Characterization of the polymer energy landscape in polymer:fullerene bulk heterojunctions with pure and mixed phases

Sean Sweetnam, Kenneth Graham, Guy Olivier Ngongang Ndjawa, Thomas Heumüller, Jonathan A. Bartelt, Timothy M. Burke, Wentao Li, Wei You, Aram Amassian, Michael D. McGehee

Research output: Contribution to journalArticlepeer-review

193 Scopus citations


Theoretical and experimental studies suggest that energetic offsets between the charge transport energy levels in different morphological phases of polymer:fullerene bulk heterojunctions may improve charge separation and reduce recombination in polymer solar cells (PSCs). In this work, we use cyclic voltammetry, UV-vis absorption, and ultraviolet photoelectron spectroscopy to characterize hole energy levels in the polymer phases of polymer:fullerene bulk heterojunctions. We observe an energetic offset of up to 150 meV between amorphous and crystalline polymer due to bandgap widening associated primarily with changes in polymer conjugation length. We also observe an energetic offset of up to 350 meV associated with polymer:fullerene intermolecular interactions. The first effect has been widely observed, but the second effect is not always considered despite being larger in magnitude for some systems. These energy level shifts may play a major role in PSC performance and must be thoroughly characterized for a complete understanding of PSC function.
Original languageEnglish (US)
Pages (from-to)14078-14088
Number of pages11
JournalJournal of the American Chemical Society
Issue number40
StatePublished - Sep 29 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This publication was based on work supported by the Center for Advanced Molecular Photovoltaics (CAMP) (award no. KUS-C1-01S-21), made possible by KAUST. S.S. acknowledges support from the National Science Foundation through the National Science Foundation Graduate Research Fellowship under grant no. DGE-114747 and support from Stanford University through a Benchmark Stanford Graduate Fellowship. K.R.G and A.A. acknowledge SABIC for a postdoctoral fellowship. G.O.N.N., K.R.G, M.D.M., and A.A. acknowledge the Office of Competitive Research Funds for a GRP-CF award. T.H. gratefully acknowledges a "DAAD Doktorantenstipendium" and the SFB 953 "Synthetic Carbon Allotropes". J.A.B. acknowledges government support by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program. We thank the group of Martin Heeney for providing the pBTTT used for this study and William R. Mateker for his assistance with manuscript preparation.

ASJC Scopus subject areas

  • Biochemistry
  • Colloid and Surface Chemistry
  • General Chemistry
  • Catalysis


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