Evaluating nanoscale molecular homogeneity in EUV resists with Nano-Projectile SIMS

Characterizing chemical changes in photoresists during fabrication processes is critical to understanding how nanometric defects contribute to film stochastics. We used Nano-Projectile Secondary Ion Mass Spectrometry (NP-SIMS) to evaluate the nanoscale homogeneity of components in positive-tone extreme ultraviolet resists. NP-SIMS was operated in the event-by-event bombardment/detection mode, where a suite of individual gold nanoprojectiles separated in time and space stochastically bombard the surface. Each impact ejects secondary ions from a volume 10-15 nm in diameter and up to 10 nm in depth allowing for analysis of colocalized moieties with high spatial resolution. Individual partially exposed EUV resists were analyzed after light exposure, post-exposure bake (PEB), and development. Results showed an expected increase in protonated quencher versus exposure dose, while after development we observed increased abundance in the remaining film. The latter we attribute to poor solubility in the developing solvent. Examining the photoacid generator, PAG, we found decreased PAG cation abundance versus exposure dose in the exposed films, likely due to photodecomposition of the PAG cation. Moreover, after development we observed decreased homogeneity of PAG ions, which we attribute to preferential extraction caused by ion-exchange interactions with the developer. We found that the insoluble moieties persisting on the surface after development were relatively rich in the protecting group, likely due to uneven deprotection of the polymer. Overall, NP-SIMS allows to characterize the resist at the nanoscale and identify conditions that lead to defect formation.