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dc.contributor.authorAnderson, Michael A.
dc.contributor.authorHamstra, Anna
dc.contributor.authorLarson, Bryon W.
dc.contributor.authorRatcliff, Erin L.
dc.date.accessioned2023-11-09T17:03:58Z
dc.date.available2023-11-09T17:03:58Z
dc.date.issued2023-08-07
dc.identifier.citationAnderson, M. A., Hamstra, A., Larson, B. W., & Ratcliff, E. L. (2023). Distinguishing photo-induced oxygen attack on alkyl chain versus conjugated backbone for alkylthienyl-benzodithiophene (BDTT)-based push–pull polymers. Journal of Materials Chemistry A, 11(33), 17858-17871.en_US
dc.identifier.issn2050-7488
dc.identifier.doi10.1039/d3ta03256f
dc.identifier.urihttp://hdl.handle.net/10150/670046
dc.description.abstractSynthetic design has enabled increasing power conversion efficiency advances in organic photovoltaics (OPV). One continuing knowledge gap is detailed understanding of single-material chemical (photo)stability. Many considerations are based on prior OPV-relevant donor homopolymer systems rather than the next-generation push-pull architectures. Generally, energetic offsets between the lowest occupied molecular orbital of the donor and molecular oxygen are assumed to dictate kinetics of photo-induced charge transfer to a super oxide radical. Herein we determine the ambient-induced photo-degradation pathways, presented as proposed site-specific arrow-pushing mechanisms, for five donor polymers all containing the same push unit - alkylthienyl-substituted-benzodithiophene (BDTT) - but with chemically distinct pull units. The donor-only polymer films were subject to controlled photobleaching in air as an accelerated degradation approach, coupled with simultaneous monitoring of absorptance. Sample subsets were periodically removed and analyzed with X-ray photoelectron spectroscopy, to evaluate near-surface chemical composition and oxygen additions to hetero reporter atoms on either the BDTT push unit or distinct pull unit (i.e., sulphur and nitrogen). This methodology allows us to distinguish between different mechanisms of bond cleavage and formation. Overall, we find that neither polymer redox properties nor individual push or pull unit stability are sufficient to predict photo-oxidative degradation of these polymers. Rather, there is a greater dependence on the susceptibility of unique structural groups within a polymeric system. Alkyl chain oxygen addition is generally the first attack site and direct sulfur oxidation on the conjugated backbone occurs after saturation of the alkyl chain initiation sites. This work provides a standard that could be used to evaluate relative photo-oxidative (in)stability for new OPV materials quickly - prior to time-consuming device optimization - and demonstrates an effective methodology for correlating optical degradation with chemical structure alterations via spectroscopic signatures to guide synthetic design.en_US
dc.description.sponsorshipNational Science Foundationen_US
dc.language.isoenen_US
dc.publisherRoyal Society of Chemistry (RSC)en_US
dc.rights© The Royal Society of Chemistry 2023.en_US
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en_US
dc.subjectGeneral Materials Scienceen_US
dc.subjectRenewable Energy, Sustainability and the Environmenten_US
dc.subjectGeneral Chemistryen_US
dc.titleDistinguishing photo-induced oxygen attack on alkyl chain versus conjugated backbone for alkylthienyl-benzodithiophene (BDTT)-based push–pull polymersen_US
dc.typeArticleen_US
dc.identifier.eissn2050-7496
dc.contributor.departmentDepartment of Materials Science and Engineering, University of Arizonaen_US
dc.contributor.departmentDepartment of Chemistry and Biochemistry, University of Arizonaen_US
dc.contributor.departmentDepartment of Chemical and Environmental Engineering, University of Arizonaen_US
dc.identifier.journalJournal of Materials Chemistry Aen_US
dc.description.note12 month embargo; first published 07 August 2023en_US
dc.description.collectioninformationThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at repository@u.library.arizona.edu.en_US
dc.eprint.versionFinal accepted manuscripten_US
dc.source.journaltitleJournal of Materials Chemistry A
dc.source.volume11
dc.source.issue33
dc.source.beginpage17858
dc.source.endpage17871


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