Synthesis, characterization and use of peroxotungstic ethoxide as a precursor to wet-chemically derived tungsten oxide thin films

In this work a new wet-chemical method of preparing tungsten oxide thin films is described. This involves the dissolution of tungsten metal in aqueous hydrogen peroxide and reaction with acetic acid to form an alcohol-soluble precursor. All synthesis stages of this new precursor, termed peroxotungstic ethoxide, are characterized to determine possible reactions. The chemical and microstructural evolution of films is described as a function of firing temperature, utilizing infrared spectroscopy, diffraction and other optical data. A novel method of increasing the crack-free thickness of the films is given: a combination of oxalic acid dihydrate as a solution additive and film firing under controlled humidity. With this combination, fired crack-free films up to one micron in thickness were prepared. Oxalic acid dihydrate roughened and also caused crystallization of these films at lower temperatures (250°C) than expected. These rougher films exhibited an improved electrochromic response, as measured by optical and electrochemical characterizations