In order to measure a complex dielectric constant of a thin film on a substrate, a method includes irradiating the thin film sample with light at a first incident angle so that the light undergoes multiple internal reflections within the thin film sample. The method also includes measuring light that has transmitted through or reflected on the thin film sample following the multiple internal reflections, and determining a complex dielectric constant of the thin film sample based upon a spectrum of the transmitted or reflected light that has undergone the multiple internal reflections.