Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers

Fauvell, Thomas J.; Cai, Zhengxu; Kirschner, Matthew S.; Helweh, Waleed; Kim, Pyosang; Zheng, Tianyue; Schaller, Richard D.; Yu, Luping; Chen, Lin X.

doi:10.3390/molecules25102441

Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers

Journal Article · Sat May 23 00:00:00 EDT 2020 · Molecules

DOI:https://doi.org/10.3390/molecules25102441· OSTI ID:1798835

Fauvell, Thomas J. ^[1]; Cai, Zhengxu ^[2]; ^[1]; Helweh, Waleed ^[3]; Kim, Pyosang ^[1]; Zheng, Tianyue ^[4]; Schaller, Richard D. ^[1]; Yu, Luping ^[5]; Chen, Lin X. ^[1]

Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Chicago, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Northwestern Univ., Evanston, IL (United States); Univ. of Chicago, IL (United States)

Recent studies have shown that molecular aggregation structures in precursor solutions of organic photovoltaic (OPV) polymers have substantial influence on polymer film morphology, exciton and charge carrier transport dynamics, and hence, the resultant device performance. To distinguish photophysical impacts due to increasing π-conjugation from chain lengthening and π–π stacking from single/multi chain aggregation in solution and film, we used oligomers of a well-studied charge transfer polymer PTB7 with different lengths as models to reveal intrinsic photophysical properties of a conjugated segment in the absence of inter-segment aggregation. In comparison with previously studied photophysical properties in polymeric PTB7, we found that oligomer dynamics are dominated by a process of planarization of the conjugated backbone into a quinoidal structure that resembles the self-folded polymer and that, when its emission is isolated, this quinoidal excited state resembling the planar polymer chain exhibits substantial charge transfer character via solvent-dependent emission shifts. Furthermore, the oligomers distinctly lack the long-lived charge separated species characteristic of PTB7, suggesting that the progression from charge transfer character in isolated chains to exciton splitting in neat polymer solution is modulated by the interchain interactions enabled by self-folding.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0001059

OSTI ID:: 1798835

Journal Information:: Molecules, Journal Name: Molecules Journal Issue: 10 Vol. 25; ISSN 1420-3049

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers

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