Influence of crystal structure and oxygen vacancies on optical properties of nanostructured multi-stoichiometric tungsten suboxides.

Four distinct tungsten suboxide (WO 3- x ) nanomaterials were synthesized via chemical vapour transport reaction and the role of their crystal structures on the optical properties was studied. These materials grow either as thin, quasi-2D crystals with the W n O 3 n -1 formula (in shape of platelets or nanotiles), or as nanowires (W 5 O 14 , W 18 O 49 ). For the quasi-2D materials, the appearance of defect states gives rise to two indirect absorption edges. One is assigned to the regular bandgap occurring between the valence and the conduction band, while the second is a defect-induced band. While the bandgap values of platelets and nanotiles are in the upper range of the reported values for the suboxides, the nanowires' bandgaps are lower due to the higher number of free charge carriers. Both types of nanowires sustain localized surface plasmon resonances, as evidenced from the extinction measurements, whereas the quasi-2D materials exhibit excitonic transitions. All four materials have photoluminescence emission peaks in the UV region. The interplay of the crystal structure, oxygen vacancies and shape can result in changes in optical behaviour, and the understanding of these effects could enable intentional tuning of selected properties.