Abstract
Inspired by the excellent device performance of imide-functionalized polymer semiconductors in organic electronics, a novel imide-based building block, dithienylbenzodiimide (TBDI), with fused backbone is designed and synthesized. Single-crystal structure analysis reveals that the TBDI unit features non-planar backbone conformation but with a tight π-stacking distance of 3.36 Å. By copolymerizing with various electron-rich co-units, a series of TBDI-based polymer semiconductors is synthesized and the optoelectronic, thermal, electrochemical and charge transport properties of the semiconductors are characterized. Attributed to the non-planar backbone and intrinsic electrical property of TBDI, all polymers exhibit wide bandgaps (∼2.0 eV) with low-lying HOMOs (<-5.5 eV). Organic thin-film transistors are fabricated by incorporating the TBDI-based polymers as the active layer to investigate their charge transport properties. The dithienylbenzodiimide-bithiophene copolymer shows ambipolar transport characteristics with an electron and hole mobility of 0.15 and 0.015 cm2 V-1 s-1, respectively. By incorporating weaker electron donor co-units, the dithienylbenzodiimide-thiophene and dithienylbenzodiimide-difluorobithiophene copolymers exhibit unipolar n-channel transistor performance with electron mobility up to 0.11 and 0.34 cm2 V-1 s-1, respectively. Most high-performance n-channel polymer semiconductors reported to date typically show narrow bandgaps with high-lying HOMOs, resulting in substantial p-channel performance. The new TBDI-based wide bandgap polymers with low-lying HOMOs greatly suppress p-channel performance and lead to improved Ion/Ioff ratios. The excellent n-channel performance is attributed to the strong electron-withdrawing capability of imide groups, low-lying frontier molecular orbitals, compact π-stacking distance, and a high degree of film crystallinity as confirmed by GIWAXS analysis with distinct interlamellar and π-stacking diffraction patterns. The result reveals that a building block with non-planar backbone can be utilized for constructing high crystalline polymer semiconductors with substantial charge carrier mobility. The study indicates that dithienylbenzodiimide is a promising unit for synthesizing wide bandgap polymeric semiconductors with unipolar n-channel performance.
| Original language | English |
|---|---|
| Pages (from-to) | 9559-9569 |
| Number of pages | 11 |
| Journal | Journal of Materials Chemistry C |
| Volume | 5 |
| Issue number | 37 |
| DOIs | |
| Publication status | Published - Jan 1 2017 |
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ASJC Scopus subject areas
- Chemistry(all)
- Materials Chemistry
Cite this
Dithienylbenzodiimide : A new electron-deficient unit for n-type polymer semiconductors. / Chen, Jianhua; Zhang, Xianhe; Wang, Gang; Uddin, Mohammad Afsar; Tang, Yumin; Wang, Yulun; Liao, Qiaogan; Facchetti, Antonio; Marks, Tobin J; Guo, Xugang.
In: Journal of Materials Chemistry C, Vol. 5, No. 37, 01.01.2017, p. 9559-9569.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Dithienylbenzodiimide
T2 - A new electron-deficient unit for n-type polymer semiconductors
AU - Chen, Jianhua
AU - Zhang, Xianhe
AU - Wang, Gang
AU - Uddin, Mohammad Afsar
AU - Tang, Yumin
AU - Wang, Yulun
AU - Liao, Qiaogan
AU - Facchetti, Antonio
AU - Marks, Tobin J
AU - Guo, Xugang
PY - 2017/1/1
Y1 - 2017/1/1
N2 - Inspired by the excellent device performance of imide-functionalized polymer semiconductors in organic electronics, a novel imide-based building block, dithienylbenzodiimide (TBDI), with fused backbone is designed and synthesized. Single-crystal structure analysis reveals that the TBDI unit features non-planar backbone conformation but with a tight π-stacking distance of 3.36 Å. By copolymerizing with various electron-rich co-units, a series of TBDI-based polymer semiconductors is synthesized and the optoelectronic, thermal, electrochemical and charge transport properties of the semiconductors are characterized. Attributed to the non-planar backbone and intrinsic electrical property of TBDI, all polymers exhibit wide bandgaps (∼2.0 eV) with low-lying HOMOs (<-5.5 eV). Organic thin-film transistors are fabricated by incorporating the TBDI-based polymers as the active layer to investigate their charge transport properties. The dithienylbenzodiimide-bithiophene copolymer shows ambipolar transport characteristics with an electron and hole mobility of 0.15 and 0.015 cm2 V-1 s-1, respectively. By incorporating weaker electron donor co-units, the dithienylbenzodiimide-thiophene and dithienylbenzodiimide-difluorobithiophene copolymers exhibit unipolar n-channel transistor performance with electron mobility up to 0.11 and 0.34 cm2 V-1 s-1, respectively. Most high-performance n-channel polymer semiconductors reported to date typically show narrow bandgaps with high-lying HOMOs, resulting in substantial p-channel performance. The new TBDI-based wide bandgap polymers with low-lying HOMOs greatly suppress p-channel performance and lead to improved Ion/Ioff ratios. The excellent n-channel performance is attributed to the strong electron-withdrawing capability of imide groups, low-lying frontier molecular orbitals, compact π-stacking distance, and a high degree of film crystallinity as confirmed by GIWAXS analysis with distinct interlamellar and π-stacking diffraction patterns. The result reveals that a building block with non-planar backbone can be utilized for constructing high crystalline polymer semiconductors with substantial charge carrier mobility. The study indicates that dithienylbenzodiimide is a promising unit for synthesizing wide bandgap polymeric semiconductors with unipolar n-channel performance.
AB - Inspired by the excellent device performance of imide-functionalized polymer semiconductors in organic electronics, a novel imide-based building block, dithienylbenzodiimide (TBDI), with fused backbone is designed and synthesized. Single-crystal structure analysis reveals that the TBDI unit features non-planar backbone conformation but with a tight π-stacking distance of 3.36 Å. By copolymerizing with various electron-rich co-units, a series of TBDI-based polymer semiconductors is synthesized and the optoelectronic, thermal, electrochemical and charge transport properties of the semiconductors are characterized. Attributed to the non-planar backbone and intrinsic electrical property of TBDI, all polymers exhibit wide bandgaps (∼2.0 eV) with low-lying HOMOs (<-5.5 eV). Organic thin-film transistors are fabricated by incorporating the TBDI-based polymers as the active layer to investigate their charge transport properties. The dithienylbenzodiimide-bithiophene copolymer shows ambipolar transport characteristics with an electron and hole mobility of 0.15 and 0.015 cm2 V-1 s-1, respectively. By incorporating weaker electron donor co-units, the dithienylbenzodiimide-thiophene and dithienylbenzodiimide-difluorobithiophene copolymers exhibit unipolar n-channel transistor performance with electron mobility up to 0.11 and 0.34 cm2 V-1 s-1, respectively. Most high-performance n-channel polymer semiconductors reported to date typically show narrow bandgaps with high-lying HOMOs, resulting in substantial p-channel performance. The new TBDI-based wide bandgap polymers with low-lying HOMOs greatly suppress p-channel performance and lead to improved Ion/Ioff ratios. The excellent n-channel performance is attributed to the strong electron-withdrawing capability of imide groups, low-lying frontier molecular orbitals, compact π-stacking distance, and a high degree of film crystallinity as confirmed by GIWAXS analysis with distinct interlamellar and π-stacking diffraction patterns. The result reveals that a building block with non-planar backbone can be utilized for constructing high crystalline polymer semiconductors with substantial charge carrier mobility. The study indicates that dithienylbenzodiimide is a promising unit for synthesizing wide bandgap polymeric semiconductors with unipolar n-channel performance.
UR - http://www.scopus.com/inward/record.url?scp=85030242710&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85030242710&partnerID=8YFLogxK
U2 - 10.1039/c7tc02903a
DO - 10.1039/c7tc02903a
M3 - Article
AN - SCOPUS:85030242710
VL - 5
SP - 9559
EP - 9569
JO - Journal of Materials Chemistry C
JF - Journal of Materials Chemistry C
SN - 2050-7526
IS - 37
ER -