Impact of morphology on polaron delocalization in a semicrystalline conjugated polymer

Handle URI:
http://hdl.handle.net/10754/622784
Title:
Impact of morphology on polaron delocalization in a semicrystalline conjugated polymer
Authors:
Steyrleuthner, Robert; Zhang, Yuexing; Zhang, Lei; Kraffert, Felix; Cherniawski, Benjamin P.; Bittl, Robert; Briseno, Alejandro L.; Bredas, Jean-Luc ( 0000-0001-7278-4471 ) ; Behrends, Jan
Abstract:
We investigate the delocalization of holes in the semicrystalline conjugated polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT) by directly measuring the hyperfine coupling between photogenerated polarons and bound nuclear spins using electron nuclear double resonance spectroscopy. An extrapolation of the corresponding oligomer spectra reveals that charges tend to delocalize over 4.0-4.8 nm with delocalization strongly dependent on molecular order and crystallinity of the PBTTT polymer thin films. Density functional theory calculations of hyperfine couplings confirm that long-range corrected functionals appropriately describe the change in coupling strength with increasing oligomer size and agree well with the experimentally measured polymer limit. Our discussion presents general guidelines illustrating the various pitfalls and opportunities when deducing polaron localization lengths from hyperfine coupling spectra of conjugated polymers.
KAUST Department:
Chemical Science Program; Solar and Photovoltaic Engineering Research Center (SPERC)
Citation:
Steyrleuthner R, Zhang Y, Zhang L, Kraffert F, Cherniawski BP, et al. (2017) Impact of morphology on polaron delocalization in a semicrystalline conjugated polymer. Phys Chem Chem Phys. Available: http://dx.doi.org/10.1039/c6cp07485e.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Phys. Chem. Chem. Phys.
Issue Date:
20-Dec-2016
DOI:
10.1039/c6cp07485e
Type:
Article
ISSN:
1463-9076; 1463-9084
Sponsors:
The authors like to thank for financial support from the DFG (SPP 1601) and the Helmholtz Association (Energie-Allianz Hybrid-Photovoltaik). This work has been partly supported by King Abdullah University of Science and Technology (KAUST). We acknowledge the KAUST IT Research Computing Team for providing computational and storage resources and thank Dr Cheng Zhong, Dr Haitao Sun, and Dr Bradley D. Rose for stimulating discussions. A. L. B. acknowledges the National Science Foundation (DMR-1508627).
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C6CP07485E#!divAbstract
Appears in Collections:
Articles; Chemical Science Program; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorSteyrleuthner, Roberten
dc.contributor.authorZhang, Yuexingen
dc.contributor.authorZhang, Leien
dc.contributor.authorKraffert, Felixen
dc.contributor.authorCherniawski, Benjamin P.en
dc.contributor.authorBittl, Roberten
dc.contributor.authorBriseno, Alejandro L.en
dc.contributor.authorBredas, Jean-Lucen
dc.contributor.authorBehrends, Janen
dc.date.accessioned2017-01-29T13:51:39Z-
dc.date.available2017-01-29T13:51:39Z-
dc.date.issued2016-12-20en
dc.identifier.citationSteyrleuthner R, Zhang Y, Zhang L, Kraffert F, Cherniawski BP, et al. (2017) Impact of morphology on polaron delocalization in a semicrystalline conjugated polymer. Phys Chem Chem Phys. Available: http://dx.doi.org/10.1039/c6cp07485e.en
dc.identifier.issn1463-9076en
dc.identifier.issn1463-9084en
dc.identifier.doi10.1039/c6cp07485een
dc.identifier.urihttp://hdl.handle.net/10754/622784-
dc.description.abstractWe investigate the delocalization of holes in the semicrystalline conjugated polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT) by directly measuring the hyperfine coupling between photogenerated polarons and bound nuclear spins using electron nuclear double resonance spectroscopy. An extrapolation of the corresponding oligomer spectra reveals that charges tend to delocalize over 4.0-4.8 nm with delocalization strongly dependent on molecular order and crystallinity of the PBTTT polymer thin films. Density functional theory calculations of hyperfine couplings confirm that long-range corrected functionals appropriately describe the change in coupling strength with increasing oligomer size and agree well with the experimentally measured polymer limit. Our discussion presents general guidelines illustrating the various pitfalls and opportunities when deducing polaron localization lengths from hyperfine coupling spectra of conjugated polymers.en
dc.description.sponsorshipThe authors like to thank for financial support from the DFG (SPP 1601) and the Helmholtz Association (Energie-Allianz Hybrid-Photovoltaik). This work has been partly supported by King Abdullah University of Science and Technology (KAUST). We acknowledge the KAUST IT Research Computing Team for providing computational and storage resources and thank Dr Cheng Zhong, Dr Haitao Sun, and Dr Bradley D. Rose for stimulating discussions. A. L. B. acknowledges the National Science Foundation (DMR-1508627).en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C6CP07485E#!divAbstracten
dc.titleImpact of morphology on polaron delocalization in a semicrystalline conjugated polymeren
dc.typeArticleen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalPhys. Chem. Chem. Phys.en
dc.contributor.institutionFreie Universität Berlin, Berlin Joint EPR Lab, Institut für Experimentalphysik, Berlin, Germany. robert.steyrleuthner@fu-berlin.de j.behrends@fu-berlin.de.en
dc.contributor.institutionDepartment of Polymer Science and Engineering, Conte Research Center, University of Massachusetts, 120 Governors Drive, Amherst, MA 01003, USA.en
kaust.authorZhang, Yuexingen
kaust.authorBredas, Jean-Lucen
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