Role of low-energy electrons in the solubility switch of Zn-based oxocluster photoresist for extreme ultraviolet lithography

The electron-induced chemistry of a resist material for extreme ultraviolet lithography (EUVL) consisting of Zn oxoclusters with methacrylate (MA) and trifluoroacetate (TFA) ligands (Zn(MA)(TFA)) has been studied. Electron energies of 80 eV and 20 eV mimic the effect of photoelectrons released by the absorption of EUV photons and low-energy secondary electrons (LESEs) produced by those photoelectrons. The chemical conversion of the resist is studied by mass spectrometry to monitor the volatile species that desorb during electron irradiation, combined with reflection absorption infrared spectra (RAIRS) measured before and after irradiation. The observed reactions are closely related to those initiated upon EUV absorption. Also, the conversion of the Zn(MA)(TFA) resist layer that is required in EUVL is achieved by a similar energy input upon electron irradiation. The dominant component of the desorbing gas is CO2, but CO detection also suggests Zn oxide formation during electron irradiation. In contrast, species deriving from the ligand side chains predominantly remain within the resist layer. RAIRS gives direct evidence that, during electron irradiation, C[double bond, length as m-dash]C bonds of the MA ligands are more rapidly consumed than the carboxylate groups. This supports that chain reactions occur and contribute to the solubility switch in the resist in EUVL. Remarkably, 20 eV electrons still evolve roughly 50% of the amount of the gas that is observed at 80 eV for the same electron dose. The present results thus provide complementary and new insight to the EUV-induced chemistry in the Zn(MA)(TFA) resist and point towards the important contribution of low-energy electrons therein.