Perhydropolysilazane-derived silica-polymethylmethacrylate hybrid thin films highly doped with spiropyran: Effects of polymethylmethacrylate on the hardness, chemical durability and photochromic properties

Polymethylmethacrylate (PMMA)-perhydropolysilazane (PHPS) hybrid thin films doped with spiropyran were prepared by spin-coating, which were then converted into 0.26-1.7 μm thick, spiropyran-doped PMMA-silica hybrid films by exposure treatment over aqueous ammonia. The spiropyran/(spiropyran + PHPS + PMMA) mass ratio was fixed at a high value of 0.2 so that the films exhibit visual photochromic changes in color, while the PMMA/(PMMA + PHPS) mass ratio, r, was varied. The spiropyran molecules in the as-prepared films were in merocyanine (MC) and spiro (SP) forms, with and without an optical absorption at 500 nm, at low (r ≤ 0.2) and high (r ≥ 0.4) PMMA contents, respectively. When PMMA content r was increased from 0 to 0.2, the degree of the MC-to-SP conversion on vis light illumination was enhanced, while at higher r's the spiropyran molecules underwent photodegradation. When the silica film (r = 0) was soaked in xylene under vis light, the spiropyran molecules were almost totally leached out, while not on soaking in the dark. On the other hand, no leaching occurred for the film of r = 0.2 either in the presence or absence of vis light. These suggest that the introduction of PMMA is effective in improving the chemical durability of the films, while the silica film (r = 0) is an interesting material with a photoresponsive controlled-release ability. The pencil hardness of the films decreased with increasing PMMA content, but remained over 9H at r ≤ 0.4.