Stability of push-pull small molecule donors for organic photovoltaics: Spectroscopic degradation of acceptor endcaps on benzo[1,2-: B:4,5-b ]dithiophene cores

Kristen E. Watts, Trung Nguyen, Bertrand J. Tremolet De Villers, Bharati Neelamraju, Michael A. Anderson, Wade A. Braunecker, Andrew J. Ferguson, Ross E. Larsen, Bryon W. Larson, Zbyslaw R. Owczarczyk, Jason R. Pfeilsticker, Jeanne E Pemberton, Erin L Ratcliff

Research output: Contribution to journalArticle

Abstract

High efficiency organic photovoltaic devices have relied on the development of new donor and acceptor materials to optimize opto-electronic properties, promote free carrier generation, and suppress recombination losses. With single junction efficiencies exceeding 15%, materials development must now target long-term stability. This work focuses on the photobleaching dynamics and degradation chemistries of a class of small molecule donors inspired by benzodithiophene terthiophene cores (BDT-3T) with rhodanine endcaps, which have demonstrated 9% efficiency in single junction devices and >11% in ternary cells. Density functional theory was used to design three additional molecules with similar synthetic pathways and opto-electronic properties by simply changing the electron accepting endcap to benzothiazoleacetonitrile, pyrazolone, or barbituric acid functional groups. This new class of semiconductors with equivalent redox properties enables systematic investigation into photobleaching dynamics under white light illumination in air. Degradation chemistries are assessed via unique spectroscopic signatures for the BDT-3T cores and the endcaps using photoelectron spectroscopies. We show that the pyrazolone undergoes significant degradation due to ring opening, resulting in complete bleaching of the chromophore. The barbituric and rhodanine endcap molecules have moderate stability, while the benzothiazoleacetonitrile group produces the most stable chromophore despite undergoing some oxidative degradation. Collectively, our results suggest the following: (i) degradation is not just dependent on redox properties; (ii) core group stability is not independent of the endcap choice; and (iii) future design of high efficiency materials must consider both photo and chemical stability of the molecule as a whole, not just individual donor or acceptor building blocks.

Original languageEnglish (US)
Pages (from-to)19984-19995
Number of pages12
JournalJournal of Materials Chemistry A
Volume7
Issue number34
DOIs
StatePublished - Jan 1 2019

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Rhodanine
Degradation
Molecules
Photobleaching
Chromophores
Electronic properties
Chemical stability
Photoelectron spectroscopy
Bleaching
Functional groups
Density functional theory
Lighting
Semiconductor materials
Acids
Electrons
Air
N-((2,3-dihydro-1,4-benzodioxin-2-yl)methyl)-5-methoxy-1H-indole-3-ethanamine
Oxidation-Reduction
pyrazolone

ASJC Scopus subject areas

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Cite this

Stability of push-pull small molecule donors for organic photovoltaics : Spectroscopic degradation of acceptor endcaps on benzo[1,2-: B:4,5-b ]dithiophene cores. / Watts, Kristen E.; Nguyen, Trung; Tremolet De Villers, Bertrand J.; Neelamraju, Bharati; Anderson, Michael A.; Braunecker, Wade A.; Ferguson, Andrew J.; Larsen, Ross E.; Larson, Bryon W.; Owczarczyk, Zbyslaw R.; Pfeilsticker, Jason R.; Pemberton, Jeanne E; Ratcliff, Erin L.

In: Journal of Materials Chemistry A, Vol. 7, No. 34, 01.01.2019, p. 19984-19995.

Research output: Contribution to journalArticle

Watts, KE, Nguyen, T, Tremolet De Villers, BJ, Neelamraju, B, Anderson, MA, Braunecker, WA, Ferguson, AJ, Larsen, RE, Larson, BW, Owczarczyk, ZR, Pfeilsticker, JR, Pemberton, JE & Ratcliff, EL 2019, 'Stability of push-pull small molecule donors for organic photovoltaics: Spectroscopic degradation of acceptor endcaps on benzo[1,2-: B:4,5-b ]dithiophene cores', Journal of Materials Chemistry A, vol. 7, no. 34, pp. 19984-19995. https://doi.org/10.1039/c9ta06310b
Watts, Kristen E. ; Nguyen, Trung ; Tremolet De Villers, Bertrand J. ; Neelamraju, Bharati ; Anderson, Michael A. ; Braunecker, Wade A. ; Ferguson, Andrew J. ; Larsen, Ross E. ; Larson, Bryon W. ; Owczarczyk, Zbyslaw R. ; Pfeilsticker, Jason R. ; Pemberton, Jeanne E ; Ratcliff, Erin L. / Stability of push-pull small molecule donors for organic photovoltaics : Spectroscopic degradation of acceptor endcaps on benzo[1,2-: B:4,5-b ]dithiophene cores. In: Journal of Materials Chemistry A. 2019 ; Vol. 7, No. 34. pp. 19984-19995.
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