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Title: The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

Abstract

Here, we report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5];  [6];  [6];  [7];  [8];  [8]; ORCiD logo [8];  [9];  [7]; ORCiD logo [10]; ORCiD logo [11];  [8];  [12]; ORCiD logo [13]
  1. Imperial College, London (United Kingdom). Dept. of Chemistry, Dept. of Physics and Centre for Plastic Electronics
  2. Imperial College, London (United Kingdom). Dept. of Chemistry
  3. Stanford Univ., CA (United States). Dept. of Chemistry
  4. Mines ParisTech, CMP-EMSE, Paris (France). Dept. of Bioelectronics
  5. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia). Physical Sciences and Engineering Division and KAUST Solar Center (KSC)
  6. Northwestern Univ., Evanston, IL (United States). Dept. of Biomedical Engineering
  7. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia). Biological and Environmental Science and Engineering
  8. Imperial College, London (United Kingdom). Dept. of Physics and Centre for Plastic Electronics
  9. Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Inst.; National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center
  10. Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Inst. and Dept. of Chemistry and Biochemistry; National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center
  11. Univ. of Cambridge (United Kingdom). Electrical Engineering Division
  12. Northwestern Univ., Evanston, IL (United States). Dept. of Biomedical Engineering and Simpson Querry Inst. for BioNanotechnology
  13. Imperial College, London (United Kingdom). Dept. of Chemistry; King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia). Physical Sciences and Engineering Division and KAUST Solar Center (KSC)
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; BASF SE, Ludwigshafen (Germany); Engineering and Physical Sciences Research Council (EPSRC); European Research Council (ERC); European Union (EU); National Science Foundation (NSF)
OSTI Identifier:
1440398
Report Number(s):
NREL/JA-5900-71212
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
AC36-08GO28308; EP/P02484X/1; EP/G037515/1; EP/M005143/1; EP/N509486/1; EC FP7 Project SC2 (610115); EC H2020 Project SOLEDLIGHT (643791); 742708
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 9; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; n-type materials; organic electrochemical transistors

Citation Formats

Giovannitti, Alexander, Maria, Iuliana P., Hanifi, David, Donahue, Mary J., Bryant, Daniel, Barth, Katrina J., Makdah, Beatrice E., Savva, Achilleas, Moia, Davide, Zetek, Matyas, Barnes, Piers R. F., Reid, Obadiah G., Inal, Sahika, Rumbles, Garry, Malliaras, George G., Nelson, Jenny, Rivnay, Jonathan, and McCulloch, Iain. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b00321.
Giovannitti, Alexander, Maria, Iuliana P., Hanifi, David, Donahue, Mary J., Bryant, Daniel, Barth, Katrina J., Makdah, Beatrice E., Savva, Achilleas, Moia, Davide, Zetek, Matyas, Barnes, Piers R. F., Reid, Obadiah G., Inal, Sahika, Rumbles, Garry, Malliaras, George G., Nelson, Jenny, Rivnay, Jonathan, & McCulloch, Iain. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes. United States. https://doi.org/10.1021/acs.chemmater.8b00321
Giovannitti, Alexander, Maria, Iuliana P., Hanifi, David, Donahue, Mary J., Bryant, Daniel, Barth, Katrina J., Makdah, Beatrice E., Savva, Achilleas, Moia, Davide, Zetek, Matyas, Barnes, Piers R. F., Reid, Obadiah G., Inal, Sahika, Rumbles, Garry, Malliaras, George G., Nelson, Jenny, Rivnay, Jonathan, and McCulloch, Iain. 2018. "The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes". United States. https://doi.org/10.1021/acs.chemmater.8b00321. https://www.osti.gov/servlets/purl/1440398.
@article{osti_1440398,
title = {The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes},
author = {Giovannitti, Alexander and Maria, Iuliana P. and Hanifi, David and Donahue, Mary J. and Bryant, Daniel and Barth, Katrina J. and Makdah, Beatrice E. and Savva, Achilleas and Moia, Davide and Zetek, Matyas and Barnes, Piers R. F. and Reid, Obadiah G. and Inal, Sahika and Rumbles, Garry and Malliaras, George G. and Nelson, Jenny and Rivnay, Jonathan and McCulloch, Iain},
abstractNote = {Here, we report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.},
doi = {10.1021/acs.chemmater.8b00321},
url = {https://www.osti.gov/biblio/1440398}, journal = {Chemistry of Materials},
issn = {0897-4756},
number = 9,
volume = 30,
place = {United States},
year = {Tue Apr 24 00:00:00 EDT 2018},
month = {Tue Apr 24 00:00:00 EDT 2018}
}

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Cited by: 144 works
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Segregated versus Mixed Interchain Stacking in Highly Oriented Films of Naphthalene Diimide Bithiophene Copolymers
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A general relationship between disorder, aggregation and charge transport in conjugated polymers
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Strategy for Enhancing the Dielectric Constant of Organic Semiconductors Without Sacrificing Charge Carrier Mobility and Solubility
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Complementary Logic Circuits Based on High-Performance n-Type Organic Electrochemical Transistors
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Morphological Origin of Charge Transport Anisotropy in Aligned Polythiophene Thin Films
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Strategy for Enhancing the Dielectric Constant of Organic Semiconductors Without Sacrificing Charge Carrier Mobility and Solubility
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Easy-to-Fabricate Conducting Polymer Microelectrode Arrays
journal, February 2013


Electrocardiographic Recording with Conformable Organic Electrochemical Transistor Fabricated on Resorbable Bioscaffold
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A High Transconductance Accumulation Mode Electrochemical Transistor
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N-Type Organic Thermoelectrics: Improved Power Factor by Tailoring Host-Dopant Miscibility
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Enhancing Molecular n-Type Doping of Donor-Acceptor Copolymers by Tailoring Side Chains
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Complementary Logic Circuits Based on High-Performance n-Type Organic Electrochemical Transistors
journal, January 2018


The organic electrochemical transistor for biological applications
journal, January 2015


Thermal degradation of polyethylene oxide and polypropylene oxide
journal, April 1959


New brightly coloured, water soluble, core-substituted naphthalene diimides for biophysical applications
journal, January 2015


Low-voltage operated solid-state electrolyte-gated ambipolar organic field-effect transistors
journal, January 2018


Enhanced n-Doping Efficiency of a Naphthalenediimide-Based Copolymer through Polar Side Chains for Organic Thermoelectrics
journal, January 2018


Ion transport in solvent-free polymers
journal, January 1988


Synthesis of a Series of Oligo(ethylene glycol)-Terminated Alkanethiol Amides Designed to Address Structure and Stability of Biosensing Interfaces
journal, June 2001


Probing Molecular and Surface Interactions of Comb-Type Polymer Polystyrene- graft -poly(ethylene oxide) (PS- g -PEO) with an SFA
journal, August 2012


Segregated versus Mixed Interchain Stacking in Highly Oriented Films of Naphthalene Diimide Bithiophene Copolymers
journal, October 2012


Organic electrochemical transistors
journal, January 2018


How much do van der Waals dispersion forces contribute to molecular recognition in solution?
journal, October 2013


Structural control of mixed ionic and electronic transport in conducting polymers
journal, April 2016


In vivo recordings of brain activity using organic transistors
journal, March 2013


A general relationship between disorder, aggregation and charge transport in conjugated polymers
journal, August 2013


Use of side-chain for rational design of n-type diketopyrrolopyrrole-based conjugated polymers: what did we find out?
journal, January 2014


Controlling the mode of operation of organic transistors through side-chain engineering
journal, October 2016


Quantitative analysis of time-resolved microwave conductivity data
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High-performance transistors for bioelectronics through tuning of channel thickness.
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High transconductance organic electrochemical transistors.
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Molecular Design of Semiconducting Polymers for High-Performance Organic Electrochemical Transistors.
journalarticle, January 2016


N-type organic electrochemical transistors with stability in water.
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Works referencing / citing this record:

Principles of Structural Design of Conjugated Polymers Showing Excellent Charge Transport toward Thermoelectrics and Bioelectronics Applications
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Amphiphilic polypyrrole-poly(Schiff base) copolymers with poly(ethylene glycol) side chains: synthesis, properties and applications
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Conjugated electrochromic polymers with amide-containing side chains enabling aqueous electrolyte compatibility
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Balancing Ionic and Electronic Conduction for High‐Performance Organic Electrochemical Transistors
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Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?
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Design and evaluation of conjugated polymers with polar side chains as electrode materials for electrochemical energy storage in aqueous electrolytes
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Using Deep Machine Learning to Understand the Physical Performance Bottlenecks in Novel Thin‐Film Solar Cells
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Biofuel powered glucose detection in bodily fluids with an n-type conjugated polymer
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Conducting Polymer‐Based Biocomposites Using Deoxyribonucleic Acid (DNA) as Counterion
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n-Type organic electrochemical transistors: materials and challenges
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Materials in Organic Electrochemical Transistors for Bioelectronic Applications: Past, Present, and Future
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Oligo(ethylene glycol) as side chains of conjugated polymers for optoelectronic applications
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