The Effect of Ring Expansion in Thienobenzo[ b]indacenodithiophene Polymers for Organic Field-Effect Transistors

Hu Chen, Andrew Wadsworth, Chun Ma, Alice Nanni, Weimin Zhang, Mark Nikolka, Alexander M.T. Luci, Luís M.A. Perdigão, Karl J. Thorley, Camila Cendra, Bryon Larson, Garry Rumbles, Thomas D. Anthopoulos, Alberto Salleo, Giovanni Costantini, Henning Sirringhaus, Iain McCulloch

Research output: Contribution to journalArticle

Abstract

A fused donor, thienobenzo[b]indacenodithiophene (TBIDT), was designed and synthesized using a novel acid-promoted cascade ring closure strategy, and then copolymerized with a benzothiadiazole (BT) monomer. The backbone of TBIDT is an expansion of the well-known indacenodithiophene (IDT) unit and was expected to enhance the charge carrier mobility by improving backbone planarity and facilitating short contacts between polymer chains. However, the optimized field-effect transistors demonstrated an average saturation hole mobility of 0.9 cm2 V-1 s-1, lower than the performance of IDT-BT (∼1.5 cm2 V-1 s-1). Mobilities extracted from time-resolved microwave conductivity measurements were consistent with the trend in hole mobilities in organic field-effect transistor devices. Scanning tunneling microscopy measurements and computational modeling illustrated that TBIDT-BT exhibits a less ordered microstructure in comparison to IDT-BT. This reveals that a regular side-chain packing density, independent of conformational isomers, is critical to avoid local free volume due to irregular packing, which can host trapping impurities. DFT calculations indicated that TBIDT-BT, despite containing a larger, planar unit, showed less stabilization of planar backbone geometries in comparison to IDT-BT. This is due to the reduced electrostatic stabilizing interactions between the peripheral thiophene of the fused core and the BT unit, resulting in a reduction of the barrier to rotation around the single bond. These insights provide a greater understanding of the general structure-property relationships required for semiconducting polymer repeat units to ensure optimal backbone planarization, as illustrated with IDT-type units, guiding the design of novel semiconducting polymers with extended fused backbones for high-performance field-effect transistors.

Original languageEnglish
JournalJournal of the American Chemical Society
DOIs
Publication statusAccepted/In press - Jan 1 2019

Fingerprint

Semiconducting polymers
Organic field effect transistors
Hole mobility
Field effect transistors
Polymers
Carrier mobility
Free volume
Scanning tunneling microscopy
Thiophene
Charge carriers
Discrete Fourier transforms
Isomers
Electrostatics
Stabilization
Monomers
Microwaves
Impurities
Microstructure
Acids
Geometry

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

The Effect of Ring Expansion in Thienobenzo[ b]indacenodithiophene Polymers for Organic Field-Effect Transistors. / Chen, Hu; Wadsworth, Andrew; Ma, Chun; Nanni, Alice; Zhang, Weimin; Nikolka, Mark; Luci, Alexander M.T.; Perdigão, Luís M.A.; Thorley, Karl J.; Cendra, Camila; Larson, Bryon; Rumbles, Garry; Anthopoulos, Thomas D.; Salleo, Alberto; Costantini, Giovanni; Sirringhaus, Henning; McCulloch, Iain.

In: Journal of the American Chemical Society, 01.01.2019.

Research output: Contribution to journalArticle

Chen, H, Wadsworth, A, Ma, C, Nanni, A, Zhang, W, Nikolka, M, Luci, AMT, Perdigão, LMA, Thorley, KJ, Cendra, C, Larson, B, Rumbles, G, Anthopoulos, TD, Salleo, A, Costantini, G, Sirringhaus, H & McCulloch, I 2019, 'The Effect of Ring Expansion in Thienobenzo[ b]indacenodithiophene Polymers for Organic Field-Effect Transistors', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b09367
Chen, Hu ; Wadsworth, Andrew ; Ma, Chun ; Nanni, Alice ; Zhang, Weimin ; Nikolka, Mark ; Luci, Alexander M.T. ; Perdigão, Luís M.A. ; Thorley, Karl J. ; Cendra, Camila ; Larson, Bryon ; Rumbles, Garry ; Anthopoulos, Thomas D. ; Salleo, Alberto ; Costantini, Giovanni ; Sirringhaus, Henning ; McCulloch, Iain. / The Effect of Ring Expansion in Thienobenzo[ b]indacenodithiophene Polymers for Organic Field-Effect Transistors. In: Journal of the American Chemical Society. 2019.
@article{814f8b93edaa4f188214c5cabc582d1f,
title = "The Effect of Ring Expansion in Thienobenzo[ b]indacenodithiophene Polymers for Organic Field-Effect Transistors",
abstract = "A fused donor, thienobenzo[b]indacenodithiophene (TBIDT), was designed and synthesized using a novel acid-promoted cascade ring closure strategy, and then copolymerized with a benzothiadiazole (BT) monomer. The backbone of TBIDT is an expansion of the well-known indacenodithiophene (IDT) unit and was expected to enhance the charge carrier mobility by improving backbone planarity and facilitating short contacts between polymer chains. However, the optimized field-effect transistors demonstrated an average saturation hole mobility of 0.9 cm2 V-1 s-1, lower than the performance of IDT-BT (∼1.5 cm2 V-1 s-1). Mobilities extracted from time-resolved microwave conductivity measurements were consistent with the trend in hole mobilities in organic field-effect transistor devices. Scanning tunneling microscopy measurements and computational modeling illustrated that TBIDT-BT exhibits a less ordered microstructure in comparison to IDT-BT. This reveals that a regular side-chain packing density, independent of conformational isomers, is critical to avoid local free volume due to irregular packing, which can host trapping impurities. DFT calculations indicated that TBIDT-BT, despite containing a larger, planar unit, showed less stabilization of planar backbone geometries in comparison to IDT-BT. This is due to the reduced electrostatic stabilizing interactions between the peripheral thiophene of the fused core and the BT unit, resulting in a reduction of the barrier to rotation around the single bond. These insights provide a greater understanding of the general structure-property relationships required for semiconducting polymer repeat units to ensure optimal backbone planarization, as illustrated with IDT-type units, guiding the design of novel semiconducting polymers with extended fused backbones for high-performance field-effect transistors.",
author = "Hu Chen and Andrew Wadsworth and Chun Ma and Alice Nanni and Weimin Zhang and Mark Nikolka and Luci, {Alexander M.T.} and Perdig{\~a}o, {Lu{\'i}s M.A.} and Thorley, {Karl J.} and Camila Cendra and Bryon Larson and Garry Rumbles and Anthopoulos, {Thomas D.} and Alberto Salleo and Giovanni Costantini and Henning Sirringhaus and Iain McCulloch",
year = "2019",
month = "1",
day = "1",
doi = "10.1021/jacs.9b09367",
language = "English",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - The Effect of Ring Expansion in Thienobenzo[ b]indacenodithiophene Polymers for Organic Field-Effect Transistors

AU - Chen, Hu

AU - Wadsworth, Andrew

AU - Ma, Chun

AU - Nanni, Alice

AU - Zhang, Weimin

AU - Nikolka, Mark

AU - Luci, Alexander M.T.

AU - Perdigão, Luís M.A.

AU - Thorley, Karl J.

AU - Cendra, Camila

AU - Larson, Bryon

AU - Rumbles, Garry

AU - Anthopoulos, Thomas D.

AU - Salleo, Alberto

AU - Costantini, Giovanni

AU - Sirringhaus, Henning

AU - McCulloch, Iain

PY - 2019/1/1

Y1 - 2019/1/1

N2 - A fused donor, thienobenzo[b]indacenodithiophene (TBIDT), was designed and synthesized using a novel acid-promoted cascade ring closure strategy, and then copolymerized with a benzothiadiazole (BT) monomer. The backbone of TBIDT is an expansion of the well-known indacenodithiophene (IDT) unit and was expected to enhance the charge carrier mobility by improving backbone planarity and facilitating short contacts between polymer chains. However, the optimized field-effect transistors demonstrated an average saturation hole mobility of 0.9 cm2 V-1 s-1, lower than the performance of IDT-BT (∼1.5 cm2 V-1 s-1). Mobilities extracted from time-resolved microwave conductivity measurements were consistent with the trend in hole mobilities in organic field-effect transistor devices. Scanning tunneling microscopy measurements and computational modeling illustrated that TBIDT-BT exhibits a less ordered microstructure in comparison to IDT-BT. This reveals that a regular side-chain packing density, independent of conformational isomers, is critical to avoid local free volume due to irregular packing, which can host trapping impurities. DFT calculations indicated that TBIDT-BT, despite containing a larger, planar unit, showed less stabilization of planar backbone geometries in comparison to IDT-BT. This is due to the reduced electrostatic stabilizing interactions between the peripheral thiophene of the fused core and the BT unit, resulting in a reduction of the barrier to rotation around the single bond. These insights provide a greater understanding of the general structure-property relationships required for semiconducting polymer repeat units to ensure optimal backbone planarization, as illustrated with IDT-type units, guiding the design of novel semiconducting polymers with extended fused backbones for high-performance field-effect transistors.

AB - A fused donor, thienobenzo[b]indacenodithiophene (TBIDT), was designed and synthesized using a novel acid-promoted cascade ring closure strategy, and then copolymerized with a benzothiadiazole (BT) monomer. The backbone of TBIDT is an expansion of the well-known indacenodithiophene (IDT) unit and was expected to enhance the charge carrier mobility by improving backbone planarity and facilitating short contacts between polymer chains. However, the optimized field-effect transistors demonstrated an average saturation hole mobility of 0.9 cm2 V-1 s-1, lower than the performance of IDT-BT (∼1.5 cm2 V-1 s-1). Mobilities extracted from time-resolved microwave conductivity measurements were consistent with the trend in hole mobilities in organic field-effect transistor devices. Scanning tunneling microscopy measurements and computational modeling illustrated that TBIDT-BT exhibits a less ordered microstructure in comparison to IDT-BT. This reveals that a regular side-chain packing density, independent of conformational isomers, is critical to avoid local free volume due to irregular packing, which can host trapping impurities. DFT calculations indicated that TBIDT-BT, despite containing a larger, planar unit, showed less stabilization of planar backbone geometries in comparison to IDT-BT. This is due to the reduced electrostatic stabilizing interactions between the peripheral thiophene of the fused core and the BT unit, resulting in a reduction of the barrier to rotation around the single bond. These insights provide a greater understanding of the general structure-property relationships required for semiconducting polymer repeat units to ensure optimal backbone planarization, as illustrated with IDT-type units, guiding the design of novel semiconducting polymers with extended fused backbones for high-performance field-effect transistors.

UR - http://www.scopus.com/inward/record.url?scp=85075440490&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85075440490&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b09367

DO - 10.1021/jacs.9b09367

M3 - Article

C2 - 31613619

AN - SCOPUS:85075440490

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

ER -