Anion Doping of Tungsten Oxide with Nitrogen: Reactive Magnetron Synthesis, Crystal Structure, Valence Composition, and Optical Properties

Abstract

Anion doping of tungsten trioxide by nitrogen is used to obtain electrochrome cathode materials, the spectral transmittance of which can be controlled by the doping level. A series of samples was synthesized by reactive magnetron sputtering of a metal tungsten target in a mixture of argon, nitrogen, and oxygen gases, the flow rate of the latter was varied at a constant pressure of the gas mixture. Warm-colored tungsten oxynitride films were prepared at higher doping levels with their morphology and elemental composition characterized using scanning electron microscopy, crystal structure described using X-ray diffraction and the valence state of constituents revealed with X-ray photoelectron spectroscopy techniques. Optical properties were measured by making use of transmission spectrophotometry and spectroscopic ellipsometry. These extensive experimental studies revealed an increase in absorption towards shorter wavelengths below the wavelength of 0.5 µm with an increase in the doping level. At the same time, it was found that with an increase in the doping level, partial reduction of the tungsten occurs, and the fraction of non-stoichiometric oxygen steadily increases to half of the total oxygen content. It is a common belief that the imperfection of the doped material facilitates the intercalation of the material by electrolyte ions.