Evaluating Nanoscale Molecular Homogeneity in Extreme Ultraviolet Resists with Nanoprojectile Secondary Ion Mass Spectrometry

Characterizing chemical changes in photoresists during fabrication processes is critical to understanding how nanometric defects contribute to film stochastics. We used nanoprojectile 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 to 15 nm in diameter and up to 10 nm in depth allowing for analysis of colocalized moieties with high spatial resolution. Individual partially exposed extreme ultraviolet resists were analyzed after light exposure, postexposure bake, 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 the 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 the 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.