Proquinoidal-Conjugated Polymer as an Effective Strategy for the Enhancement of Electrical Conductivity and Thermoelectric Properties

Proquinoidal-Conjugated Polymer as an Effective Strategy for the Enhancement of Electrical Conductivity and Thermoelectric Properties
Title:
Proquinoidal-Conjugated Polymer as an Effective Strategy for the Enhancement of Electrical Conductivity and Thermoelectric Properties
Other Titles:
Chemistry of Materials
Publication Date:
19 September 2019
Citation:
Chem. Mater. 2019, 31, 20, 8543–8550
Abstract:
P-doping of conjugated polymers requires electron transfer from the conjugated polymer to the p-dopant. This implies that the highest occupied molecular orbital (HOMO) of the conjugated polymer has to be higher than the lowest unoccupied molecular orbital (LUMO) of the p-dopant. Although commonly used p-dopants such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) have a low LUMO of −5.24 eV, most conjugated polymers used in high-performance field-effect transistors are donor–acceptor-type polymers with deep HOMO values, making them difficult to be effectively doped by F4TCNQ. Here, we utilized the proquinoidal 2,6-dialkyl-benzo[1,2-d;4,5-d′]bistriazole (BBTa26) moiety in conjugated polymers to destabilize HOMO, allowing effective p-doping using very dilute F4TCNQ solutions. The extent of the quinoidal character and hence their intrinsic conductivities and the ability to be doped are dependent on the dihedral angles and aromaticity of the aryl spacer groups along the polymer backbone. Intrinsic conductivities as high as 10–2 S cm–1 were achieved. Upon doping using F4TCNQ, highly delocalized polarons were observed. As such, electrical conductivities of over 100 S cm–1 and an enhancement of the Seebeck coefficient from carrier-induced softening can be achieved. A maximum power factor of 11.8 μW m–1 K–2 was achieved in thin-film thermoelectric devices. These results are among the highest for solution-phase p-doping using F4TCNQ without additional processing.
License type:
PublisherCopyrights
Funding Info:
The authors thank Jozel Tan and Dr. Martin Van Meurs from ICES, A*STAR for their help in the high-temperature GPC measurements. T.L.D.T. and J.X. would like to acknowledge the A*STAR, SERC Thermoelectric Materials Program (grant numbers: 1527200019 & 1527200021). W.L.L. would like to acknowledge funding support from her NTU start-up grant (M4081866), Ministry of Education (MOE) under Tier 2 grant (2018-T2-1-075) as well as A*STAR AME Young Individual Research Grant (project number A1784c019).
Description:
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.chemmater.9b03684
ISSN:
0897-4756
1520-5002
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