Ionic Dopant-Induced Ordering Enhances the Thermoelectric Properties of a Polythiophene-Based Block Copolymer

Dong, Ban Xuan; Liu, Ziwei; Onorato, Jonathan W.; Ma, Tengzhou; Strzalka, Joseph; Bennington, Peter; Luscombe, Christine K.; Ober, Christopher K.; Nealey, Paul F.; Patel, Shrayesh N.

doi:10.1002/adfm.202106991

Title: Ionic Dopant-Induced Ordering Enhances the Thermoelectric Properties of a Polythiophene-Based Block Copolymer

Journal Article · Wed Sep 15 00:00:00 EDT 2021 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202106991· OSTI ID:1865092

^[1]; Liu, Ziwei ^[2];

^[3]; Ma, Tengzhou ^[1];

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Univ. of Chicago, IL (United States)
Cornell Univ., Ithaca, NY (United States)
Univ. of Washington, Seattle, WA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Abstract Conjugated polymer‐based block copolymers (CP‐BCPs) are an unexplored class of materials for organic thermoelectrics. Herein, the authors report on the electronic conductivity (σ) and Seebeck coefficient (α) of a newly synthesized CP‐BCP, poly(3‐hexylthiophene)‐ block ‐poly (oligo‐oxyethylene methacrylate) (P3HT‐ b ‐POEM), upon solution co‐processing with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and subsequently vapor‐doping with a molecular dopant, 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ). It is found that the addition of the hydrophilic block POEM greatly enhances the processability of P3HT, enabling homogeneous solution‐mixing with LiTFSI. Notably, interactions between P3HT‐ b ‐POEM with ionic species significantly improve molecular order and unexpectedly cause electrical oxidizing doping of P3HT block both in solution and solid‐states, a phenomenon that has not been previously observed in Li‐salt containing P3HT. Vapor doping of P3HT‐ b ‐POEM‐LiTFSI thin films with F4TCNQ further enhances σ and yields a thermoelectric power factor PF = α ² σ of 13.0 µ W m ⁻¹ K ⁻² , which is more than 20 times higher than salt‐free P3HT‐ b ‐POEM sample. Through modeling thermoelectric behaviors of P3HT‐ b‐ POEM with the Kang‐Snyder transport model, the improvement in PF is attributed to higher electronic charge mobility originating from the enhanced molecular ordering of P3HT. The results demonstrate that solution co‐processing CP‐BCPs with a salt is a powerful method to control structure and performance of organic thermoelectric materials.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357; 1629369; DMR-1719875; NSF ECCS-2025633

OSTI ID:: 1865092

Alternate ID(s):: OSTI ID: 1820226

Journal Information:: Advanced Functional Materials, Vol. 31, Issue 51; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
conjugated polymer-based block copolymers
ionic dopants
molecular dopants
organic thermoelectrics
Seebeck-conductivity relation

Title: Ionic Dopant-Induced Ordering Enhances the Thermoelectric Properties of a Polythiophene-Based Block Copolymer

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