Marked Consequences of Systematic Oligothiophene Catenation in Thieno[3,4-c]pyrrole-4,6-dione and Bithiopheneimide Photovoltaic Copolymers

Nanjia Zhou, Xugang Guo, Rocio Ponce Ortiz, Tobias Harschneck, Eric F. Manley, Sylvia J. Lou, Patrick E. Hartnett, Xinge Yu, Noah E. Horwitz, Paula Mayorga Burrezo, Thomas J. Aldrich, Juan T. López Navarrete, Michael R Wasielewski, Lin X. Chen, Robert P. H. Chang, Antonio Facchetti, Tobin J Marks

Research output: Contribution to journalArticle

63 Citations (Scopus)

Abstract

As effective building blocks for high-mobility transistor polymers, oligothiophenes are receiving attention for polymer solar cells (PSCs) because the resulting polymers can effectively suppress charge recombination. Here we investigate two series of in-chain donor-acceptor copolymers, PTPDnT and PBTInT, based on thieno[3,4-c]pyrrole-4,6-dione (TPD) or bithiopheneimide (BTI) as electron acceptor units, respectively, and oligothiophenes (nTs) as donor counits, for high-performance PSCs. Intramolecular S···O interaction leads to more planar TPD polymer backbones, however backbone torsion yields greater open-circuit voltages for BTI polymers. Thiophene addition progressively raises polymer HOMOs but marginally affects their band gaps. FT-Raman spectra indicate that PTPDnT and PBTInT conjugation lengths scale with nT catenation up to n = 3 and then saturate for longer oligomer. Furthermore, the effects of oligothiophene alkylation position are explored, revealing that the alkylation pattern greatly affects film morphology and PSC performance. The 3T with "outward" alkylation in PTPD3T and PBTI3T affords optimal π-conjugation, close stacking, long-range order, and high hole mobilities (0.1 cm2/(V s)). These characteristics contribute to the exceptional ∼80% fill factors for PTPD3T-based PSCs with PCE = 7.7%. The results demonstrate that 3T is the optimal donor unit among nTs (n = 1-4) for photovoltaic polymers. Grazing incidence wide-angle X-ray scattering, transmission electron microscopy, and time-resolved microwave conductivity measurements reveal that the terthiophene-based PTPD3T blend maintains high crystallinity with appreciable local mobility and long charge carrier lifetime. These results provide fundamental materials structure-device performance correlations and suggest guidelines for designing oligothiophene-based polymers with optimal thiophene catenation and appropriate alkylation pattern to maximize PSC performance.

Original languageEnglish
Pages (from-to)12565-12579
Number of pages15
JournalJournal of the American Chemical Society
Volume137
Issue number39
DOIs
Publication statusPublished - Oct 7 2015

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Polymers
Copolymers
Alkylation
Thiophenes
Thiophene
Temperature programmed desorption
Hole mobility
Carrier lifetime
Open circuit voltage
thieno(3,4-c)pyrrole-4,6-dione
Charge carriers
X ray scattering
Oligomers
Torsional stress
Raman scattering
Transistors
Energy gap
Microwaves
Polymer solar cells
Transmission electron microscopy

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Marked Consequences of Systematic Oligothiophene Catenation in Thieno[3,4-c]pyrrole-4,6-dione and Bithiopheneimide Photovoltaic Copolymers. / Zhou, Nanjia; Guo, Xugang; Ortiz, Rocio Ponce; Harschneck, Tobias; Manley, Eric F.; Lou, Sylvia J.; Hartnett, Patrick E.; Yu, Xinge; Horwitz, Noah E.; Burrezo, Paula Mayorga; Aldrich, Thomas J.; López Navarrete, Juan T.; Wasielewski, Michael R; Chen, Lin X.; Chang, Robert P. H.; Facchetti, Antonio; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 137, No. 39, 07.10.2015, p. 12565-12579.

Research output: Contribution to journalArticle

Zhou, N, Guo, X, Ortiz, RP, Harschneck, T, Manley, EF, Lou, SJ, Hartnett, PE, Yu, X, Horwitz, NE, Burrezo, PM, Aldrich, TJ, López Navarrete, JT, Wasielewski, MR, Chen, LX, Chang, RPH, Facchetti, A & Marks, TJ 2015, 'Marked Consequences of Systematic Oligothiophene Catenation in Thieno[3,4-c]pyrrole-4,6-dione and Bithiopheneimide Photovoltaic Copolymers', Journal of the American Chemical Society, vol. 137, no. 39, pp. 12565-12579. https://doi.org/10.1021/jacs.5b06462
Zhou, Nanjia ; Guo, Xugang ; Ortiz, Rocio Ponce ; Harschneck, Tobias ; Manley, Eric F. ; Lou, Sylvia J. ; Hartnett, Patrick E. ; Yu, Xinge ; Horwitz, Noah E. ; Burrezo, Paula Mayorga ; Aldrich, Thomas J. ; López Navarrete, Juan T. ; Wasielewski, Michael R ; Chen, Lin X. ; Chang, Robert P. H. ; Facchetti, Antonio ; Marks, Tobin J. / Marked Consequences of Systematic Oligothiophene Catenation in Thieno[3,4-c]pyrrole-4,6-dione and Bithiopheneimide Photovoltaic Copolymers. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 39. pp. 12565-12579.
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AU - Guo, Xugang

AU - Ortiz, Rocio Ponce

AU - Harschneck, Tobias

AU - Manley, Eric F.

AU - Lou, Sylvia J.

AU - Hartnett, Patrick E.

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AU - Burrezo, Paula Mayorga

AU - Aldrich, Thomas J.

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