Time-dependent lateral diffusion in WO₃ thin films

Abstract

We have studied the anomalous lateral diffusion process in thin tungsten trioxide films by optical means. The diffusion process seems to start at imperfections within the film a few seconds after the H+ ion intercalation begins, and progresses parallel to the surface of the film. We measured the mean square displacement of the diffusion front and used its time-dependence to calculate the instantaneous diffusion coefficient. The anomalous exponents are found to be 2.24 and 2.92 for 400 nm and 270 nm thick films, respectively. We explain the observed large diffusion coefficients and depth dependence of the expansion of the film by interfacial job-sharing diffusion of electrons and protons. Raman measurements were also carried out on virgin films, and on films after the lateral diffusion. Although the observed spectrum after the lateral diffusion is, in general, consistent with the literature for H+ intercalated films, we observe an additional strong band at 855 cm−1. This lateral diffusion process is observed to be irreversible; therefore, it has to be avoided in electrochromic switching devices based on WO3.