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

Abstract

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.

Authors:
 [1];  [2]; ORCiD logo [1];  [3];  [1];  [4];  [1];  [5];  [1]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Chicago, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Northwestern Univ., Evanston, IL (United States); Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1798835
Grant/Contract Number:  
AC02-06CH11357; SC0001059
Resource Type:
Accepted Manuscript
Journal Name:
Molecules
Additional Journal Information:
Journal Volume: 25; Journal Issue: 10; Journal ID: ISSN 1420-3049
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; PTB7; OPV; excited state; oligomer; structural dynamics; electronic processes

Citation Formats

Fauvell, Thomas J., Cai, Zhengxu, Kirschner, Matthew S., Helweh, Waleed, Kim, Pyosang, Zheng, Tianyue, Schaller, Richard D., Yu, Luping, and Chen, Lin X. Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers. United States: N. p., 2020. Web. doi:10.3390/molecules25102441.
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Fauvell, Thomas J., Cai, Zhengxu, Kirschner, Matthew S., Helweh, Waleed, Kim, Pyosang, Zheng, Tianyue, Schaller, Richard D., Yu, Luping, & Chen, Lin X. Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers. United States. https://doi.org/10.3390/molecules25102441
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Fauvell, Thomas J., Cai, Zhengxu, Kirschner, Matthew S., Helweh, Waleed, Kim, Pyosang, Zheng, Tianyue, Schaller, Richard D., Yu, Luping, and Chen, Lin X. Sat . "Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers". United States. https://doi.org/10.3390/molecules25102441. https://www.osti.gov/servlets/purl/1798835.
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@article{osti_1798835,
title = {Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers},
author = {Fauvell, Thomas J. and Cai, Zhengxu and Kirschner, Matthew S. and Helweh, Waleed and Kim, Pyosang and Zheng, Tianyue and Schaller, Richard D. and Yu, Luping and Chen, Lin X.},
abstractNote = {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.},
doi = {10.3390/molecules25102441},
journal = {Molecules},
number = 10,
volume = 25,
place = {United States},
year = {Sat May 23 00:00:00 EDT 2020},
month = {Sat May 23 00:00:00 EDT 2020}
}
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