Electronic and vibrational spectroscopy studies of PffBT4T π -conjugated donor-acceptor copolymer

Shai R. Vardeny, Sangita Baniya, Evan Lafalce, Nasser Peyghambarian, Z. Valy Vardeny

Research output: Contribution to journalArticlepeer-review

3 Scopus citations


We used a variety of optical spectroscopies to investigate the charge excitations and correlated infrared (IR)-active and Raman-active vibrations in poly[(difluoro-benzothiadiazol-diyl)-alt-(di(2-octyldodecyl)-quaterthiophen-diyl)], PffBT4T, a π-conjugated donor-acceptor (DA) copolymer, which, when blended with fullerene PCBM molecules, serves as an active layer in high-performance photovoltaic solar cells. The applied optical spectroscopies in films of pristine PffBT4T and PffBT4T/PCBM blend include absorption, photoluminescence, electroabsorption, photoinduced absorption (PA), and resonant Raman scattering. We found that the PffBT4T copolymer chain contains 11 strongly coupled Raman-active vibrational modes, which are renormalized upon photogeneration of charge polarons onto the chain. As the lower energy polaron absorption band overlaps with the renormalized vibrational modes, they appear in the PA spectrum as antiresonance (AR) lines superposed onto the induced polaron absorption band. We show that the Raman scattering, doping induced, and photoinduced AR spectra in PffBT4T are well explained by the amplitude mode model (AMM), where a single vibrational propagator describes the renormalized Raman modes and their related photoinduced AR intensities in detail. Surprisingly, we found that two of the IR-active modes in the pristine copolymer must be included in the AMM propagator for explaining the complete photoinduced AR spectrum. This feature is unique to DA-copolymers and indicates that some intrachain C 2v symmetry breaking occurs because of the different electron affinities of the donor and acceptor moieties.

Original languageEnglish (US)
Article number032203
JournalJournal of Photonics for Energy
Issue number3
StatePublished - Jul 1 2018


  • amplitude modes model
  • doping-induced absorption
  • electroabsorption
  • infrared-absorption
  • photoinduced absorption
  • polaron excitations, antiresonances
  • resonant Raman scattering
  • π-conjugated copolymer

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Renewable Energy, Sustainability and the Environment


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