Modulation of refractive index and thickness of poly(methyl methacrylate) thin films with UV irradiation and heat treatment

This paper reports changes in refractive index and thickness of spin-coated poly(methyl methacrylate) (PMMA) thin films upon irradiation by a conventional high-pressure mercury UV lamp. Significant increase in refractive index and reduction in thickness are detected. Index modulations of greater than 0.01 are achieved in the thin films after 4 min of irradiation. The thickness reduction of an irradiated PMMA film is consistent with its weight loss. This is caused by the escape of the volatile molecules generated during the irradiation process. A slight increase in the refractive index is also found in the film, heat-treated above its glass transition temperature (Tg). This thermal effect is detected in the UV irradiation process. We propose three possible aliphatic structures that are formed during the photochemical reaction and may exist in the main chain of irradiated PMMA after the irradiation. Their refractive indices in aggregate state are greater than that of PMMA based on an evaluation using the Lorentz-Lorenz equation. This is suggested to be an important reason for the refractive index increase in the UV-irradiated PMMA films. A UV-irradiated film, heat-treated above its Tg, has a rough surface with many tiny holes as illustrated by atomic force microscopy. These holes are attributed to the evaporation of the small molecules generated during the irradiation process.