High-Efficiency Ion-Exchange Doping of Conducting Polymers

Ian E. Jacobs; Yue Lin; Yuxuan Huang; Xinglong Ren; Dimitrios Simatos; Chen Chen; Dion Tjhe; Martin Statz; Lianglun Lai; Peter A. Finn; William G. Neal; Gabriele D'Avino; Vincent Lemaur; Simone Fratini; David Beljonne; Joseph Strzalka; Christian B. Nielsen; Stephen Barlow; Seth R. Marder; Iain McCulloch; Henning Sirringhaus

doi:10.1002/adma.202102988

High-Efficiency Ion-Exchange Doping of Conducting Polymers

Ian E. Jacobs, Yue Lin, Yuxuan Huang, Xinglong Ren, Dimitrios Simatos, Chen Chen, Dion Tjhe, Martin Statz, Lianglun Lai, Peter A. Finn, William G. Neal, Gabriele D'Avino, Vincent Lemaur, Simone Fratini, David Beljonne, Joseph Strzalka, Christian B. Nielsen, Stephen Barlow, Seth R. Marder, Iain McCullochHenning Sirringhaus

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

97 Scopus citations

Abstract

Molecular doping—the use of redox-active small molecules as dopants for organic semiconductors—has seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redox-active character of these materials. A recent breakthrough was a doping technique based on ion-exchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene) (PBTTT) doped with FeCl3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm−1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl3, are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential.

Original language	English (US)
Pages (from-to)	2102988
Journal	Advanced Materials
DOIs	https://doi.org/10.1002/adma.202102988
State	Published - Aug 21 2021

Bibliographical note

KAUST Repository Item: Exported on 2021-08-23
Acknowledgements: I.E.J acknowledges funding through a Royal Society Newton International Fellowship. Financial support from the European Research Council for a Synergy grant SC2 (no. 610115) and from the Engineering and Physical Sciences Research Council (EP/R031894/1) is gratefully acknowledged. Y.L. thanks the European Commission for a Marie–Sklodowska–Curie fellowship. For Ph.D. fellowships D.S. thanks the EPSRC CDT in Sensor Technologies for a Healthy and Sustainable Future (Grant No. EP/L015889/1), L.L. the EPSRC CDT in graphene technology, and D.T. the Jardine Foundation and Cambridge Commonwealth European and International Trust. S.B. and S.R.M. thank National Science Foundation (through the DMREF program, DMR-1729737). 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. The authors thank Yadong Zhang for some dopant synthesis, and Mohamed Al-Hada for assistance with XPS measurements.

ASJC Scopus subject areas

Mechanics of Materials
General Materials Science
Mechanical Engineering

Access to Document

10.1002/adma.202102988

https://repository.kaust.edu.sa/bitstream/10754/670707/1/adma.202102988.pdf

Cite this

Jacobs, I. E., Lin, Y., Huang, Y., Ren, X., Simatos, D., Chen, C., Tjhe, D., Statz, M., Lai, L., Finn, P. A., Neal, W. G., D'Avino, G., Lemaur, V., Fratini, S., Beljonne, D., Strzalka, J., Nielsen, C. B., Barlow, S., Marder, S. R., ... Sirringhaus, H. (2021). High-Efficiency Ion-Exchange Doping of Conducting Polymers. Advanced Materials, 2102988. https://doi.org/10.1002/adma.202102988

@article{017dc693f9844ce79bb8acbab4901cea,

title = "High-Efficiency Ion-Exchange Doping of Conducting Polymers",

abstract = "Molecular doping—the use of redox-active small molecules as dopants for organic semiconductors—has seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redox-active character of these materials. A recent breakthrough was a doping technique based on ion-exchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene) (PBTTT) doped with FeCl3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm−1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl3, are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential.",

author = "Jacobs, {Ian E.} and Yue Lin and Yuxuan Huang and Xinglong Ren and Dimitrios Simatos and Chen Chen and Dion Tjhe and Martin Statz and Lianglun Lai and Finn, {Peter A.} and Neal, {William G.} and Gabriele D'Avino and Vincent Lemaur and Simone Fratini and David Beljonne and Joseph Strzalka and Nielsen, {Christian B.} and Stephen Barlow and Marder, {Seth R.} and Iain McCulloch and Henning Sirringhaus",

note = "KAUST Repository Item: Exported on 2021-08-23 Acknowledgements: I.E.J acknowledges funding through a Royal Society Newton International Fellowship. Financial support from the European Research Council for a Synergy grant SC2 (no. 610115) and from the Engineering and Physical Sciences Research Council (EP/R031894/1) is gratefully acknowledged. Y.L. thanks the European Commission for a Marie–Sklodowska–Curie fellowship. For Ph.D. fellowships D.S. thanks the EPSRC CDT in Sensor Technologies for a Healthy and Sustainable Future (Grant No. EP/L015889/1), L.L. the EPSRC CDT in graphene technology, and D.T. the Jardine Foundation and Cambridge Commonwealth European and International Trust. S.B. and S.R.M. thank National Science Foundation (through the DMREF program, DMR-1729737). 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. The authors thank Yadong Zhang for some dopant synthesis, and Mohamed Al-Hada for assistance with XPS measurements.",

year = "2021",

month = aug,

day = "21",

doi = "10.1002/adma.202102988",

language = "English (US)",

pages = "2102988",

journal = "Advanced Materials",

issn = "0935-9648",

publisher = "Wiley",

}

Jacobs, IE, Lin, Y, Huang, Y, Ren, X, Simatos, D, Chen, C, Tjhe, D, Statz, M, Lai, L, Finn, PA, Neal, WG, D'Avino, G, Lemaur, V, Fratini, S, Beljonne, D, Strzalka, J, Nielsen, CB, Barlow, S, Marder, SR, McCulloch, I & Sirringhaus, H 2021, 'High-Efficiency Ion-Exchange Doping of Conducting Polymers', Advanced Materials, pp. 2102988. https://doi.org/10.1002/adma.202102988

TY - JOUR

T1 - High-Efficiency Ion-Exchange Doping of Conducting Polymers

AU - Jacobs, Ian E.

AU - Lin, Yue

AU - Huang, Yuxuan

AU - Ren, Xinglong

AU - Simatos, Dimitrios

AU - Chen, Chen

AU - Tjhe, Dion

AU - Statz, Martin

AU - Lai, Lianglun

AU - Finn, Peter A.

AU - Neal, William G.

AU - D'Avino, Gabriele

AU - Lemaur, Vincent

AU - Fratini, Simone

AU - Beljonne, David

AU - Strzalka, Joseph

AU - Nielsen, Christian B.

AU - Barlow, Stephen

AU - Marder, Seth R.

AU - McCulloch, Iain

AU - Sirringhaus, Henning

N1 - KAUST Repository Item: Exported on 2021-08-23 Acknowledgements: I.E.J acknowledges funding through a Royal Society Newton International Fellowship. Financial support from the European Research Council for a Synergy grant SC2 (no. 610115) and from the Engineering and Physical Sciences Research Council (EP/R031894/1) is gratefully acknowledged. Y.L. thanks the European Commission for a Marie–Sklodowska–Curie fellowship. For Ph.D. fellowships D.S. thanks the EPSRC CDT in Sensor Technologies for a Healthy and Sustainable Future (Grant No. EP/L015889/1), L.L. the EPSRC CDT in graphene technology, and D.T. the Jardine Foundation and Cambridge Commonwealth European and International Trust. S.B. and S.R.M. thank National Science Foundation (through the DMREF program, DMR-1729737). 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. The authors thank Yadong Zhang for some dopant synthesis, and Mohamed Al-Hada for assistance with XPS measurements.

PY - 2021/8/21

Y1 - 2021/8/21

N2 - Molecular doping—the use of redox-active small molecules as dopants for organic semiconductors—has seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redox-active character of these materials. A recent breakthrough was a doping technique based on ion-exchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene) (PBTTT) doped with FeCl3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm−1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl3, are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential.

AB - Molecular doping—the use of redox-active small molecules as dopants for organic semiconductors—has seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redox-active character of these materials. A recent breakthrough was a doping technique based on ion-exchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene) (PBTTT) doped with FeCl3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm−1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl3, are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential.

UR - http://hdl.handle.net/10754/670707

UR - https://onlinelibrary.wiley.com/doi/10.1002/adma.202102988

U2 - 10.1002/adma.202102988

DO - 10.1002/adma.202102988

M3 - Article

C2 - 34418878

SN - 0935-9648

SP - 2102988

JO - Advanced Materials

JF - Advanced Materials

ER -

High-Efficiency Ion-Exchange Doping of Conducting Polymers

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this