Accurate and efficient evaluation of the ionization potentials of extreme ultraviolet photoresists using density functionals and semi-empirical methods

AbstractExtreme ultraviolet (EUV) photoresists have become the core materials in lithography with nanometer-sized patterns and are actively explored on the path to realizing smaller critical dimensions. These photoresists can be small molecule-, polymer-, or organic–inorganic hybrid-based, with the full molecular working mechanism under investigation. For the rational design of EUV photoresists, theoretical guidance using tools like first-principle calculations and multi-scale simulations can be of great help. Considering the extremely high standard of accuracy in EUV lithography, it is critical to ensure the adoption of the appropriate methodologies in the theoretical evaluation of EUV photoresists. However, it is known that density functionals and semi-empirical methods differ in accuracy and efficiency, without a universal rule across materials. This poses a challenge in developing a reliable theoretical framework for calculating EUV photoresists. Here, we present a benchmark investigation of density functionals and semi-empirical methods on the three main types of EUV photoresists, focusing on the ionization potential, a key parameter in their microscopic molecular reactions. The vertical detachment energies (VDE) and adiabatic detachment energies (ADE) were calculated using 12 functionals, including pure functionals, hybrid functionals, Minnesota functionals, and the recently developed optimally tuned range-separated (OTRS) functionals. Several efficient semi-empirical methods were also chosen, including AM1, PM6, PM7, and GFN1-xTB in the extended tight-binding theoretical framework. These results guide the accurate and efficient calculation of EUV photoresists and are valuable for the development of multi-scale lithography protocols. Graphical Abstract