Amorphous and crystalline electrochromic WO3 films exhibit quite different optical properties during coloration process. In the present work, amorphous and crystalline electrochromic WO3 films prepared by a solution method were characterized using X-ray diffraction, scanning electron microscope, and transmission electron microscope techniques. A double-layer model with sharp interfaces was established for the fitting of the ellipsometry parameters. The results show that the proton favors amorphous films more than crystalline WO3 films. The refractive indices of both amorphous and polycrystalline WO3 films decrease while extinction coefficients increase with the inserting of H+ during the coloration process. But the optical parameters of the latter are much more sensitive to the H+ ions injected compared to the amorphous WO3 during the coloration process. That is the refractive index modulation of the crystalline WO3 films is about 53% at 633 nm while that of the amorphous films about 15% at the same wavelength. The Drude-like free electron model for crystalline WO3 and hopping mechanism of small polaron for amorphous WO3 are used to explain the difference in detail. These results are very helpful for the better understanding of the coloration process and for the design of electrochromic devices.
