Side chain engineering control of mixed conduction in oligoethylene glycol-substituted polythiophenes

Onorato, Jonathan W.; Wang, Zhongyang; Sun, Yangyang; Nowak, Christian; Flagg, Lucas Q.; Li, Ruipeng; Dong, Ban Xuan; Richter, Lee J.; Escobedo, Fernando A.; Nealey, Paul F.; Patel, Shrayesh N.; Luscombe, Christine K.

doi:10.1039/d1ta05379e

Title: Side chain engineering control of mixed conduction in oligoethylene glycol-substituted polythiophenes

Journal Article · 30 August 2021 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/d1ta05379e · OSTI ID:1837224

Onorato, Jonathan W. ^[1];

^[2];

^[3];

^[4]; Li, Ruipeng ^[5]; Dong, Ban Xuan ^[2];

^[4];

^[3]; Nealey, Paul F. ^[6];

^[6];

^[1]

Univ. of Washington, Seattle, WA (United States)
Univ. of Chicago, IL (United States)
Cornell Univ., Ithaca, NY (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

A major limitation for polymeric mixed ionic/electronic conductors (MIECs) is the trade-off between ionic and electronic conductivity; changes made that improve one typically hinder the other. In order to address this fundamental problem, this work provides insight into ways that we could improve one type of conduction without hindering the other. Here, we investigated a common oligoethylene glycol side chain polymer by adjusting the oxygen atom content and position, providing structural insights for materials that better balanced the two conduction pathways. The investigated polymer series showed the prototypical conflict between ionic and electronic conduction for oxygen atom content, with increasing oxygen atom content increasing ionic conductivity, but decreasing electronic conductivity; however, by increasing the oxygen atom distance from the polymer backbone, both ionic and electronic conductivity could be improved. Following these rules, we show that poly(3-(methoxyethoxybutyl)thiophene), when blended with lithium bistrifluoromethanesulfonimide (LiTFSI), matches the ionic conductivity of a comparable MIEC [poly(3-(methoxyethoxyethoxymethyl)thiophene)], while simultaneously showing higher electronic conductivity, highlighting the potential of this design strategy. We also provide strategies for tuning the MIEC performance to fit a desired application, depending on if electronic, ionic, or balanced conduction is most important. These results have implications beyond just polythiophene-based MIECs, as these strategies for balancing backbone crystallization and coordinating group interconnectivity apply for all semicrystalline conjugated polymers.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1837224

Report Number(s):: BNL-222192-2021-JAAM

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 37 Vol. 9; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

A High Transconductance Accumulation Mode Electrochemical Transistor Inal, Sahika; Rivnay, Jonathan; Leleux, Pierre Advanced Materials, Vol. 26, Issue 44 https://doi.org/10.1002/adma.201403150	journal	October 2014
In Situ Electrochemical Synthesis of a Conducting Polymer Composite for Multimetabolite Sensing Wustoni, Shofarul; Hidalgo, Tania C.; Hama, Adel Advanced Materials Technologies, Vol. 5, Issue 3 https://doi.org/10.1002/admt.201900943	journal	December 2019
Mixed electron and proton conductivity of polyaniline films in aqueous solutions of acids: beyond the 1000 S cm ⁻¹ limit: Electron and proton conductivity of PANI films in acids Stejskal, Jaroslav; Bogomolova, Olga E.; Blinova, Natalia V. Polymer International, Vol. 58, Issue 8 https://doi.org/10.1002/pi.2605	journal	June 2009
The Polymer Physics of Multiscale Charge Transport in Conjugated Systems Gu, Kaichen; Loo, Yueh‐Lin Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 23 https://doi.org/10.1002/polb.24873	journal	August 2019
Challenge and Solution of Characterizing Glass Transition Temperature for Conjugated Polymers by Differential Scanning Calorimetry Qian, Zhiyuan; Galuska, Luke; McNutt, William W. Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 23 https://doi.org/10.1002/polb.24889	journal	August 2019
Glassy Carbon as an Absolute Intensity Calibration Standard for Small-Angle Scattering Zhang, Fan; Ilavsky, Jan; Long, Gabrielle G. Metallurgical and Materials Transactions A, Vol. 41, Issue 5 https://doi.org/10.1007/s11661-009-9950-x	journal	August 2009
Nonphysical sampling distributions in Monte Carlo free-energy estimation: Umbrella sampling Torrie, G. M.; Valleau, J. P. Journal of Computational Physics, Vol. 23, Issue 2 https://doi.org/10.1016/0021-9991(77)90121-8	journal	February 1977
Study of ionic conductivity and microstructure of a cross-linked polyurethane acrylate electrolyte Digar, M. Polymer, Vol. 43, Issue 3 https://doi.org/10.1016/S0032-3861(01)00655-3	journal	February 2002
Designing a high-loading sulfur cathode with a mixed ionic-electronic conducting polymer for electrochemically stable lithium-sulfur batteries Han, Pauline; Chung, Sheng-Heng; Manthiram, Arumugam Energy Storage Materials, Vol. 17 https://doi.org/10.1016/j.ensm.2018.11.002	journal	February 2019
Measuring the Glass Transition Temperature of Conjugated Polymer Films with Ultraviolet–Visible Spectroscopy Root, Samuel E.; Alkhadra, Mohammad A.; Rodriquez, Daniel Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.7b00242	journal	March 2017
The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David Chemistry of Materials, Vol. 30, Issue 9 https://doi.org/10.1021/acs.chemmater.8b00321	journal	April 2018
Influence of Water on the Performance of Organic Electrochemical Transistors Savva, Achilleas; Cendra, Camila; Giugni, Andrea Chemistry of Materials, Vol. 31, Issue 3 https://doi.org/10.1021/acs.chemmater.8b04335	journal	January 2019
Influence of Side-Chain Chemistry on Structure and Ionic Conduction Characteristics of Polythiophene Derivatives: A Computational and Experimental Study Dong, Ban Xuan; Nowak, Christian; Onorato, Jonathan W. Chemistry of Materials, Vol. 31, Issue 4 https://doi.org/10.1021/acs.chemmater.8b05257	journal	February 2019
Expanded Theory of H- and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer Hestand, Nicholas J.; Spano, Frank C. Chemical Reviews, Vol. 118, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00581	journal	April 2018
Revisiting the Vibrational and Optical Properties of P3HT: A Combined Experimental and Theoretical Study Farouil, Léa; Alary, Fabienne; Bedel-Pereira, Eléna The Journal of Physical Chemistry A, Vol. 122, Issue 32 https://doi.org/10.1021/acs.jpca.8b03814	journal	July 2018
Ionic Liquid for PEDOT:PSS Treatment. Ion Binding Free Energy in Water Revealing the Importance of Anion Hydrophobicity de Izarra, Ambroise; Choi, Changwon; Jang, Yun Hee The Journal of Physical Chemistry B, Vol. 125, Issue 7 https://doi.org/10.1021/acs.jpcb.0c10068	journal	February 2021
Unraveling the Lithium Bis(trifluoromethanesulfonyl)imide (LiTFSI) Doping Mechanism of Regioregular Poly(3-hexylthiophene): Experimental and Theoretical Study Mombrú, Dominique; Romero, Mariano; Faccio, Ricardo The Journal of Physical Chemistry C, Vol. 124, Issue 13 https://doi.org/10.1021/acs.jpcc.0c00407	journal	March 2020
Solution Processing with a Good Solvent Additive for Highly Reliable Organic Thin-Film Transistors Na, Jin Yeong; Kim, Min; Park, Yeong Don The Journal of Physical Chemistry C, Vol. 121, Issue 25 https://doi.org/10.1021/acs.jpcc.7b03833	journal	June 2017
Origin of the π–π Spacing Change upon Doping of Semiconducting Polymers Liu, Wenlan; Müller, Lars; Ma, Shuangying The Journal of Physical Chemistry C, Vol. 122, Issue 49 https://doi.org/10.1021/acs.jpcc.8b10845	journal	November 2018
Replacing Alkyl with Oligo(ethylene glycol) as Side Chains of Conjugated Polymers for Close π–π Stacking Meng, Bin; Song, Haiyang; Chen, Xingxing Macromolecules, Vol. 48, Issue 13 https://doi.org/10.1021/acs.macromol.5b00702	journal	June 2015
Influence of Side Chains on the n-Type Organic Electrochemical Transistor Performance Ohayon, David; Savva, Achilleas; Du, Weiyuan ACS Applied Materials & Interfaces, Vol. 13, Issue 3 https://doi.org/10.1021/acsami.0c18599	journal	January 2021
The Key Role of Side Chain Linkage in Structure Formation and Mixed Conduction of Ethylene Glycol Substituted Polythiophenes Schmode, Philip; Savva, Achilleas; Kahl, Robert ACS Applied Materials & Interfaces, Vol. 12, Issue 11 https://doi.org/10.1021/acsami.9b21604	journal	February 2020
Percolation, Tie-Molecules, and the Microstructural Determinants of Charge Transport in Semicrystalline Conjugated Polymers Mollinger, Sonya A.; Krajina, Brad A.; Noriega, Rodrigo ACS Macro Letters, Vol. 4, Issue 7 https://doi.org/10.1021/acsmacrolett.5b00314	journal	June 2015
Structure Control of a π-Conjugated Oligothiophene-Based Liquid Crystal for Enhanced Mixed Ion/Electron Transport Characteristics Dong, Ban Xuan; Liu, Ziwei; Misra, Mayank ACS Nano, Vol. 13, Issue 7 https://doi.org/10.1021/acsnano.9b01055	journal	June 2019
Oligoethylene-Glycol-Functionalized Polyoxythiophenes for Cell Engineering: Syntheses, Characterizations, and Cell Compatibilities Zhao, Haichao; Zhu, Bo; Sekine, Jun ACS Applied Materials & Interfaces, Vol. 4, Issue 2 https://doi.org/10.1021/am2012905	journal	January 2012
Enhanced Mobility of Poly(3-hexylthiophene) Transistors by Spin-Coating from High-Boiling-Point Solvents Chang, Jui-Fen; Sun, Baoquan; Breiby, Dag W. Chemistry of Materials, Vol. 16, Issue 23, p. 4772-4776 https://doi.org/10.1021/cm049617w	journal	November 2004
Interaction of Oxygen with Conjugated Polymers: Charge Transfer Complex Formation with Poly(3-alkylthiophenes) Abdou, Mohamed S. A.; Orfino, Francesco P.; Son, Yongkeun Journal of the American Chemical Society, Vol. 119, Issue 19 https://doi.org/10.1021/ja964229j	journal	May 1997
Polymer Crystallinity Controls Water Uptake in Glycol Side-Chain Polymer Organic Electrochemical Transistors Flagg, Lucas Q.; Bischak, Connor G.; Onorato, Jonathan W. Journal of the American Chemical Society, Vol. 141, Issue 10 https://doi.org/10.1021/jacs.8b12640	journal	February 2019
Distinct Difference in Ionic Transport Behavior in Polymer Electrolytes Depending on the Matrix Polymers and Incorporated Salts Seki, Shiro; Susan, Md. Abu Bin Hasan; Kaneko, Taketo The Journal of Physical Chemistry B, Vol. 109, Issue 9 https://doi.org/10.1021/jp045328j	journal	March 2005
Charge Transport in a Mixed Ionically/Electronically Conducting, Cationic, Polyacetylene Ionomer between Ion-Blocking Electrodes Cheng, Calvin H. W.; Lin, Fuding; Lonergan, Mark C. The Journal of Physical Chemistry B, Vol. 109, Issue 20 https://doi.org/10.1021/jp0505431	journal	May 2005
Quantifying Crystallinity in High Molar Mass Poly(3-hexylthiophene) Snyder, Chad R.; Nieuwendaal, Ryan C.; DeLongchamp, Dean M. Macromolecules, Vol. 47, Issue 12 https://doi.org/10.1021/ma500136d	journal	June 2014
High Ionic Conductivity of Polyether-Based Network Polymer Electrolytes with Hyperbranched Side Chains Nishimoto, Atsushi; Agehara, Kunihiro; Furuya, Noriyuki Macromolecules, Vol. 32, Issue 5 https://doi.org/10.1021/ma981436q	journal	March 1999
Simultaneous Conduction of Electronic Charge and Lithium Ions in Block Copolymers Patel, Shrayesh N.; Javier, Anna E.; Stone, Greg M. ACS Nano, Vol. 6, Issue 2 https://doi.org/10.1021/nn2045664	journal	January 2012
N-type organic electrochemical transistors with stability in water Giovannitti, Alexander; Nielsen, Christian B.; Sbircea, Dan-Tiberiu Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13066	journal	October 2016
Electrochemical strain microscopy probes morphology-induced variations in ion uptake and performance in organic electrochemical transistors Giridharagopal, R.; Flagg, L. Q.; Harrison, J. S. Nature Materials, Vol. 16, Issue 7 https://doi.org/10.1038/nmat4918	journal	June 2017
Benchmarking organic mixed conductors for transistors Inal, Sahika; Malliaras, George G.; Rivnay, Jonathan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01812-w	journal	November 2017
Influence of π-conjugation length on mobilities of charge carriers in conducting polymers Harima, Yutaka; Jiang, Xiaoqing; Kunugi, Yoshihito J. Mater. Chem., Vol. 13, Issue 6 https://doi.org/10.1039/B301780J	journal	January 2003
Light absorption of poly(3-hexylthiophene) single crystals Rahimi, Khosrow; Botiz, Ioan; Agumba, John O. RSC Adv., Vol. 4, Issue 22 https://doi.org/10.1039/C3RA47064D	journal	January 2014
“Ionic liquids-in-salt” – a promising electrolyte concept for high-temperature lithium batteries? Marczewski, Maciej J.; Stanje, Bernhard; Hanzu, Ilie Phys. Chem. Chem. Phys., Vol. 16, Issue 24 https://doi.org/10.1039/C4CP01133C	journal	January 2014
Ionic-to-electronic coupling efficiency in PEDOT:PSS films operated in aqueous electrolytes Savva, Achilleas; Wustoni, Shofarul; Inal, Sahika Journal of Materials Chemistry C, Vol. 6, Issue 44 https://doi.org/10.1039/C8TC02195C	journal	January 2018
Chloride transport in conductive polymer films for an n-type thermoelectric platform Kim, Byeonggwan; Hwang, Jong Un; Kim, Eunkyoung Energy & Environmental Science, Vol. 13, Issue 3 https://doi.org/10.1039/C9EE02399B	journal	January 2020
Oligo(ethylene glycol) as side chains of conjugated polymers for optoelectronic applications Meng, Bin; Liu, Jun; Wang, Lixiang Polymer Chemistry, Vol. 11, Issue 7 https://doi.org/10.1039/C9PY01469A	journal	January 2020
Lithium salts as “redox active” p-type dopants for organic semiconductors and their impact in solid-state dye-sensitized solar cells Abate, Antonio; Leijtens, Tomas; Pathak, Sandeep Physical Chemistry Chemical Physics, Vol. 15, Issue 7 https://doi.org/10.1039/c2cp44397j	journal	January 2013
Effects of molecular oxygen and ozone on polythiophene-based thin-film transistors Chabinyc, Michael L.; Street, Robert A.; Northrup, John E. Applied Physics Letters, Vol. 90, Issue 12 https://doi.org/10.1063/1.2715445	journal	March 2007
Dynamics and reversibility of oxygen doping and de-doping for conjugated polymer Liao, Hua-Hsien; Yang, Chia-Ming; Liu, Chien-Cheng Journal of Applied Physics, Vol. 103, Issue 10 https://doi.org/10.1063/1.2917419	journal	May 2008
Controlling the mode of operation of organic transistors through side-chain engineering Giovannitti, Alexander; Sbircea, Dan-Tiberiu; Inal, Sahika Proceedings of the National Academy of Sciences, Vol. 113, Issue 43 https://doi.org/10.1073/pnas.1608780113	journal	October 2016
Nika : software for two-dimensional data reduction Ilavsky, Jan Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004037	journal	March 2012
Direct metabolite detection with an n-type accumulation mode organic electrochemical transistor Pappa, Anna Maria; Ohayon, David; Giovannitti, Alexander Science Advances, Vol. 4, Issue 6 https://doi.org/10.1126/sciadv.aat0911	journal	June 2018
Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes Sharon, Daniel; Bennington, Peter; Liu, Claire Journal of The Electrochemical Society, Vol. 165, Issue 16 https://doi.org/10.1149/2.0291816jes	journal	January 2018