Anthracenedicarboximide-based semiconductors for air-stable, n-channel organic thin-film transistors: Materials design, synthesis, and structural characterization

Hakan Usta, Choongik Kim, Zhiming Wang, Shaofeng Lu, Hui Huang, Antonio Facchetti, Tobin J. Marks

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44 Citations (Scopus)

Abstract

A family of six n-channel organic semiconductors (1-6) based on the N,N'-dialkyl-2,3:6,7-anthracenedicarboximide (ADI) core was synthesized and characterized. These new semiconductors are functionalized with n-octyl (-n-C 8H 17), 1H,1H-perfluorobutyl (-n-CH 2C 3F 7), cyano (-CN), and bromo (-Br) substituents, which results in wide HOMO and LUMO energy variations (∼1 eV) but negligible optical absorbance (λ max = 418-436 nm) in the visible region of the solar spectrum. Organic thin-film transistors (OTFTs) were fabricated via semiconductor vapor-deposition, and the resulting devices exhibit exclusively electron transport with good carrier mobilities (μ e) of 10 -3 to 0.06 cm 2 V -1 s -1. Within this semiconductor family, cyano core-substitution plays a critical role in properly tuning the LUMO energy to enable good electron transport in ambient conditions while maintaining a low level of ambient doping (i.e., low I off). Core-cyanated ADIs 3 and 6 exhibit air-stable TFT device operation with electron mobilities up to 0.04 cm 2 V -1 s -1 in air. Very high current on/off ratios of >10 7 are measured with positive threshold voltages (V th = 5-15 V) and low off currents (I off = 10 -9 to 10 -12 A). Single-crystal structures of N,N'-1H,1H-perfluorobutyl ADIs 5 and 6 exhibit slipped-stack cofacial crystal packing with close π-π stacking distances of ∼3.2 Å. Additionally, close intermolecular interactions between imide-carbonyl oxygen and anthracene core-hydrogen are identified, which lead to the assembly of highly planar lamellar layers. Analysis of the air-stability of 1-6 thin films suggests that air-stability is mainly controlled by the LUMO energetics, and an electrochemical threshold of E red1 = -0.3 to -0.4 V is estimated to stabilize n-channel transport in this family of materials.

Original languageEnglish
Pages (from-to)4459-4472
Number of pages14
JournalJournal of Materials Chemistry
Volume22
Issue number10
DOIs
Publication statusPublished - Mar 14 2012

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ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Chemistry

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