Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography

Zhu-Lu Xie; Fu-Wei Kong; Jia-Hui Chen; Jie Yan; Bo-Ting Wang; Tian-Ren Zhao; Shuo-Feng Liang; Si Wu

doi:10.1007/s10118-026-3637-2

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Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography

RESEARCH ARTICLE | Updated：2026-07-01

- Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography
- Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography
- Chinese Journal of Polymer Science 2026年44卷第7期页码：2239-2247
- Affiliations：
  
  Hefei National Research Center for Physical Sciences at the Microscale, Anhui Key Laboratory of Optoelectronic Science and Technology, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
- Author bio：
  
  liangsf@ustc.edu.cn (S.F.L.)
  siwu@ustc.edu.cn (S.W.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 52503162, 52425302, 52120105004, and 52350233), Hefei Municipal Natural Science Foundation (No. HZR2518), Fundamental Research Funds for the Central Universities (Nos. WK3450000006 and WK2060190102), Anhui Provincial Natural Science Foundation (Nos. 1908085MB38 and 2508085QB046), and Postdoctoral Fellowship Program of CPSF (No. GZB20250013). This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication and the Instruments Center for Physical Science, University of Science and Technology of China.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3637-2.The data supporting the findings of this study are available from the corresponding authors upon reasonable request.
- DOI：10.1007/s10118-026-3637-2
  中图分类号：
- 收稿：2026-02-03，
  
  录用：2026-02-27，
  
  网络首发：2026-06-03，
  
  纸质出版：2026-07-05
- Accepted：
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Xie, Z. L.; Kong, F. W.; Chen, J. H.; Yan, J.; Wang, B. T.; Zhao, T. R.; Liang, S. F.; Wu, S. Long alkyl tails amplify photoswitchable glass transition temperatures of azopolymers for nanoimprint lithography. Chinese J. Polym. Sci. 2026, 44, 2239–2247

Zhu-Lu Xie, Fu-Wei Kong, Jia-Hui Chen, et al. Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2239-2247.
Xie, Z. L.; Kong, F. W.; Chen, J. H.; Yan, J.; Wang, B. T.; Zhao, T. R.; Liang, S. F.; Wu, S. Long alkyl tails amplify photoswitchable glass transition temperatures of azopolymers for nanoimprint lithography. Chinese J. Polym. Sci. 2026, 44, 2239–2247 DOI： 10.1007/s10118-026-3637-2.

Zhu-Lu Xie, Fu-Wei Kong, Jia-Hui Chen, et al. Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2239-2247. DOI： 10.1007/s10118-026-3637-2.

摘要

Azobenzene-containing polymers exhibit photoswitchable glass-transition temperatures when modified with long alkyl tails. This tail-engineering approach fundamentally overcomes the spacer length limitations and establishes a generalizable design principle for reversible nanoimprint photoresists.

Abstract

Azobenzene-containing polymers (azopolymers) exhibit photoinduced reversible solid-to-liquid transitions

enabling unique light-assisted nanoimprint lithography (NIL).

Cis

azopolymers possess sub-room-temperature glass transition temperatures (

)

exhibiting liquid-like behavior for flow processing

while

trans

azopolymers feature above-room-temperature

values that enable solid-state shape fixation. Although many side-chain azopolymers demonstrate photoswitchable

conventional short-spacer derivatives show negligible switching in

as their

cis

isomers remain solid. This work overcomes this limitation in ethylene-spacer azopolymers through extended alkyl tails. We synthesized tailless (P0)

-butyl-tailed (P4)

and

-decyl-tailed (P10) derivatives

revealing that only P10 exhibits a

cis

near room temperature (22 °C) and an amplified Δ

between its

cis

isomer and

trans

isomer. P10 with photoswitchable

s enables complete nanostructure replication as a nanoimprint lithography photoresist. This work demonstrates that long alkyl tails counteract short-spacer limitations

effectively reducing the

cis

azopolymers and establishing a design principle for nanoimprint photoresists with photoswitchable

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references

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