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

Research output: Contribution to journalArticle

41 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

Fingerprint

Thin film transistors
Semiconductor materials
Air
Imides
Vapor deposition
Semiconducting organic compounds
Anthracene
Electron mobility
Carrier mobility
Threshold voltage
Hydrogen
Substitution reactions
Tuning
Crystal structure
Doping (additives)
Single crystals
Oxygen
Thin films
Crystals
Electron Transport

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemistry(all)

Cite this

Anthracenedicarboximide-based semiconductors for air-stable, n-channel organic thin-film transistors : Materials design, synthesis, and structural characterization. / Usta, Hakan; Kim, Choongik; Wang, Zhiming; Lu, Shaofeng; Huang, Hui; Facchetti, Antonio; Marks, Tobin J.

In: Journal of Materials Chemistry, Vol. 22, No. 10, 14.03.2012, p. 4459-4472.

Research output: Contribution to journalArticle

Usta, Hakan ; Kim, Choongik ; Wang, Zhiming ; Lu, Shaofeng ; Huang, Hui ; Facchetti, Antonio ; Marks, Tobin J. / Anthracenedicarboximide-based semiconductors for air-stable, n-channel organic thin-film transistors : Materials design, synthesis, and structural characterization. In: Journal of Materials Chemistry. 2012 ; Vol. 22, No. 10. pp. 4459-4472.
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