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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Bibliographic Details
Published in:Advanced materials (Weinheim) Vol. 34; no. 22; pp. e2102988 - n/a
Main Authors: 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
Language:English
Published: Germany Wiley Subscription Services, Inc 01.06.2022
Wiley-VCH Verlag
Wiley Blackwell (John Wiley & Sons)
Subjects:
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 Access:Get full text
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Summary: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.
Bibliography:Dedicated to Professor Daoben Zhu on the occasion of his 80th birthday
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USDOE Office of Science (SC)
AC02-06CH11357; 610115; EP/R031894/1; EP/L015889/1; DMR-1729737
European Commission (EC)
Royal Society Newton International Fellowship
European Research Council (ERC)
National Science Foundation (NSF)
Engineering and Physical Sciences Research Council
ISSN:0935-9648
1521-4095
1521-4095
DOI:10.1002/adma.202102988