Counterion Control and the Spectral Signatures of Polarons, Coupled Polarons, and Bipolarons in Doped P3HT Films

Wu, Eric C.; Salamat, Charlene Z.; Ruiz, Omar León; Qu, Thomas; Kim, Alexis; Tolbert, Sarah H.; Schwartz, Benjamin J.

doi:10.1002/adfm.202213652

Counterion Control and the Spectral Signatures of Polarons, Coupled Polarons, and Bipolarons in Doped P3HT Films

Journal Article · Mon Feb 20 00:00:00 EST 2023 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202213652· OSTI ID:2423331

Wu, Eric C. ^[1]; Salamat, Charlene Z. ^[1]; Ruiz, Omar León ^[1]; Qu, Thomas ^[1]; Kim, Alexis ^[1]; Tolbert, Sarah H. ^[1]; ^[1]

Univ. of California, Los Angeles, CA (United States)

When an electron is removed from a conjugated polymer, such as poly(3-hexylthiophene-2,5-diyl) (P3HT), the remaining hole and associated change in the polymer backbone structure from aromatic to quinoidal are referred to as a polaron. Bipolarons are created by removing the unpaired electron from an already-oxidized polymer segment. In electrochemically-doped P3HT films, polarons, and bipolarons are readily observed, but in chemically-doped P3HT films, bipolarons rarely form. This is explained by studying the effects of counterion position on the formation of polarons, strongly coupled polarons, and bipolarons using both spectroscopic and X-ray diffraction experiments and time-dependent density functional theory calculations. The counterion positions control whether two polarons spin-pair to form a bipolaron or whether they strongly couple without spin-pairing are found. When two counterions lie close to the same polymer segment, bipolarons can form, with an absorption spectrum that is blueshifted from that of a single polaron. Otherwise, polarons at high concentrations do not spin-pair, but instead J-couple, leading to a redshifted absorption spectrum. The counterion location needed for bipolaron formation is accompanied by a loss of polymer crystallinity. Finally, these results explain the observed formation order of single polarons, coupled single polarons, and singlet bipolarons in electrochemically- and chemically-doped conjugated polymers.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2423331

Alternate ID(s):: OSTI ID: 1957847

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 19 Vol. 33; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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