Tin-oxo nanoclusters for extreme ultraviolet photoresists: Effects of ligands, counterions, and doping.

ABSTRACT

The extreme ultraviolet (EUV) nanolithography technology is the keystone for developing the next-generation chips. As conventional chemically amplified resists are approaching the resolution limit, metal-containing photoresists, especially tin-oxo clusters, seize the opportunity to embrace this challenge owing to their small sizes, precise atomic structures, and strong EUV absorption. However, atomistic insights into the mechanism for regulating their photolithographic behavior are lacking. Herein, we systematically explored the effects of ligands, counterions, and endohedral doping on the photophysical properties of tin-oxo cage clusters by first-principles calculations combined with molecular dynamics simulations. Photoresists assembled by allyl-protected clusters with small-size OH- or Cl- counterions have a high absorption coefficient at the EUV wavelength of 13.5 nm and a low energy cost for ligand detachment and superior stability to ensure high sensitivity and strong etch resistance, respectively. The photoresist performance can further be improved by endohedral doping of the metal-oxo nanocage with Ag+ and Cd2+ ions, which exhibit superatomic characteristics and are likely to be synthesized in laboratory. These theoretical results provide useful guidance for modification of metal-oxo clusters for high-resolution EUV photolithography.