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 · 15 September 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)

Conjugated polymer-based block copolymers (CP-BCPs) are an unexplored class of materials for organic thermoelectrics. In this study, 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 = α²σ of 13.0 μW 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

OSTI ID:: 1865092

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

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
Seebeck-conductivity relation
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ionic dopants
molecular dopants
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Title: Ionic Dopant-Induced Ordering Enhances the Thermoelectric Properties of a Polythiophene-Based Block Copolymer

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