Effect of resist components on image spreading during postexposure bake of chemically amplified resists

The ultimate feature size achievable using a chemically amplified resist is determined by chemical and physical processes occurring during the post-exposure bake process. Using a combined experimental-modelling procedure we previously have developed a physically accurate predictive descriptive of coupled deprotection and diffusion in poly(p-tert-butyloxycarbonyloxystyrene) (PTBOCST) resist containing a diaryliodonium perfluorobutanesulfonate salt as photoacid generator (PAG). In the present work we extend that study to quantify the impact of anion size and of added base on resist reaction diffusion kinetics. Our results show that both short and long range mobility of the PAG anion influence image spreading; the small triflate counterion leads to acid diffusion larger by a factor of 9-70 than that observed with the larger perfluorobutanesulfonate counterion: The addition of tetra-n-butylammonium hydroxide leads to an overall suppression of image spreading in the exposed resist. This effect can be analyzed quantitatively using a proportional neutralization model which reveals that base addition can lead to an overall sharpening of the developable latent image of deprotection even in the absence of acid diffusion.