Long-lived charge carrier generation in ordered films of a covalent perylenediimide-diketopyrrolopyrrole-perylenediimide molecule

The photophysics of a covalently linked perylenediimide-diketopyrrolopyrrole-perylenediimide acceptor-donor-acceptor molecule (PDI-DPP-PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in tau = 3.1 +/- 0.2 ps, with charge recombination in tau = 340 +/- 10 ps, while in unannealed/disordered films of 1, charge separation occurs in tau < 250 fs, while charge recombination displays a multiexponential decay in similar to 6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, upon CH2Cl2 vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron-hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for similar to 4 mu s. This result has significant implications for the design of organic solar cells based on covalent donor-acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems.