title: Control of intrachain charge transfer in model systems for block copolymer photovoltaic materials.
abstract: We report the electronic properties of the conjugated coupling between a donor polymer and an acceptor segment serving as a model for the coupling in conjugated donor-acceptor block copolymers. These structures allow the study of possible intrachain photoinduced charge separation, in contrast to the interchain separation achieved in conventional donor-acceptor blends. Depending on the nature of the conjugated linkage, we observe varying degrees of modification of the excited states, including the formation of intrachain charge transfer excitons. The polymers comprise a block (typically 18 repeat units) of P3HT, poly(3-hexyl thiophene), coupled to a single unit of F8-TBT (where F8 is dioctylfluorene, and TBT is thiophene-benzothiadiazole-thiophene). When the P3HT chain is linked to the TBT unit, we observe formation of a localized charge transfer state, with red-shifted absorption and emission. Independent of the excitation energy, this state is formed very rapidly (<40 fs) and efficiently. Because there is only a single TBT unit present, there is little scope for long-range charge separation and it is relatively short-lived, <1 ns. In contrast, when the P3HT chain and TBT unit are separated by the wider bandgap F8 unit, there is little indication for modification of either ground or excited electronic states, and longer-lived charge separated states are observed.
authors.affiliation: Cavendish Laboratory, University of Cambridge , J. J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom.
authors.forename: Kerr
authors.initials: K
authors.lastname: Johnson
authors.forename: Ya-Shih
authors.initials: YS
authors.lastname: Huang
authors.forename: Sven
authors.initials: S
authors.lastname: Huettner
authors.forename: Michael
authors.initials: M
authors.lastname: Sommer
authors.forename: Martin
authors.initials: M
authors.lastname: Brinkmann
authors.forename: Rhiannon
authors.initials: R
authors.lastname: Mulherin
authors.forename: Dorota
authors.initials: D
authors.lastname: Niedzialek
authors.forename: David
authors.initials: D
authors.lastname: Beljonne
authors.forename: Jenny
authors.initials: J
authors.lastname: Clark
authors.forename: Wilhelm T S
authors.initials: WT
authors.lastname: Huck
authors.forename: Richard H
authors.initials: RH
authors.lastname: Friend