The volume and depth distributions of open spaces in photoresist films designed for ArF-excimer laser light exposure were studied with monoenergetic positron beams. We measured the Doppler broadening spectra of the annihilation radiation and lifetime spectra of positrons for acrylate and cyclic olefin-co-maleic anhydride (COMA) polymers spin-coated onto Si wafers with methyl amyl ketone, cyclohexanone, and propylene glycol methyl ether acetate solvents. The volume of open spaces in both prebaked acrylate and COMA films was estimated to be 0.12 nm(3). The volume of open spaces in acrylate films decreased up to 20% by postexposure baking, but no large change was observed for COMA films. The decrease in the open volume was attributed to the removal of large molecules (adamantyl) from flexible main chains after the chemically amplified reaction of acrylate. (C) 2003 Wiley Periodicals, Inc.