Tungsten oxides. II. The metallic nature of Magnéli phases

In the first part [D. B. Migas et al., J. Appl. Phys. 108, 093713 (2010)] electronic and optical properties of different phases of WO3 have been considered. In this part we present results of our ab initio calculations which clearly show that all Magnéli phases of tungsten oxides WOx (namely, W32O84, W3O8, W18O49, W17O47, W5O14, W20O58, and W25O73) are characterized by metal-like properties. Their band structures display an energy gap in the valence band just below the Fermi level. We discuss how addition (removal) of oxygen atoms to (from) the unit cell of W18O49 affects the position of the Fermi level with respect to the energy gap and the charge carrier concentration. A possible mechanism has been suggested in order to switch from metallic to semiconducting properties for W18O49 and to explain experimental observations.