Fluorine-Substituted Dithienylbenzodiimide-Based n-Type Polymer Semiconductors for Organic Thin-Film Transistors

Kui Feng, Xianhe Zhang, Ziang Wu, Yongqiang Shi, Mengyao Su, Kun Yang, Yang Wang, Huiliang Sun, Jie Min, Yujie Zhang, Xing Cheng, Han Young Woo, Xugang Guo

Research output: Contribution to journalArticle

Abstract

Imide functionalization is one of the most effective approaches to develop electron-deficient building blocks for constructing n-type organic semiconductors. Driven by the attractive properties of imide-functionalized dithienylbenzodiimide (TBDI) and the promising device performance of TBDI-based polymers, a novel acceptor with increased electron affinity, fluorinated dithienylbenzodiimide (TFBDI), was designed with the hydrogen replaced by fluorine on the benzene core, and the synthetic challenges associated with this highly electron-deficient fluorinated imide building block are successfully overcome. TFBDI showed suppressed frontier molecular orbital energy levels as compared with TBDI. Copolymerizing this new electron-withdrawing TBDI with various donor co-units afforded a series of n-type polymer semiconductors TFBDI-T, TFBDI-Se, and TFBDI-BSe. All these TFBDI-based polymers exhibited a lower-lying lowest unoccupied molecular orbital (LUMO) energy level than the polymer analogue without fluorine. When applied in organic thin-film transistors, three polymers showed unipolar electron transport with large on-current/off-current ratios (Ion/Ioff) of 105-107. Among them, the selenophene-based polymer TFBDI-Se with the deepest-positioned LUMO and optimal chain stacking exhibited the highest electron mobility of 0.30 cm2 V-1 s-1. This result demonstrates that the new TFBDI is a highly attractive electron-deficient unit for enabling n-type polymer semiconductors, and the fluorination of imide-functionalized arenes offers an effective approach to develop more electron-deficient building blocks in organic electronics.

Original languageEnglish
Pages (from-to)35924-35934
Number of pages11
JournalACS Applied Materials and Interfaces
Volume11
Issue number39
DOIs
Publication statusPublished - 2019 Oct 2

Keywords

  • dithienylbenzodiimide
  • fluorination
  • imide functionalization
  • n-type polymer semiconductors
  • organic thin-film transistors

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Fluorine-Substituted Dithienylbenzodiimide-Based n-Type Polymer Semiconductors for Organic Thin-Film Transistors. / Feng, Kui; Zhang, Xianhe; Wu, Ziang; Shi, Yongqiang; Su, Mengyao; Yang, Kun; Wang, Yang; Sun, Huiliang; Min, Jie; Zhang, Yujie; Cheng, Xing; Woo, Han Young; Guo, Xugang.

In: ACS Applied Materials and Interfaces, Vol. 11, No. 39, 02.10.2019, p. 35924-35934.

Research output: Contribution to journalArticle

Feng, K, Zhang, X, Wu, Z, Shi, Y, Su, M, Yang, K, Wang, Y, Sun, H, Min, J, Zhang, Y, Cheng, X, Woo, HY & Guo, X 2019, 'Fluorine-Substituted Dithienylbenzodiimide-Based n-Type Polymer Semiconductors for Organic Thin-Film Transistors', ACS Applied Materials and Interfaces, vol. 11, no. 39, pp. 35924-35934. https://doi.org/10.1021/acsami.9b13138
Feng, Kui ; Zhang, Xianhe ; Wu, Ziang ; Shi, Yongqiang ; Su, Mengyao ; Yang, Kun ; Wang, Yang ; Sun, Huiliang ; Min, Jie ; Zhang, Yujie ; Cheng, Xing ; Woo, Han Young ; Guo, Xugang. / Fluorine-Substituted Dithienylbenzodiimide-Based n-Type Polymer Semiconductors for Organic Thin-Film Transistors. In: ACS Applied Materials and Interfaces. 2019 ; Vol. 11, No. 39. pp. 35924-35934.
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abstract = "Imide functionalization is one of the most effective approaches to develop electron-deficient building blocks for constructing n-type organic semiconductors. Driven by the attractive properties of imide-functionalized dithienylbenzodiimide (TBDI) and the promising device performance of TBDI-based polymers, a novel acceptor with increased electron affinity, fluorinated dithienylbenzodiimide (TFBDI), was designed with the hydrogen replaced by fluorine on the benzene core, and the synthetic challenges associated with this highly electron-deficient fluorinated imide building block are successfully overcome. TFBDI showed suppressed frontier molecular orbital energy levels as compared with TBDI. Copolymerizing this new electron-withdrawing TBDI with various donor co-units afforded a series of n-type polymer semiconductors TFBDI-T, TFBDI-Se, and TFBDI-BSe. All these TFBDI-based polymers exhibited a lower-lying lowest unoccupied molecular orbital (LUMO) energy level than the polymer analogue without fluorine. When applied in organic thin-film transistors, three polymers showed unipolar electron transport with large on-current/off-current ratios (Ion/Ioff) of 105-107. Among them, the selenophene-based polymer TFBDI-Se with the deepest-positioned LUMO and optimal chain stacking exhibited the highest electron mobility of 0.30 cm2 V-1 s-1. This result demonstrates that the new TFBDI is a highly attractive electron-deficient unit for enabling n-type polymer semiconductors, and the fluorination of imide-functionalized arenes offers an effective approach to develop more electron-deficient building blocks in organic electronics.",
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AU - Zhang, Xianhe

AU - Wu, Ziang

AU - Shi, Yongqiang

AU - Su, Mengyao

AU - Yang, Kun

AU - Wang, Yang

AU - Sun, Huiliang

AU - Min, Jie

AU - Zhang, Yujie

AU - Cheng, Xing

AU - Woo, Han Young

AU - Guo, Xugang

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AB - Imide functionalization is one of the most effective approaches to develop electron-deficient building blocks for constructing n-type organic semiconductors. Driven by the attractive properties of imide-functionalized dithienylbenzodiimide (TBDI) and the promising device performance of TBDI-based polymers, a novel acceptor with increased electron affinity, fluorinated dithienylbenzodiimide (TFBDI), was designed with the hydrogen replaced by fluorine on the benzene core, and the synthetic challenges associated with this highly electron-deficient fluorinated imide building block are successfully overcome. TFBDI showed suppressed frontier molecular orbital energy levels as compared with TBDI. Copolymerizing this new electron-withdrawing TBDI with various donor co-units afforded a series of n-type polymer semiconductors TFBDI-T, TFBDI-Se, and TFBDI-BSe. All these TFBDI-based polymers exhibited a lower-lying lowest unoccupied molecular orbital (LUMO) energy level than the polymer analogue without fluorine. When applied in organic thin-film transistors, three polymers showed unipolar electron transport with large on-current/off-current ratios (Ion/Ioff) of 105-107. Among them, the selenophene-based polymer TFBDI-Se with the deepest-positioned LUMO and optimal chain stacking exhibited the highest electron mobility of 0.30 cm2 V-1 s-1. This result demonstrates that the new TFBDI is a highly attractive electron-deficient unit for enabling n-type polymer semiconductors, and the fluorination of imide-functionalized arenes offers an effective approach to develop more electron-deficient building blocks in organic electronics.

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