Photochemical free-volume generation in poly(methyl methacrylate) photoresists

The dissolution rates of poly(methyl methacrylate) [PMMA] thin films on quartz substrates are studied by a combination of laser interferometry and fluorescence quenching methods. In this way one can monitor the penetration, rate of the solvent (2-butanone, 2-pentanone) into the film. When these films were prepared containing 2 to 8 percent Meldrum's diazo (1) as a dopant, the dopant acted as a mild retarder of film dissolution. Upon irradiation at 254 nm, 1 is converted to CO, N2 + acetone, and this process leads to a pronounced acceleration' of the PMMA film dissolution rate.