# Reference-Free Quantitative Mass Spectrometry Enables Sequencing of Resist Copolymers and Reveals Sequence-Dependent Deprotection Sensitivity

https://mdr.nims.go.jp/datasets/5cc80794-fb64-48aa-9401-8b23f1b9c81d

## Files

- [reference-free-quantitative-mass-spectrometry-enables-sequencing-of-resist-copolymers-and-reveals-sequence-dependent.pdf](https://mdr.nims.go.jp/filesets/a0626a73-5d6d-4b86-b326-4e3de58c5bf3/download) ([Detail](https://mdr.nims.go.jp/filesets/a0626a73-5d6d-4b86-b326-4e3de58c5bf3.md))

## Id

5cc80794-fb64-48aa-9401-8b23f1b9c81d

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2026-02-12T02:39:11.161136Z

## Updated at

2026-02-13T07:30:15.061300Z

## Published at

2026-02-13T05:13:27.217828Z

## Doi



## First published url

https://doi.org/10.1021/acs.macromol.5c03032

## Date published

2026-02-10

## Recorded date published

2026-2-10

## Resource type

journal_article

## Manuscript type

vor

## Collection



## Title

- title: Reference-Free Quantitative Mass Spectrometry Enables Sequencing of Resist
    Copolymers and Reveals Sequence-Dependent Deprotection Sensitivity
  title_type: original
  lang: en

## Description

- 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.
  description_type: abstract
  lang: und

## Creator

- name: Yusuke Hibi
  role: author
  orcid: https://orcid.org/0000-0003-4006-1070
- name: Yasuyuki Nakamura
  role: author
  orcid: https://orcid.org/0000-0003-0078-6413
- name: Shiho Uesaka
  role: author
- name: Masanobu Naito
  role: author
  orcid: https://orcid.org/0000-0001-7198-819X

## Contact agent



## Publisher

organization: American Chemical Society (ACS)

## Managing organization



## Keyword

- subject: polymer sequencing
  schema: not_defined
- subject: monomer sequence analysis
  schema: not_defined
- subject: pyrolysis mass spectrometry
  schema: not_defined
- subject: photoresist
  schema: not_defined
- subject: non-negative matrix factorization
  schema: not_defined
- subject: reference-free quantitative mass spectrometry
  schema: not_defined

## Rights

- identifier: https://creativecommons.org/licenses/by/4.0/

## Other identifier(s)



## Data origin



## Embargo



## Journal

- title: Macromolecules
  issn: '00249297'
  volume: '59'
  issue: '3'
  start_page: 1640
  end_page: 1649

## Conference



## Related item



## Funding

- identifier: JPMJCR19J3
  funder_name: Core Research for Evolutional Science and Technology
- identifier: JP23K04845
  funder_name: Japan Society for the Promotion of Science
- identifier: JP24K08520
  funder_name: Japan Society for the Promotion of Science

## Instrument



## Instrument operator



## Instrument managing organization



## Measurement method



## Specimen



## Chemical composition



## Structure for specimen



## Structural feature for specimen



## Specific property for specimen



## Process for specimen treatment



## Computational method



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## Fileset

- id: a0626a73-5d6d-4b86-b326-4e3de58c5bf3
  filename: reference-free-quantitative-mass-spectrometry-enables-sequencing-of-resist-copolymers-and-reveals-sequence-dependent.pdf
  content_type: application/pdf
  size: 5801832
  md5: 74e6f262c02497c339c775c9c55f3eff

## Thumbnail

fileset_id: a0626a73-5d6d-4b86-b326-4e3de58c5bf3
filename: reference-free-quantitative-mass-spectrometry-enables-sequencing-of-resist-copolymers-and-reveals-sequence-dependent.pdf