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

doi:10.1021/jacs.9b09367

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

37 Citations (Scopus)

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 language	English
Pages (from-to)	18806-18813
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	141
Issue number	47
DOIs	https://doi.org/10.1021/jacs.9b09367
Publication status	Published - 27 Nov 2019

Bibliographical note

Funding Information:
The authors thank KAUST and BASF for financial support and acknowledge EC FP7 Project SC2 (610115), EC H2020 (643791), and Engineering and Physical Sciences Research Council (EPSRC) Projects EP/G037515/1 and EP/M005143/1. M.N. and H.S. acknowledge financial support from the EPSRC though a Programme Grant (EP/M005141/1). G.C. acknowledges financial support from the University of Warwick. A.S. and C.C. gratefully acknowledge financial support from the National Science Foundation, Division of Materials Research, Award No. 1808401. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515. The transient microwave conductivity work was funded from the through the Solar Photochemistry Program of Office of Basic Energy Sciences. This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy under Contract No. DE-AC36-08GO28308.

Publisher Copyright:
Copyright © 2019 American Chemical Society.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.9b09367

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Chen, H., Wadsworth, A., Ma, C., Nanni, A., Zhang, W., Nikolka, M., Luci, A. M. T., Perdigão, L. M. A., Thorley, K. J., Cendra, C., Larson, B., Rumbles, G., Anthopoulos, T. D., 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, 141(47), 18806-18813. https://doi.org/10.1021/jacs.9b09367

@article{4cbd6e80dd0544f4af1faf4267838c5d,

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",

note = "Funding Information: The authors thank KAUST and BASF for financial support and acknowledge EC FP7 Project SC2 (610115), EC H2020 (643791), and Engineering and Physical Sciences Research Council (EPSRC) Projects EP/G037515/1 and EP/M005143/1. M.N. and H.S. acknowledge financial support from the EPSRC though a Programme Grant (EP/M005141/1). G.C. acknowledges financial support from the University of Warwick. A.S. and C.C. gratefully acknowledge financial support from the National Science Foundation, Division of Materials Research, Award No. 1808401. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515. The transient microwave conductivity work was funded from the through the Solar Photochemistry Program of Office of Basic Energy Sciences. This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy under Contract No. DE-AC36-08GO28308. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = nov,

day = "27",

doi = "10.1021/jacs.9b09367",

language = "English",

volume = "141",

pages = "18806--18813",

journal = "Journal of the American Chemical Society",

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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, vol. 141, no. 47, pp. 18806-18813. https://doi.org/10.1021/jacs.9b09367

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

N1 - Funding Information: The authors thank KAUST and BASF for financial support and acknowledge EC FP7 Project SC2 (610115), EC H2020 (643791), and Engineering and Physical Sciences Research Council (EPSRC) Projects EP/G037515/1 and EP/M005143/1. M.N. and H.S. acknowledge financial support from the EPSRC though a Programme Grant (EP/M005141/1). G.C. acknowledges financial support from the University of Warwick. A.S. and C.C. gratefully acknowledge financial support from the National Science Foundation, Division of Materials Research, Award No. 1808401. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515. The transient microwave conductivity work was funded from the through the Solar Photochemistry Program of Office of Basic Energy Sciences. This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy under Contract No. DE-AC36-08GO28308. Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/11/27

Y1 - 2019/11/27

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.

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

Abstract

Bibliographical note

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