High Conductivity and Electron-Transfer Validation in an n-Type Fluoride-Anion-Doped Polymer for Thermoelectrics in Air

Zhao, Xingang; Madan, Deepa; Cheng, Yan; Zhou, Jiawang; Li, Hui; Thon, Susanna M.; Bragg, Arthur E.; DeCoster, Mallory E.; Hopkins, Patrick E.; Katz, Howard E.

doi:10.1002/adma.201606928

Title: High Conductivity and Electron-Transfer Validation in an n-Type Fluoride-Anion-Doped Polymer for Thermoelectrics in Air

Journal Article · Fri Jul 14 00:00:00 EDT 2017 · Advanced Materials

DOI:https://doi.org/10.1002/adma.201606928· OSTI ID:1533038

Zhao, Xingang ^[1]; Madan, Deepa ^[2]; Cheng, Yan ^[3]; Zhou, Jiawang ^[4]; Li, Hui ^[1]; Thon, Susanna M. ^[3]; Bragg, Arthur E. ^[4]; DeCoster, Mallory E. ^[5]; Hopkins, Patrick E. ^[5];

^[6]

Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Materials Science and Engineering
Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Materials Science and Engineering; Univ. of Maryland Baltimore County (UMBC), Baltimore, MD (United States). Dept. of Mechanical Engineering
Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Electrical and Computer Engineering
Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry
Univ. of Virginia, Charlottesville, VA (United States). Dept. of Mechanical and Aerospace Engineering
Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Materials Science and Engineering. Dept. of Chemistry

Air‐stable and soluble tetrabutylammonium fluoride (TBAF) is demonstrated as an efficient n‐type dopant for the conjugated polymer ClBDPPV. Electron transfer from F ⁻ anions to the π‐electron‐deficient ClBDPPV through anion–π electronic interactions is strongly corroborated by the combined results of electron spin resonance, UV–vis–NIR, and ultraviolet photoelectron spectroscopy. Doping of ClBDPPV with 25 mol% TBAF boosts electrical conductivity to up to 0.62 S cm ⁻¹ , among the highest conductivities that have been reported for solution‐processed n‐type conjugated polymers, with a thermoelectric power factor of 0.63 µW m ⁻¹ K ⁻² in air. Importantly, the Seebeck coefficient agrees with recently published correlations to conductivity. Moreover, the F ⁻ ‐doped ClBDPPV shows significant air stability, maintaining the conductivity of over 0.1 S cm ⁻¹ in a thick film after exposure to air for one week, to the best of our knowledge the first report of an air‐stable solution‐processable n‐doped conductive polymer with this level of conductivity. The result shows that using solution‐processable small‐anion salts such as TBAF as an n‐dopant of organic conjugated polymers possessing lower LUMO (lowest unoccupied molecular orbital), less than −4.2 eV) can open new opportunities toward high‐performance air‐stable solution‐processable n‐type thermoelectric (TE) conjugated polymers.

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Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Army Research Ofﬁce (ARO) (United States)

Grant/Contract Number:: FG02-07ER46465; W911NF-16-1-0320

OSTI ID:: 1533038

Alternate ID(s):: OSTI ID: 1380023

Journal Information:: Advanced Materials, Vol. 29, Issue 34; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 125 works

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36 MATERIALS SCIENCE
chemical doping
fluoride salts
n-type conjugated polymers
organic semiconductors
thermoelectrics

Title: High Conductivity and Electron-Transfer Validation in an n-Type Fluoride-Anion-Doped Polymer for Thermoelectrics in Air

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