Synthesis, Molecular Packing, and Electrical Properties of New Regioisomeric n-type Semiconducting Molecules with Modification of Alkyl Substituents Position

Hwa Sook Ryu, Min Je Kim, Young Woong Lee, Seung Hun Lee, Tae Joo Shin, Jeong Ho Cho, Han Young Woo

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4 Citations (Scopus)

Abstract

We design and synthesize a series of regioisomeric n-type small molecules, which have an identical diketopyrrolopyrrole (DPP) core and 2-(2,3-dihydro-3-oxo-1H-inden-1-ylidene)propanedinitrile (INCN) terminal groups with octyl substituents at different positions. The isomeric structures are confirmed by two-dimensional NMR spectroscopy based on the heteronuclear multiple-bond coupling method. Incorporation of the electron-deficient DPP and strongly electron-withdrawing INCN groups yields deep frontier molecular orbitals with n-type charge-transport properties in solution-processed organic field-effect transistors (OFETs). Interestingly, a minor change in the substitution position of the octyl side chains significantly influences the optoelectronic and morphological properties of the thin film. The polycrystalline morphology of the as-cast films is reorganized differently with thermal annealing depending on the octyl topology, significantly affecting the OFET performance. With thermal treatment at 200 °C, the kinked DPP(EH)-INCNO1 (EH = 2-ethylhexyl) structures transform into single crystalline-like structures, exhibiting a remarkably improved electron mobility up to ∼0.6 cm2V-1 s-1 compared with DPP(EH)-INCNO2 isomers. The more linear DPP(EH or HD)-INCNO2 (HD = 2-hexyldecyl) molecules become more crystalline with thermal treatments, but their polycrystalline packing structures with large grain boundaries are the main reason for their lower electron mobility. When the solubilizing alkyl substituents are selected, careful molecular design is needed, with consideration of both the solubility and intermolecular packing, for optimizing the optoelectronic properties.

Original languageEnglish
Pages (from-to)47170-47181
Number of pages12
JournalACS Applied Materials and Interfaces
Volume11
Issue number50
DOIs
Publication statusPublished - 2019 Dec 18

Bibliographical note

Funding Information:
H.S.R. and M.J.K. contributed equally to this work. This work was supported by the National Research Foundation (NRF) of Korea (Grant Nos. NRF-2019R1A2C2085290, 2017K2A9A2A12000315, 2019R1A6A1A11044070, and 2018R1A5A1025224). Experiments at the PLS-II 9A and 6D UNIST PAL beamline were supported in part by MSIT, POSTECH, and UNIST.

Publisher Copyright:
© 2019 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Materials Science(all)

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