Regiochemistry-Driven Organic Electrochemical Transistor Performance Enhancement in Ethylene Glycol-Functionalized Polythiophenes

Rawad K. Hallani; Bryan D. Paulsen; Anthony J. Petty; Rajendar Sheelamanthula; Maximilian Moser; Karl J. Thorley; Wonil Sohn; Reem B. Rashid; Achilleas Savva; Stefania Moro; Joseph P. Parker; Oscar Drury; Maryam Alsufyani; Marios Neophytou; Jan Kosco; Sahika Inal; Giovanni Costantini; Jonathan Rivnay; Iain McCulloch

doi:10.1021/jacs.1c03516

Regiochemistry-Driven Organic Electrochemical Transistor Performance Enhancement in Ethylene Glycol-Functionalized Polythiophenes

Rawad K. Hallani, Bryan D. Paulsen, Anthony J. Petty, Rajendar Sheelamanthula, Maximilian Moser, Karl J. Thorley, Wonil Sohn, Reem B. Rashid, Achilleas Savva, Stefania Moro, Joseph P. Parker, Oscar Drury, Maryam Alsufyani, Marios Neophytou, Jan Kosco, Sahika Inal, Giovanni Costantini, Jonathan Rivnay, Iain McCulloch^*

^*Corresponding author for this work

Chemistry

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

51 Citations (Scopus)

Abstract

Novel p-type semiconducting polymers that can facilitate ion penetration, and operate in accumulation mode are much desired in bioelectronics. Glycol side chains have proven to be an efficient method to increase bulk electrochemical doping and optimize aqueous swelling. One early polymer which exemplifies these design approaches was p(g2T-TT), employing a bithiophene-co-thienothiophene backbone with glycol side chains in the 3,3′ positions of the bithiophene repeat unit. In this paper, the analogous regioisomeric polymer, namely pgBTTT, was synthesized by relocating the glycol side chains position on the bithiophene unit of p(g2T-TT) from the 3,3′ to the 4,4′ positions and compared with the original p(g2T-TT). By changing the regio-positioning of the side chains, the planarizing effects of the S-O interactions were redistributed along the backbone, and the influence on the polymer's microstructure organization was investigated using grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The newly designed pgBTTT exhibited lower backbone disorder, closer π-stacking, and higher scattering intensity in both the in-plane and out-of-plane GIWAXS measurements. The effect of the improved planarity of pgBTTT manifested as higher hole mobility (μ) of 3.44 ± 0.13 cm² V^-1 s^-1. Scanning tunneling microscopy (STM) was in agreement with the GIWAXS measurements and demonstrated, for the first time, that glycol side chains can also facilitate intermolecular interdigitation analogous to that of pBTTT. Electrochemical quartz crystal microbalance with dissipation of energy (eQCM-D) measurements revealed that pgBTTT maintains a more rigid structure than p(g2T-TT) during doping, minimizing molecular packing disruption and maintaining higher hole mobility in operation mode.

Original language	English
Pages (from-to)	11007-11018
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	143
Issue number	29
Early online date	30 Jun 2021
DOIs	https://doi.org/10.1021/jacs.1c03516
Publication status	Published - 28 Jul 2021

Bibliographical note

Funding Information:
The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST), including Office of Sponsored Research (OSR) awards no. OSR-2018-CRG/CCF-3079, OSR-2019-CRG8-4086 and OSR-2018-CRG7-3749. We acknowledge funding from ERC Synergy Grant SC2 (610115), the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 952911, project BOOSTER and grant agreement no. 862474, project RoLA-FLEX, as well as EPSRC Project EP/T026219/1. B.D.P. and J.R. gratefully acknowledge support from the National Science Foundation grant no. NSF DMR-1751308. W.S. gratefully acknowledges support from the Northwestern University Office of Undergraduate Research. Special thanks to Joseph Strzalka and Qingteng Zhang for beamline assistance. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work made use of the Keck-II and NUFAB facilities of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). This work utilized Keck-II facility of Northwestern University’s NUANCE Center and Northwestern University Micro/Nano Fabrication Facility (NUFAB), which are both partially supported by Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (NSF DMR-1720139), the State of Illinois, and Northwestern University. Additionally, the Keck-II facility is partially supported by the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. S.M. acknowledges funding though an EU Chancellor’s Scholarship by the University of Warwick. J.P.P. acknowledges support by the Biotechnology and Biological Sciences Research Council (BBSRC) and University of Warwick funded Midlands Integrative Biosciences Training Partnership (MIBTP) (grant number BB/M01116X/1).

Publisher Copyright:
© 2021 American Chemical Society.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.1c03516

Cite this

Hallani, R. K., Paulsen, B. D., Petty, A. J., Sheelamanthula, R., Moser, M., Thorley, K. J., Sohn, W., Rashid, R. B., Savva, A., Moro, S., Parker, J. P., Drury, O., Alsufyani, M., Neophytou, M., Kosco, J., Inal, S., Costantini, G., Rivnay, J., & McCulloch, I. (2021). Regiochemistry-Driven Organic Electrochemical Transistor Performance Enhancement in Ethylene Glycol-Functionalized Polythiophenes. Journal of the American Chemical Society, 143(29), 11007-11018. https://doi.org/10.1021/jacs.1c03516

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title = "Regiochemistry-Driven Organic Electrochemical Transistor Performance Enhancement in Ethylene Glycol-Functionalized Polythiophenes",

abstract = "Novel p-type semiconducting polymers that can facilitate ion penetration, and operate in accumulation mode are much desired in bioelectronics. Glycol side chains have proven to be an efficient method to increase bulk electrochemical doping and optimize aqueous swelling. One early polymer which exemplifies these design approaches was p(g2T-TT), employing a bithiophene-co-thienothiophene backbone with glycol side chains in the 3,3′ positions of the bithiophene repeat unit. In this paper, the analogous regioisomeric polymer, namely pgBTTT, was synthesized by relocating the glycol side chains position on the bithiophene unit of p(g2T-TT) from the 3,3′ to the 4,4′ positions and compared with the original p(g2T-TT). By changing the regio-positioning of the side chains, the planarizing effects of the S-O interactions were redistributed along the backbone, and the influence on the polymer's microstructure organization was investigated using grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The newly designed pgBTTT exhibited lower backbone disorder, closer π-stacking, and higher scattering intensity in both the in-plane and out-of-plane GIWAXS measurements. The effect of the improved planarity of pgBTTT manifested as higher hole mobility (μ) of 3.44 ± 0.13 cm2 V-1 s-1. Scanning tunneling microscopy (STM) was in agreement with the GIWAXS measurements and demonstrated, for the first time, that glycol side chains can also facilitate intermolecular interdigitation analogous to that of pBTTT. Electrochemical quartz crystal microbalance with dissipation of energy (eQCM-D) measurements revealed that pgBTTT maintains a more rigid structure than p(g2T-TT) during doping, minimizing molecular packing disruption and maintaining higher hole mobility in operation mode.",

author = "Hallani, {Rawad K.} and Paulsen, {Bryan D.} and Petty, {Anthony J.} and Rajendar Sheelamanthula and Maximilian Moser and Thorley, {Karl J.} and Wonil Sohn and Rashid, {Reem B.} and Achilleas Savva and Stefania Moro and Parker, {Joseph P.} and Oscar Drury and Maryam Alsufyani and Marios Neophytou and Jan Kosco and Sahika Inal and Giovanni Costantini and Jonathan Rivnay and Iain McCulloch",

note = "Funding Information: The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST), including Office of Sponsored Research (OSR) awards no. OSR-2018-CRG/CCF-3079, OSR-2019-CRG8-4086 and OSR-2018-CRG7-3749. We acknowledge funding from ERC Synergy Grant SC2 (610115), the European Union{\textquoteright}s Horizon 2020 research and innovation programme under grant agreement no. 952911, project BOOSTER and grant agreement no. 862474, project RoLA-FLEX, as well as EPSRC Project EP/T026219/1. B.D.P. and J.R. gratefully acknowledge support from the National Science Foundation grant no. NSF DMR-1751308. W.S. gratefully acknowledges support from the Northwestern University Office of Undergraduate Research. Special thanks to Joseph Strzalka and Qingteng Zhang for beamline assistance. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work made use of the Keck-II and NUFAB facilities of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern{\textquoteright}s MRSEC program (NSF DMR-1720139). This work utilized Keck-II facility of Northwestern University{\textquoteright}s NUANCE Center and Northwestern University Micro/Nano Fabrication Facility (NUFAB), which are both partially supported by Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (NSF DMR-1720139), the State of Illinois, and Northwestern University. Additionally, the Keck-II facility is partially supported by the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. S.M. acknowledges funding though an EU Chancellor{\textquoteright}s Scholarship by the University of Warwick. J.P.P. acknowledges support by the Biotechnology and Biological Sciences Research Council (BBSRC) and University of Warwick funded Midlands Integrative Biosciences Training Partnership (MIBTP) (grant number BB/M01116X/1). Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = jul,

day = "28",

doi = "10.1021/jacs.1c03516",

language = "English",

volume = "143",

pages = "11007--11018",

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Hallani, RK, Paulsen, BD, Petty, AJ, Sheelamanthula, R, Moser, M, Thorley, KJ, Sohn, W, Rashid, RB, Savva, A, Moro, S, Parker, JP, Drury, O, Alsufyani, M, Neophytou, M, Kosco, J, Inal, S, Costantini, G, Rivnay, J & McCulloch, I 2021, 'Regiochemistry-Driven Organic Electrochemical Transistor Performance Enhancement in Ethylene Glycol-Functionalized Polythiophenes', Journal of the American Chemical Society, vol. 143, no. 29, pp. 11007-11018. https://doi.org/10.1021/jacs.1c03516

TY - JOUR

T1 - Regiochemistry-Driven Organic Electrochemical Transistor Performance Enhancement in Ethylene Glycol-Functionalized Polythiophenes

AU - Hallani, Rawad K.

AU - Paulsen, Bryan D.

AU - Petty, Anthony J.

AU - Sheelamanthula, Rajendar

AU - Moser, Maximilian

AU - Thorley, Karl J.

AU - Sohn, Wonil

AU - Rashid, Reem B.

AU - Savva, Achilleas

AU - Moro, Stefania

AU - Parker, Joseph P.

AU - Drury, Oscar

AU - Alsufyani, Maryam

AU - Neophytou, Marios

AU - Kosco, Jan

AU - Inal, Sahika

AU - Costantini, Giovanni

AU - Rivnay, Jonathan

AU - McCulloch, Iain

N1 - Funding Information: The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST), including Office of Sponsored Research (OSR) awards no. OSR-2018-CRG/CCF-3079, OSR-2019-CRG8-4086 and OSR-2018-CRG7-3749. We acknowledge funding from ERC Synergy Grant SC2 (610115), the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 952911, project BOOSTER and grant agreement no. 862474, project RoLA-FLEX, as well as EPSRC Project EP/T026219/1. B.D.P. and J.R. gratefully acknowledge support from the National Science Foundation grant no. NSF DMR-1751308. W.S. gratefully acknowledges support from the Northwestern University Office of Undergraduate Research. Special thanks to Joseph Strzalka and Qingteng Zhang for beamline assistance. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work made use of the Keck-II and NUFAB facilities of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). This work utilized Keck-II facility of Northwestern University’s NUANCE Center and Northwestern University Micro/Nano Fabrication Facility (NUFAB), which are both partially supported by Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (NSF DMR-1720139), the State of Illinois, and Northwestern University. Additionally, the Keck-II facility is partially supported by the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. S.M. acknowledges funding though an EU Chancellor’s Scholarship by the University of Warwick. J.P.P. acknowledges support by the Biotechnology and Biological Sciences Research Council (BBSRC) and University of Warwick funded Midlands Integrative Biosciences Training Partnership (MIBTP) (grant number BB/M01116X/1). Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/7/28

Y1 - 2021/7/28

N2 - Novel p-type semiconducting polymers that can facilitate ion penetration, and operate in accumulation mode are much desired in bioelectronics. Glycol side chains have proven to be an efficient method to increase bulk electrochemical doping and optimize aqueous swelling. One early polymer which exemplifies these design approaches was p(g2T-TT), employing a bithiophene-co-thienothiophene backbone with glycol side chains in the 3,3′ positions of the bithiophene repeat unit. In this paper, the analogous regioisomeric polymer, namely pgBTTT, was synthesized by relocating the glycol side chains position on the bithiophene unit of p(g2T-TT) from the 3,3′ to the 4,4′ positions and compared with the original p(g2T-TT). By changing the regio-positioning of the side chains, the planarizing effects of the S-O interactions were redistributed along the backbone, and the influence on the polymer's microstructure organization was investigated using grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The newly designed pgBTTT exhibited lower backbone disorder, closer π-stacking, and higher scattering intensity in both the in-plane and out-of-plane GIWAXS measurements. The effect of the improved planarity of pgBTTT manifested as higher hole mobility (μ) of 3.44 ± 0.13 cm2 V-1 s-1. Scanning tunneling microscopy (STM) was in agreement with the GIWAXS measurements and demonstrated, for the first time, that glycol side chains can also facilitate intermolecular interdigitation analogous to that of pBTTT. Electrochemical quartz crystal microbalance with dissipation of energy (eQCM-D) measurements revealed that pgBTTT maintains a more rigid structure than p(g2T-TT) during doping, minimizing molecular packing disruption and maintaining higher hole mobility in operation mode.

AB - Novel p-type semiconducting polymers that can facilitate ion penetration, and operate in accumulation mode are much desired in bioelectronics. Glycol side chains have proven to be an efficient method to increase bulk electrochemical doping and optimize aqueous swelling. One early polymer which exemplifies these design approaches was p(g2T-TT), employing a bithiophene-co-thienothiophene backbone with glycol side chains in the 3,3′ positions of the bithiophene repeat unit. In this paper, the analogous regioisomeric polymer, namely pgBTTT, was synthesized by relocating the glycol side chains position on the bithiophene unit of p(g2T-TT) from the 3,3′ to the 4,4′ positions and compared with the original p(g2T-TT). By changing the regio-positioning of the side chains, the planarizing effects of the S-O interactions were redistributed along the backbone, and the influence on the polymer's microstructure organization was investigated using grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The newly designed pgBTTT exhibited lower backbone disorder, closer π-stacking, and higher scattering intensity in both the in-plane and out-of-plane GIWAXS measurements. The effect of the improved planarity of pgBTTT manifested as higher hole mobility (μ) of 3.44 ± 0.13 cm2 V-1 s-1. Scanning tunneling microscopy (STM) was in agreement with the GIWAXS measurements and demonstrated, for the first time, that glycol side chains can also facilitate intermolecular interdigitation analogous to that of pBTTT. Electrochemical quartz crystal microbalance with dissipation of energy (eQCM-D) measurements revealed that pgBTTT maintains a more rigid structure than p(g2T-TT) during doping, minimizing molecular packing disruption and maintaining higher hole mobility in operation mode.

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U2 - 10.1021/jacs.1c03516

DO - 10.1021/jacs.1c03516

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 29

ER -

Regiochemistry-Driven Organic Electrochemical Transistor Performance Enhancement in Ethylene Glycol-Functionalized Polythiophenes

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