Ring-fusion as a perylenediimide dimer design concept for high-performance non-fullerene organic photovoltaic acceptors

Patrick E. Hartnett, H. S S Ramakrishna Matte, Nicholas D. Eastham, Nicholas E. Jackson, Yilei Wu, Lin X. Chen, Mark A Ratner, Robert P. H. Chang, Mark C Hersam, Michael R Wasielewski, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

A series of perylenediimide (PDI) dimers are evaluated as acceptors for organic photovoltaic (OPV) cells. The materials are characterized using a wide variety of physical and computational techniques. These dimers are first linked at the bay position of each PDI molecule via an aromatic spacer; subsequent photocyclization affords ring-fused dimers. Thus, photocyclization of the thiophene-linked dimer 2,5-bis-[N,N′-bis-perylenediimide-1-yl]-Thiophene (T1) affords the twisted acceptor [2,3-b:2′,3′-d]-bis-[N,N′-bis-perylenediimide-1,12-yl]-Thiophene (T2), while photocyclization of the thienothiophene-linked dimer, 2,5-bis-[N,N′-bis-perylenediimide-1-yl]-Thienothiophene (TT1) affords the planar acceptor [2,3-b:2′,3′-d]-bis-[N,N′-bis-perylenediimide-1,12-yl]-Thienothiophene (TT2). Furthermore, a dimer linked by a phenylene group, 1,4-bis-[N,N′-bis-perylenediimide-1-yl]-benzene (Ph1), can be selectively photocyclized to form either the twisted dimer, [1,2:3,4]-bis-[N,N′-bis-perylenediimide-1,12-yl]-benzene (Ph1a) or the planar dimer [1,2:4,5]-bis-[N,N′-bis-perylenediimide-1,12-yl]-benzene (Ph2b). Ring-fusion results in increased electronic coupling between the PDI units, and increased space-charge limited thin film electron mobility. While charge transport is efficient in bulk-heterojunction blends of each dimer with the polymeric donor PBDTT-FTTE, in the case of the twisted dimers ring fusion leads to a significant decrease in geminate recombination, hence increased OPV photocurrent density and power conversion efficiency. This effect is not observed in planar dimers where ring fusion leads to increased crystallinity and excimer formation, decreased photocurrent density, and decreased power conversion efficiency. These results argue that ring fusion is an effective approach to increasing OPV bulk-heterojunction charge carrier generation efficiency in PDI dimers as long as they remain relatively amorphous, thereby suppressing excimer formation and coulombically trapped charge transfer states.

Original languageEnglish
Pages (from-to)3543-3555
Number of pages13
JournalChemical Science
Volume7
Issue number6
DOIs
Publication statusPublished - 2016

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Dimers
Fusion reactions
Thiophenes
Benzene
Photocurrents
Conversion efficiency
Heterojunctions
perylenediimide
Charge transfer
Photovoltaic cells
Electron mobility
Charge carriers
Electric space charge
Thin films
Molecules

ASJC Scopus subject areas

  • Chemistry(all)

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Hartnett, P. E., Ramakrishna Matte, H. S. S., Eastham, N. D., Jackson, N. E., Wu, Y., Chen, L. X., ... Marks, T. J. (2016). Ring-fusion as a perylenediimide dimer design concept for high-performance non-fullerene organic photovoltaic acceptors. Chemical Science, 7(6), 3543-3555. https://doi.org/10.1039/c5sc04956c

Ring-fusion as a perylenediimide dimer design concept for high-performance non-fullerene organic photovoltaic acceptors. / Hartnett, Patrick E.; Ramakrishna Matte, H. S S; Eastham, Nicholas D.; Jackson, Nicholas E.; Wu, Yilei; Chen, Lin X.; Ratner, Mark A; Chang, Robert P. H.; Hersam, Mark C; Wasielewski, Michael R; Marks, Tobin J.

In: Chemical Science, Vol. 7, No. 6, 2016, p. 3543-3555.

Research output: Contribution to journalArticle

Hartnett, Patrick E. ; Ramakrishna Matte, H. S S ; Eastham, Nicholas D. ; Jackson, Nicholas E. ; Wu, Yilei ; Chen, Lin X. ; Ratner, Mark A ; Chang, Robert P. H. ; Hersam, Mark C ; Wasielewski, Michael R ; Marks, Tobin J. / Ring-fusion as a perylenediimide dimer design concept for high-performance non-fullerene organic photovoltaic acceptors. In: Chemical Science. 2016 ; Vol. 7, No. 6. pp. 3543-3555.
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AU - Jackson, Nicholas E.

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N2 - A series of perylenediimide (PDI) dimers are evaluated as acceptors for organic photovoltaic (OPV) cells. The materials are characterized using a wide variety of physical and computational techniques. These dimers are first linked at the bay position of each PDI molecule via an aromatic spacer; subsequent photocyclization affords ring-fused dimers. Thus, photocyclization of the thiophene-linked dimer 2,5-bis-[N,N′-bis-perylenediimide-1-yl]-Thiophene (T1) affords the twisted acceptor [2,3-b:2′,3′-d]-bis-[N,N′-bis-perylenediimide-1,12-yl]-Thiophene (T2), while photocyclization of the thienothiophene-linked dimer, 2,5-bis-[N,N′-bis-perylenediimide-1-yl]-Thienothiophene (TT1) affords the planar acceptor [2,3-b:2′,3′-d]-bis-[N,N′-bis-perylenediimide-1,12-yl]-Thienothiophene (TT2). Furthermore, a dimer linked by a phenylene group, 1,4-bis-[N,N′-bis-perylenediimide-1-yl]-benzene (Ph1), can be selectively photocyclized to form either the twisted dimer, [1,2:3,4]-bis-[N,N′-bis-perylenediimide-1,12-yl]-benzene (Ph1a) or the planar dimer [1,2:4,5]-bis-[N,N′-bis-perylenediimide-1,12-yl]-benzene (Ph2b). Ring-fusion results in increased electronic coupling between the PDI units, and increased space-charge limited thin film electron mobility. While charge transport is efficient in bulk-heterojunction blends of each dimer with the polymeric donor PBDTT-FTTE, in the case of the twisted dimers ring fusion leads to a significant decrease in geminate recombination, hence increased OPV photocurrent density and power conversion efficiency. This effect is not observed in planar dimers where ring fusion leads to increased crystallinity and excimer formation, decreased photocurrent density, and decreased power conversion efficiency. These results argue that ring fusion is an effective approach to increasing OPV bulk-heterojunction charge carrier generation efficiency in PDI dimers as long as they remain relatively amorphous, thereby suppressing excimer formation and coulombically trapped charge transfer states.

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