More is not always better: Dissociative photoionization limits the EUV absorbing photoacid generator pentafluorophenyl triflate in photolithography
Abstract
Pentafluorophenyl triflate has been explored as a highly absorbing neutral photoacid generator (PAG) candidate for next-generation chemically amplified resists used in extreme ultraviolet (EUV) lithography. Although increased fluorination enhances EUV absorption, this study demonstrates that such an approach does not necessarily improve photoacid generation efficiency. Using photoelectron-photoion coincidence spectroscopy at the 92 eV photon energy of the EUV scanners in combination with quantum-chemical calculations, the dissociative photoionization of pentafluorophenyl triflate was systematically investigated. The photoionization mass spectrum reveals extensive fragmentation, with the parent ion contributing only 3.1% of the total signal and CF3+ representing the dominant product ion. Computed appearance energies align well with experimental trends and support a sequential fragmentation pathway involving loss of SO2, CF3, and CO. Crucially, none of the major dissociation channels yield precursors capable of forming triflic acid, the strong photoacid required for efficient deprotection reactions in chemically amplified resists. Combined with previous dissociative electron attachment studies indicating similarly unfavorable fragmentation, the results demonstrate that despite its high EUV absorption cross section, pentafluorophenyl triflate is unsuitable as a PAG for EUV lithography. The findings highlight the importance of understanding fundamental photoionization and electron-interaction mechanisms to guide the rational design of next-generation high-performance EUV photoresists.
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BibTeX
@article{holzmeier2026more,
title = {{More is not always better: Dissociative photoionization limits the EUV absorbing photoacid generator pentafluorophenyl triflate in photolithography}},
author = {Fabian Holzmeier and Michiel J. van Setten and Ragnar Björnsson and Robert Richter and Filipe Ferreira da Silva and Oddur Ingólfsson},
journal = {The Journal of Chemical Physics},
year = {2026},
month = sep,
doi = {10.1063/5.0349498},
eprint = {2609.09958},
archivePrefix = {arXiv},
url = {https://hal.science/hal-05774371v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - More is not always better: Dissociative photoionization limits the EUV absorbing photoacid generator pentafluorophenyl triflate in photolithography
AU - Fabian Holzmeier
AU - Michiel J. van Setten
AU - Ragnar Björnsson
AU - Robert Richter
AU - Filipe Ferreira da Silva
AU - Oddur Ingólfsson
PY - 2026
DA - 2026/09/11
JO - The Journal of Chemical Physics
DO - 10.1063/5.0349498
UR - https://hal.science/hal-05774371v1
AB - Pentafluorophenyl triflate has been explored as a highly absorbing neutral photoacid generator (PAG) candidate for next-generation chemically amplified resists used in extreme ultraviolet (EUV) lithography. Although increased fluorination enhances EUV absorption, this study demonstrates that such an approach does not necessarily improve photoacid generation efficiency. Using photoelectron-photoion coincidence spectroscopy at the 92 eV photon energy of the EUV scanners in combination with quantum-chemical calculations, the dissociative photoionization of pentafluorophenyl triflate was systematically investigated. The photoionization mass spectrum reveals extensive fragmentation, with the parent ion contributing only 3.1% of the total signal and CF3+ representing the dominant product ion. Computed appearance energies align well with experimental trends and support a sequential fragmentation pathway involving loss of SO2, CF3, and CO. Crucially, none of the major dissociation channels yield precursors capable of forming triflic acid, the strong photoacid required for efficient deprotection reactions in chemically amplified resists. Combined with previous dissociative electron attachment studies indicating similarly unfavorable fragmentation, the results demonstrate that despite its high EUV absorption cross section, pentafluorophenyl triflate is unsuitable as a PAG for EUV lithography. The findings highlight the importance of understanding fundamental photoionization and electron-interaction mechanisms to guide the rational design of next-generation high-performance EUV photoresists.
SN - 0021-9606
SN - 1089-7690
ER -