A useful protocol is presented for evaluation of the lithographic performance of chemically amplified photoresists that differ by formulation. A standard addition technique, infrared spectroscopy, and a development rate monitor were used, respectively, to measure the efficiency of photoacid generation upon exposure, the extent of polymer deprotection after the postexposure bake (PEB), and the dissolution rate of the resist in aqueous base developer. The combination of these experimental methods enabled the determination of (1) the concentration of photoacid that was generated in the resists as a function of exposure dose, (2) the extent of polymer deprotection that was achieved after the PEB as a function of the concentration of photoacid, and (3) the dissolution rate of the resist as a function of the extent of polymer deprotection. Photoresists may be compared using these three key relationships to evaluate the effects of formulation on resist performance. These methods were applied to investigate the impact of the chemical structure of two photoacid generators, norbornene dicarboximidyl triflate and triphenylsulfonium triflate, on the performance of photoresist comprised of poly(p-t-butoxycarbonyloxystyrene-co-p-hydroxystyrene) as the matrix polymer. The chemical structure of the photoacid generator affected the performance of these resist formulations in at least three key ways: (1) the efficiency of photoacid generation upon exposure to ionizing radiation, (2) the reaction-diffusion process of photoacid to deprotect the polymer during postexposure 'processing, and (3) the inhibition of resist dissolution in aqueous base. These three processes synergistically contributed to the sensitivity of the resist. The differences in the performance between these two resists were directly related to the chemical structure of the photoacid generator, in ways beyond the type of photogenerated acid, since both molecules produce triflic acid upon exposure and the matrix polymer and processing conditions were identical for both resist systems. (C) 2004 American Vacuum Society.