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Description:

The influence of monomer sequence in resist polymers on line-edge roughness (LER) has long remained elusive in semiconductor lithography. Although the arrangement of degradable and non-degradable monomers should affect polymer solubility in developer solutions, the lack of sequencing methods has prevented analysis of sequence–LER correlations. Here, we present a sequencing approach for resist polymers using pyrolysis mass spectrometry (pyrolysis-MS), which quantifies short-sequence frequencies from pyrolyzed oligomer fragments. Methacrylate-based resist polymers, however, undergo depolymerization and side chain cleavage, generating fragments too small to retain sequence information. Nevertheless, we found these instabilities themselves are sequence-dependent, as shown by computational modeling, encoding sequence information in decomposition temperature profiles. By exploiting both mass- and temperature-domains, our strategy enables sequencing of resist copolymers previously considered inaccessible. Moreover, sequence-dependent sidechain instabilities imply that resist responsiveness in deprotection processes may also depend on sequence. The proposed sequencer offers a path to unravel the long-standing sequence–LER relationship.

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• Creative Commons BY Attribution 4.0 International
  

Keyword: polymer sequencing, monomer sequence analysis, pyrolysis mass spectrometry, photoresist, non-negative matrix factorization, reference-free quantitative mass spectrometry

Date published: 2026-02-10

Publisher: American Chemical Society (ACS)

Journal:

• Macromolecules (ISSN: 00249297) vol. 59 issue. 3 p. 1640-1649

Funding:

• Core Research for Evolutional Science and Technology JPMJCR19J3
• Japan Society for the Promotion of Science JP23K04845
• Japan Society for the Promotion of Science JP24K08520

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1021/acs.macromol.5c03032

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Updated at: 2026-02-13 16:30:15 +0900

Published on MDR: 2026-02-13 14:13:27 +0900