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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 themore » 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.« less

Authors:
 [1]; ORCiD logo [2];  [1];  [1];  [1];  [3];  [4];  [4];  [2];  [5];  [6]; ORCiD logo [6]; ORCiD logo [1];  [5]; ORCiD logo [4];  [3]; ORCiD logo [7]
+ Show Author Affiliations
  1. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)
  2. Imperial College London (United Kingdom)
  3. Univ. of Cambridge (United Kingdom)
  4. Univ. of Warwick, Coventry (United Kingdom)
  5. Stanford Univ. CA (United States)
  6. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  7. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia); Imperial College London (United Kingdom)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Solar Photochemistry Program; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1579641
Alternate Identifier(s):
OSTI ID: 1596274
Report Number(s):
NREL/JA-5F00-74867
Journal ID: ISSN 0002-7863; TRN: US2102236
Grant/Contract Number:  
AC36-08GO28308; AC02-76SF00515; EP/G037515/1; EP/M005143/1; EP/M005141/1; 643791; 610115; 1808401
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 47; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; singlet fission; microwave conductivity; triplet state dissociation; Marcus inverted region

Citation Formats

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, and McCulloch, Iain. The Effect of Ring Expansion in Thienobenzo[b]indacenodithiophene Polymers for Organic Field-Effect Transistors. United States: N. p., 2019. Web. doi:10.1021/jacs.9b09367.
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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. United States. https://doi.org/10.1021/jacs.9b09367
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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, and McCulloch, Iain. Tue . "The Effect of Ring Expansion in Thienobenzo[b]indacenodithiophene Polymers for Organic Field-Effect Transistors". United States. https://doi.org/10.1021/jacs.9b09367. https://www.osti.gov/servlets/purl/1579641.
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@article{osti_1579641,
title = {The Effect of Ring Expansion in Thienobenzo[b]indacenodithiophene Polymers for Organic Field-Effect Transistors},
author = {Chen, Hu and Wadsworth, Andrew and Ma, Chun and Nanni, Alice and Zhang, Weimin and Nikolka, Mark and Luci, Alexander M. T. and Perdigão, Luís M. A. and Thorley, Karl J. and Cendra, Camila and Larson, Bryon and Rumbles, Garry and Anthopoulos, Thomas D. and Salleo, Alberto and Costantini, Giovanni and Sirringhaus, Henning and McCulloch, Iain},
abstractNote = {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.},
doi = {10.1021/jacs.9b09367},
journal = {Journal of the American Chemical Society},
number = 47,
volume = 141,
place = {United States},
year = {Tue Oct 15 00:00:00 EDT 2019},
month = {Tue Oct 15 00:00:00 EDT 2019}
}
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Journal Article:
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https://doi.org/10.1021/jacs.9b09367
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Cited by: 27 works
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Figures / Tables:

Scheme 1 Scheme 1: Synthetic Transformation of IDT to TBIDT
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    The impact of [1,2,5]chalcogenazolo[3,4‐ f ]‐benzo[1,2,3]triazole structure on the optoelectronic properties of conjugated polymers
    journal, April 2020

    • Alkan, Ecem Aydan; Goker, Seza; Sarigul, Hatice
    • Journal of Polymer Science, Vol. 58, Issue 7
    • DOI: 10.1002/pol.20190275
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