Reference-Free Quantitative Mass Spectrometry Enables Sequencing of Resist Copolymers and Reveals Sequence-Dependent Deprotection Sensitivity
Yusuke Hibi, Yasuyuki Nakamura, Shiho Uesaka, Masanobu Naito
TL;DR
A new mass spectrometry method can sequence resist copolymers and shows that polymer sequence affects deprotection sensitivity, which could impact semiconductor lithography.
Contribution
A reference-free pyrolysis-MS sequencing method is introduced for resist polymers, revealing sequence-dependent deprotection behavior.
Findings
Pyrolysis mass spectrometry can quantify short-sequence frequencies in resist polymers.
Sequence-dependent decomposition temperature profiles encode sequence information.
Sequence influences deprotection sensitivity, potentially affecting lithography performance.
Abstract
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 nondegradable 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-…
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Taxonomy
TopicsBlock Copolymer Self-Assembly · Advancements in Photolithography Techniques · Copper Interconnects and Reliability