The effect of aromatic ring size in electron deficient semiconducting polymers for n-type organic thermoelectrics

Maryam Alsufyani, Rawad Hallani, Suhao Wang, Mingfei Xiao, Xudong Ji, Bryan D. Paulsen, Kai Xu, Helen Bristow, Hu Chen, Xingxing Chen, Henning Sirringhaus, Jonathan Rivnay, Simone Fabiano, Andrew Wadsworth

Research output: Contribution to journalArticlepeer-review

24 Scopus citations


N-type semiconducting polymers have been recently utilized in thermoelectric devices, however they have typically exhibited low electrical conductivities and poor device stability, in contrast to p-type semiconductors, which have been much higher performing. This is due in particular to the n-type semiconductor's low doping efficiency, and poor charge carrier mobility. Strategies to enhance the thermoelectric performance of n-type materials include optimizing the electron affinity (EA) with respect to the dopant to improve the doping process and increasing the charge carrier mobility through enhanced molecular packing. Here, we report the design, synthesis and characterization of fused electron-deficient n-type copolymers incorporating the electron withdrawing lactone unit along the backbone. The polymers were synthesized using metal-free aldol condensation conditions to explore the effect of enlarging the central phenyl ring to a naphthalene ring, on the electrical conductivity. When n-doped with N-DMBI, electrical conductivities of up to 0.28 S cm-1, Seebeck coefficients of -75 μV K-1 and maximum Power factors of 0.16 μW m-1 K-2 were observed from the polymer with the largest electron affinity of -4.68 eV. Extending the aromatic ring reduced the electron affinity, due to reducing the density of electron withdrawing groups and subsequently the electrical conductivity reduced by almost two orders of magnitude. This journal is
Original languageEnglish (US)
Pages (from-to)15150-15157
Number of pages8
JournalJournal of Materials Chemistry C
Issue number43
StatePublished - 2020

Bibliographical note

KAUST Repository Item: Exported on 2020-11-25
Acknowledged KAUST grant number(s): OSR-2018-CARF/CCF-3079, OSR-2015-CRG4-2572, OSR4106 CPF2019
Acknowledgements: The research reported in this publication was supported by funding from King Abdullah University of Science and Technology Office of Sponsored Research (OSR) under awards no. OSR-2018-CARF/CCF-3079, no. OSR-2015-CRG4-2572 and OSR4106 CPF2019. We acknowledge EC FP7 Project SC2 (610115), EC H2020 (643791), and EPSRC Projects EP/G037515/1, EP/M005143/1, and EP/L016702/1. X. D., B. P., and J. R. gratefully acknowledge support from the National Science FoundationGrant No. NSF DMR-1751308. Special thanks to Joseph Strzalka and Qingteng Zhang for beam line assistance. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory
under Contract No. DE-AC02-06CH11357. S. F. acknowledges the Swedish Research Council (2016-03979), ÅForsk (18-313,19-310), Olle Engkvists Stiftelse (204-0256), and the Advanced Functional Materials Center at Linko¨ping University (2009-00971)
for financial support.


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