled immobilization and tip-induced electric field-triggered electronic manipulation of nanoscopic W₃O₉ clusters. Depending on the operating conditions, two different stable oxide phases, z'-TiO and w'-TiO , were produced. These phases show a strong effect on the adsorption characteristics and reactivity of W₃O₉ clusters, which are formed as a result of thermal evaporation of WO₃ powder on the complex TiO /Pt₃Ti(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 W₃O₉-capped hexagonal scaffold of W₃O₉ units. By applying scanning tunneling microscopy to the W₃O₉-(W₃O₉)₆ structures, individual units underwent a tip-induced reduction to W₃O₈. At elevated temperatures, agglomeration and growth of large WO₃ 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.