High‐Efficiency Ion‐Exchange Doping of Conducting Polymers

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...

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Veröffentlicht in:	Advanced materials (Weinheim) Jg. 34; H. 22; S. e2102988 - n/a
Hauptverfasser:	Jacobs, Ian E., Lin, Yue, Huang, Yuxuan, Ren, Xinglong, Simatos, Dimitrios, Chen, Chen, Tjhe, Dion, Statz, Martin, Lai, Lianglun, Finn, Peter A., Neal, William G., D'Avino, Gabriele, Lemaur, Vincent, Fratini, Simone, Beljonne, David, Strzalka, Joseph, Nielsen, Christian B., Barlow, Stephen, Marder, Seth R., McCulloch, Iain, Sirringhaus, Henning
Format:	Journal Article
Sprache:	Englisch
Veröffentlicht:	Germany Wiley Subscription Services, Inc 01.06.2022 Wiley-VCH Verlag Wiley Blackwell (John Wiley & Sons)
Schlagworte:	Acetonitrile Chemical Sciences Condensed Matter Conducting polymers conjugated polymers Doping electrical conductivity electrochemistry Ferric chloride Ion exchange Ionic liquids MATERIALS SCIENCE Organic semiconductors Physics Polymers Stability doping electrochemistry electrical conductivity conjugated polymers ion exchange
ISSN:	0935-9648, 1521-4095, 1521-4095
Online-Zugang:	Volltext
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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. An extremely efficient ion‐exchange doping process for conjugated polymers which enables conductivities exceeding 1000 S cm−1 is demonstrated. Factors which affect ion exchange, such as electrolyte concentration, doping solvent, and film crystallinity are discussed. When exchange is efficient there is a direct correspondence between ion exchange electrochemical doping, which is used to reveal the detrimental impact of off‐target oxidation reactions.
AbstractList	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 FeCl 3 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 FeCl 3 , 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. 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. An extremely efficient ion‐exchange doping process for conjugated polymers which enables conductivities exceeding 1000 S cm−1 is demonstrated. Factors which affect ion exchange, such as electrolyte concentration, doping solvent, and film crystallinity are discussed. When exchange is efficient there is a direct correspondence between ion exchange electrochemical doping, which is used to reveal the detrimental impact of off‐target oxidation reactions. 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 FeCl and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm 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 FeCl , 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. 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. 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.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. 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 FeCl 3 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 FeCl 3 , 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. 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, we study the equilibrium and kinetics of ion exchange doping in a model system, PBTTT doped with FeCl 3 and BMP TFSI, which reaches conductivities in excess of 1000 S/cm and ion exchange efficiencies above 99%. We demonstrate several factors which 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 FeCl 3. In this high ion exchange efficiency regime, we illustrate a simple connection between electrochemical doping and ion exchange, and show that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential.
Author	Marder, Seth R. Lemaur, Vincent Fratini, Simone McCulloch, Iain Strzalka, Joseph Barlow, Stephen Statz, Martin Simatos, Dimitrios Huang, Yuxuan Finn, Peter A. Lai, Lianglun Sirringhaus, Henning D'Avino, Gabriele Chen, Chen Jacobs, Ian E. Neal, William G. Lin, Yue Ren, Xinglong Tjhe, Dion Beljonne, David Nielsen, Christian B.
Author_xml	– sequence: 1 givenname: Ian E. surname: Jacobs fullname: Jacobs, Ian E. organization: University of Cambridge – sequence: 2 givenname: Yue surname: Lin fullname: Lin, Yue organization: University of Cambridge – sequence: 3 givenname: Yuxuan surname: Huang fullname: Huang, Yuxuan organization: University of Cambridge – sequence: 4 givenname: Xinglong surname: Ren fullname: Ren, Xinglong organization: University of Cambridge – sequence: 5 givenname: Dimitrios surname: Simatos fullname: Simatos, Dimitrios organization: University of Cambridge – sequence: 6 givenname: Chen surname: Chen fullname: Chen, Chen organization: University of Cambridge – sequence: 7 givenname: Dion surname: Tjhe fullname: Tjhe, Dion organization: University of Cambridge – sequence: 8 givenname: Martin surname: Statz fullname: Statz, Martin organization: University of Cambridge – sequence: 9 givenname: Lianglun surname: Lai fullname: Lai, Lianglun organization: University of Cambridge – sequence: 10 givenname: Peter A. surname: Finn fullname: Finn, Peter A. organization: Queen Mary University of London – sequence: 11 givenname: William G. surname: Neal fullname: Neal, William G. organization: Queen Mary University of London – sequence: 12 givenname: Gabriele surname: D'Avino fullname: D'Avino, Gabriele organization: Institut Néel – sequence: 13 givenname: Vincent surname: Lemaur fullname: Lemaur, Vincent organization: University of Mons – sequence: 14 givenname: Simone surname: Fratini fullname: Fratini, Simone organization: Institut Néel – sequence: 15 givenname: David surname: Beljonne fullname: Beljonne, David organization: University of Mons – sequence: 16 givenname: Joseph surname: Strzalka fullname: Strzalka, Joseph organization: Argonne National Laboratory – sequence: 17 givenname: Christian B. surname: Nielsen fullname: Nielsen, Christian B. organization: Queen Mary University of London – sequence: 18 givenname: Stephen surname: Barlow fullname: Barlow, Stephen organization: Georgia Institute of Technology – sequence: 19 givenname: Seth R. surname: Marder fullname: Marder, Seth R. organization: Georgia Institute of Technology – sequence: 20 givenname: Iain surname: McCulloch fullname: McCulloch, Iain organization: University of Oxford – sequence: 21 givenname: Henning orcidid: 0000-0001-9827-6061 surname: Sirringhaus fullname: Sirringhaus, Henning email: hs220@cam.ac.uk organization: University of Cambridge
BackLink	https://www.ncbi.nlm.nih.gov/pubmed/34418878$$D View this record in MEDLINE/PubMed https://hal.science/hal-03411915$$DView record in HAL https://www.osti.gov/biblio/1821038$$D View this record in Osti.gov
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Copyright	2021 The Authors. Advanced Materials published by Wiley‐VCH GmbH 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH. 2021. This article is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License. licence_http://creativecommons.org/publicdomain/zero
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Snippet	Molecular doping—the use of redox‐active small molecules as dopants for organic semiconductors—has seen a surge in research interest driven by emerging... Molecular doping-the use of redox-active small molecules as dopants for organic semiconductors-has seen a surge in research interest driven by emerging... Abstract Molecular doping—the use of redox‐active small molecules as dopants for organic semiconductors—has seen a surge in research interest driven by...
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SubjectTerms	Acetonitrile Chemical Sciences Condensed Matter Conducting polymers conjugated polymers Doping electrical conductivity electrochemistry Ferric chloride Ion exchange Ionic liquids MATERIALS SCIENCE Organic semiconductors Physics Polymers Stability
Title	High‐Efficiency Ion‐Exchange Doping of Conducting Polymers
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