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

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 x and w’-TiO x , 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 x /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.

Tailoring Crystalline Structure of Titanium Oxide Films for Optical Applications Using Non-Biased Filtered Cathodic Vacuum Arc Deposition at Room Temperature

Titanium oxide films were deposited at room temperature and with no applied bias using a filtered cathodic vacuum arc (FCVA) system in a reactive oxygen environment. The dependence of film growth on two process parameters, the working pressure (Pw) and the O2 partial pressure (pO2), is described in detail. The composition, morphological features, crystalline structure, and optical properties of the deposited films were systematically studied by Rutherford Back Scattering (RBS), Scanning Electron Microscopy (SEM), X-Ray diffraction (XRD), Raman Spectroscopy, UV-vis spectroscopy, and spectroscopic ellipsometry. This systematic investigation allowed the identification of three different groups or growth regimes according to the stoichiometry and the phase structure of the titanium oxide films. RBS analysis revealed that a wide range of TiOx stoichiometries (0.6 < × < 2.2) were obtained, including oxygen-deficient, stoichiometric TiO2 and oxygen-rich films. TiO, Ti2O3, rutile-type TiO2, and amorphous TiO2 phase structures could be achieved, as confirmed both by Raman and XRD. Therefore, the results showed a highly versatile approach, in which different titanium oxide stoichiometries and crystalline phases especially suited for diverse optical applications can be obtained by changing only two process parameters, in a process at room temperature and without applied bias. Of particular interest are crystalline rutile films with high density to be used in ultra-high reflectance metal-dielectric multilayered mirrors, and reduced-TiO2 rutile samples with absorption in the visible range as a very promising photocatalyst material.

Изменение оптических свойств оксида титана при кристаллизации

Crystallization of amorphous titanium oxide films synthesized by magnetron sputtering was carried out at temperatures of 700, 800, and 900 oC in an oxygen atmosphere. The refractive index of the films increases during crystallization with a time constant that depends on temperature, which made it possible to determine the activation energy of the crystallization process on the order of 0.6 eV. The growth kinetics model for the titanium oxide nanocrystals, which is used in this work, showed that the indicated activation energy corresponds to the diffusion energy of oxygen vacancies. This process is decisive for the growth of titanium oxide nanocrystals upon annealing in an oxygen atmosphere. The study of photoluminescence has shown that crystallization leads to a change in the ratio of intensities of different emission bands. The bands that are associated with the oxygen vacancy are extinguished. A decrease in the concentration of these vacancies in films leads to an increase in their resistance and stabilization of the films in time.