Ellipsometric studies are generally carried out in the reflection mode rather than in the transmission mode, requiring invariably opaque substrates or substrates in which the backreflection is minimized or suppressed by different methods. In the present research we used a transmission and reflection photoellipsometry method to study electrochromic materials and their multilayer systems deposited on thick substrates. The role of the substrate is examined carefully, and the contributions from multiple reflections in the substrate are taken into account in the theoretical treatment. This procedure not only allows the study of thin films deposited on quasi-transparent substrates, but when carried out in conjunction with reflection measurements it greatly improves the accuracy in the determination of the optical constants. Optical measurements are carried out on an automatic reflection transmission spectroscopic ellipsometer. Solid-state ionic materials used in electrochromic systems such as indium tin oxide, tungsten oxide, and their multilayer structures deposited on glass substrates are used as examples. A software based on the above theory, optikan, was developed to model and analyze such systems. It is demonstrated that the photoellipsometry method proposed is especially suited to analyzing electrochromic materials and transmitting devices in a nondestructive way.
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