Cyano-substituted benzochalcogenadiazole-based polymer semiconductors for balanced ambipolar organic thin-film transistors

Shengbin Shi, Hang Wang, Peng Chen, Mohammad Afsar Uddin, Yuxi Wang, Yumin Tang, Han Guo, Xing Cheng, Shiming Zhang, Han Young Woo, Xugang Guo

Research output: Contribution to journalArticlepeer-review

21 Citations (Scopus)


Due to their high-lying lowest unoccupied molecular orbitals (LUMOs), π-conjugated polymers based on benzothiadiazole and its derivatives typically are p-type. We report here the successful development of two narrow bandgap, ambipolar donor-acceptor copolymers, PDCNBT2T and PDCNBSe2T, which are based on new cyano-substituted strong electron acceptors, 4,7-dibromo-5,6-dicyano-2,1,3-benzothiadiazole (DCNBT) and 4,7-dibromo-5,6-dicyano-2,1,3-benzoselenadiazole (DCNBSe), respectively. Compared to their polymer analogues with fluorine substituents, the LUMO was lowered by a big margin of ca. 0.6 eV and the bandgap was reduced by 0.2-0.3 eV for the cyano-substituted polymers. Therefore, the cyano-substituted benzothiadiazole polymers showed very low-lying LUMO levels of ca. 4.3 eV. Benefiting from their narrow bandgaps of 1.1-1.2 eV and appropriately positioned LUMO levels, both polymers exhibit well balanced ambipolar transport characteristics in organic thin-film transistors, which differ from the p-type dominating transport properties of their fluorinated polymer analogues. A balanced hole/electron mobility of 0.59/0.47 cm2 V-1 s-1 was achieved for polymer PDCNBT2T, and a reduced hole/electron mobility of 0.018/0.014 cm2 V-1 s-1 was observed for the benzoselenadiazole-based PDCNBSe2T due to its lower crystallinity. These results show that the electron mobility can be enhanced by approximately two orders versus the electron mobility of the previously reported 4,7-di(thiophen-2-yl)-5,6-dicyano-2,1,3-benzothiadiazole-based polymer. This improvement was achieved by using the new acceptor units without additional electron-rich thiophene flanks, which allow a higher degree of freedom in selecting the donor co-unit and more effective tuning of energy levels of frontier molecular orbitals.

Original languageEnglish
Pages (from-to)3873-3884
Number of pages12
JournalPolymer Chemistry
Issue number28
Publication statusPublished - 2018 Jul 28

ASJC Scopus subject areas

  • Bioengineering
  • Biochemistry
  • Polymers and Plastics
  • Organic Chemistry


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