Unraveling the Reaction Mechanisms in a Chemically Amplified EUV Photoresist from a Combined Theoretical and Experimental Approach

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Main Authors: Galleni, Laura, Singh, Dhirendra P., Conard, Thierry, Pourtois, Geoffrey, van der Heide, Paul, Petersen, John, Dorney, Kevin M., van Setten, Michiel J.
Format: Preprint
Published: 2025
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author Galleni, Laura
Singh, Dhirendra P.
Conard, Thierry
Pourtois, Geoffrey
van der Heide, Paul
Petersen, John
Dorney, Kevin M.
van Setten, Michiel J.
author_facet Galleni, Laura
Singh, Dhirendra P.
Conard, Thierry
Pourtois, Geoffrey
van der Heide, Paul
Petersen, John
Dorney, Kevin M.
van Setten, Michiel J.
contents Extreme ultraviolet (EUV) lithography has revolutionized high-volume manufacturing of nanoscale components, enabling the production of smaller, denser, and more energy efficient integrated circuit devices. Yet, the use of EUV light results in ionization driven chemistry within the imaging materials of lithography, the photoresists. The complex interplay of ionization, generation of primary and secondary electrons, and the subsequent chemical mechanisms leading to image formation in photoresists has been notoriously difficult to study. In this work, we deploy photoemission spectroscopy with a 92 eV EUV light source combined with first-principles simulations to unravel the chemical changes occurring during exposure in a model chemically amplified photoresist. The results reveal a surprising chemical reaction pathway, namely the EUV-induced breakdown of the photoacid generator (PAG), which is a critical component in the EUV mechanism. This previously unobserved reaction mechanism manifests as changes in intensity of the valence band peaks of the EUV photoemission spectrum, which are linked to degradation of the PAG via an advanced atomistic simulation framework. Our combined experimental and theoretical approach shows that EUV photoemission can simultaneously resolve chemical dynamics and the production of primary and secondary electrons, giving unique insights into the chemical transformation of photoresist materials. Our results pave the way for utilizing accessible, table-top EUV spectroscopy systems for observing EUV photoresist chemical dynamics, with the potential for time-resolved measurements of photoemission processes in the future.
format Preprint
id arxiv_https___arxiv_org_abs_2505_07346
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Unraveling the Reaction Mechanisms in a Chemically Amplified EUV Photoresist from a Combined Theoretical and Experimental Approach
Galleni, Laura
Singh, Dhirendra P.
Conard, Thierry
Pourtois, Geoffrey
van der Heide, Paul
Petersen, John
Dorney, Kevin M.
van Setten, Michiel J.
Materials Science
Extreme ultraviolet (EUV) lithography has revolutionized high-volume manufacturing of nanoscale components, enabling the production of smaller, denser, and more energy efficient integrated circuit devices. Yet, the use of EUV light results in ionization driven chemistry within the imaging materials of lithography, the photoresists. The complex interplay of ionization, generation of primary and secondary electrons, and the subsequent chemical mechanisms leading to image formation in photoresists has been notoriously difficult to study. In this work, we deploy photoemission spectroscopy with a 92 eV EUV light source combined with first-principles simulations to unravel the chemical changes occurring during exposure in a model chemically amplified photoresist. The results reveal a surprising chemical reaction pathway, namely the EUV-induced breakdown of the photoacid generator (PAG), which is a critical component in the EUV mechanism. This previously unobserved reaction mechanism manifests as changes in intensity of the valence band peaks of the EUV photoemission spectrum, which are linked to degradation of the PAG via an advanced atomistic simulation framework. Our combined experimental and theoretical approach shows that EUV photoemission can simultaneously resolve chemical dynamics and the production of primary and secondary electrons, giving unique insights into the chemical transformation of photoresist materials. Our results pave the way for utilizing accessible, table-top EUV spectroscopy systems for observing EUV photoresist chemical dynamics, with the potential for time-resolved measurements of photoemission processes in the future.
title Unraveling the Reaction Mechanisms in a Chemically Amplified EUV Photoresist from a Combined Theoretical and Experimental Approach
topic Materials Science
url https://arxiv.org/abs/2505.07346