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Optimization of fluorinated phenyl azides as universal photocrosslinkers for semiconducting polymers

Author

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  • Zhao-Siu Tan

    (National University of Singapore)

  • Zaini Jamal

    (National University of Singapore)

  • Desmond W. Y. Teo

    (National University of Singapore)

  • Hor-Cheng Ko

    (National University of Singapore)

  • Zong-Long Seah

    (National University of Singapore)

  • Hao-Yu Phua

    (National University of Singapore)

  • Peter K. H. Ho

    (National University of Singapore)

  • Rui-Qi Png

    (National University of Singapore)

  • Lay-Lay Chua

    (National University of Singapore)

Abstract

Fluorinated phenyl azides (FPA) enable photo-structuring of π-conjugated polymer films for electronic device applications. Despite their potential, FPAs have faced limitations regarding their crosslinking efficiency, and more importantly, their impact on critical semiconductor properties, such as charge-carrier mobility. Here, we report that azide photolysis and photocrosslinking can achieve unity quantum efficiencies for specific FPAs. This suggests preferential nitrene insertion into unactivated C‒H bonds over benzazirine and ketenimine reactions, which we attribute to rapid interconversion between the initially formed hot states. Furthermore, we establish a structure‒activity relationship for carrier mobility quenching. The binding affinity of FPA crosslinker to polymer π-stacks governs its propensity for mobility quenching in both PM6 and PBDB-T used as model conjugated polymers. This binding affinity can be suppressed by FPA ring substitution, but varies in a non-trivial way with π-stack order. Utilizing the optimal FPA, photocrosslinking enables the fabrication of morphology-stabilized, acceptor-infiltrated donor polymer networks (that is, PBDB-T: ITIC and PM6: Y6) for solar cells. Our findings demonstrate the exceptional potential of the FPA photochemistry and offer a promising approach to address the challenges of modelling realistic molecular interactions in complex polymer morphologies, moving beyond the limitations of Flory‒Huggins mean field theory.

Suggested Citation

  • Zhao-Siu Tan & Zaini Jamal & Desmond W. Y. Teo & Hor-Cheng Ko & Zong-Long Seah & Hao-Yu Phua & Peter K. H. Ho & Rui-Qi Png & Lay-Lay Chua, 2024. "Optimization of fluorinated phenyl azides as universal photocrosslinkers for semiconducting polymers," Nature Communications, Nature, vol. 15(1), pages 1-14, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-50257-5
    DOI: 10.1038/s41467-024-50257-5
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    References listed on IDEAS

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    1. Min Je Kim & Myeongjae Lee & Honggi Min & Seunghan Kim & Jeehye Yang & Hyukmin Kweon & Wooseop Lee & Do Hwan Kim & Jong-Ho Choi & Du Yeol Ryu & Moon Sung Kang & BongSoo Kim & Jeong Ho Cho, 2020. "Universal three-dimensional crosslinker for all-photopatterned electronics," Nature Communications, Nature, vol. 11(1), pages 1-11, December.
    2. Bo Liu & Rui-Qi Png & Li-Hong Zhao & Lay-Lay Chua & Richard H. Friend & Peter K.H. Ho, 2012. "High internal quantum efficiency in fullerene solar cells based on crosslinked polymer donor networks," Nature Communications, Nature, vol. 3(1), pages 1-8, January.
    3. Chao Zhao & Cindy G. Tang & Zong-Long Seah & Qi-Mian Koh & Lay-Lay Chua & Rui-Qi Png & Peter K. H. Ho, 2021. "Improving organic photovoltaic cells by forcing electrode work function well beyond onset of Ohmic transition," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    4. Yu Zheng & Zhiao Yu & Song Zhang & Xian Kong & Wesley Michaels & Weichen Wang & Gan Chen & Deyu Liu & Jian-Cheng Lai & Nathaniel Prine & Weimin Zhang & Shayla Nikzad & Christopher B. Cooper & Donglai , 2021. "A molecular design approach towards elastic and multifunctional polymer electronics," Nature Communications, Nature, vol. 12(1), pages 1-11, December.
    5. Cindy G. Tang & Mazlan Nur Syafiqah & Qi-Mian Koh & Chao Zhao & Jamal Zaini & Qiu-Jing Seah & Michael J. Cass & Martin J. Humphries & Ilaria Grizzi & Jeremy H. Burroughes & Rui-Qi Png & Lay-Lay Chua &, 2019. "Multivalent anions as universal latent electron donors," Nature, Nature, vol. 573(7775), pages 519-525, September.
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