Growth process conditions of tungsten oxide thin films using hot-wire chemical vapor deposition

We report the growth conditions of nanostructured tungsten oxide (WO3−x) thin films using hot-wire chemical vapor deposition (HWCVD). Two tungsten filaments were resistively heated to various temperatures and exposed to an air flow at various subatmospheric pressures. The oxygen partial pressure was varied from 6.0 × 10−6 to 1.0 mbar and the current through the filaments was varied from 4.0 to 9.0 A, which constitutes a filament temperature of 1390–2340 °C in vacuum. It is observed that the deposition rate of the films is predominantly determined by the oxygen partial pressure; it changes from about 1 to about 36,000 nm min−1 in the investigated range. Regardless of the oxygen partial pressure and filament temperature used, thin films with a nanogranular morphology are obtained, provided that the depositions last for 30 min or shorter. The films consist either of amorphous or partially crystallized WO3−x with high averaged transparencies of over 70% and an indirect optical band gap of 3.3 ± 0.1 eV. A prolonged deposition time entails an extended exposure of the films to thermal radiation from the filaments, which causes crystallization to monoclinic WO3 with diffraction maxima due to the (0 0 2), (2 0 0) and (0 2 0) crystallographic planes, furthermore the nanograins sinter and the films exhibit a cone-shaped growth. By simultaneously influencing the surface mobility, by heating the substrates to Tsurface = 700 ± 100 °C, and the deposition rate, a very good control of the morphology of the deposited films is obtained. Nanowire films, nanocrystallite films and closed crystallite films were thus deposited. These differently nanostructured c-WO3 films all possess an indirect optical band gap of 2.5 ± 0.1 eV.