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 language | English |
|---|---|
| Pages (from-to) | 4459-4472 |
| Number of pages | 14 |
| Journal | Journal of Materials Chemistry |
| Volume | 22 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - Mar 14 2012 |
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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 journal › Article
}
TY - JOUR
T1 - Anthracenedicarboximide-based semiconductors for air-stable, n-channel organic thin-film transistors
T2 - Materials design, synthesis, and structural characterization
AU - Usta, Hakan
AU - Kim, Choongik
AU - Wang, Zhiming
AU - Lu, Shaofeng
AU - Huang, Hui
AU - Facchetti, Antonio
AU - Marks, Tobin J
PY - 2012/3/14
Y1 - 2012/3/14
N2 - 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.
AB - 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.
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U2 - 10.1039/c1jm14713g
DO - 10.1039/c1jm14713g
M3 - Article
VL - 22
SP - 4459
EP - 4472
JO - Journal of Materials Chemistry
JF - Journal of Materials Chemistry
SN - 0959-9428
IS - 10
ER -