ABSTRACT
We report transient photoinduced absorption (t-PA) and magnetic field ( B)-dependent t-PA (t-MPA( B)) in a pristine low band gap π-conjugated copolymer composed of donor and acceptor moieties, namely, the poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thi-eno[3,4- b]thiophenediyl]]) (or PTB7) used in photovoltaic applications. Unlike traditional π-conjugated polymers in which the primary photoexcitations are singlet excitons (SE), in pristine PTB7 we find at short times coexistence of two primary photoexcitation species, namely, SE and triplet-triplet (TT) pair. Both species are photogenerated directly from the ground state and are spin-correlated. Although the TT pair decomposes into two separate triplet excitons (TEs) in â¼100 ps, the separated TE spins are still entangled up to â¼6 µs. At longer times, the t-MPA( B) response of the surviving TEs shows transient narrowing effect, which is attributed to a distribution of the TE size.
ABSTRACT
We have utilized a plethora of transient and steady state optical and magneto-optical spectroscopies in a broad spectral range (0.25-2.5 eV) for elucidating the primary and long-lived photoexcitations in a low band-gap π-conjugated donor-acceptor (DA) copolymer used for efficient photovoltaic solar cells. We show that both singlet excitons (SE) and intrachain triplet-triplet (TT) pairs are photogenerated in the DA-copolymer chains. From the picosecond transient magnetic field response of these species we conclude that the SE and TT spin states are coupled. The TT decomposition into two intrachain geminate triplet excitons maintains spin coherence and thus their spin entanglement lasts into the microsecond time domain.
ABSTRACT
We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally.
