Photophysics of excitons in quasi-one-dimensional organic semiconductors: Single-walled carbon nanotubes and π-conjugated polymers

摘要

The nature of the primary photoexcitations in semiconducting single-walled carbon nanotubes (S-SWCNTs) is of strong current interest. We have studied the emission spectra of S-SWCNTs and two different π-conjugated polymers in solutions and films, and have also performed ultrafast pump-probe spectroscopy on these systems with unprecedented spectral range from 0.1 to 2.6 eV. The emission spectra relative to the absorption bands are very similar in S-SWCNTs and polymers, with redshifted photoluminescence in films showing exciton migration. We also found that the transient excited state spectra of both polymers and SWCNTs contain two prominent photoinduced absorption (PA) bands (PA_1 and PA_2) that are due to photoge-nerated excitons; in the polymers these PA bands are correlated with a stimulated emission band, which is absent in the S-SWCNTs. In order to understand the similarities in the PA spectra we have performed theoretical calculations of excited state absorptions in π-conjugated polymers as well as S-SWCNTs within the same correlated electron Hamiltonian. We find strong similarities in the excitonic energy spectra of these two classes of quasi-one-dimensional materials, although there exist also subtle differences such as the occurrence of dark excitons below the optical excitons in the S-SWCNTs. In the polymers PA_1 is an excited state absorption from the optical exciton to a two-photon exciton that occurs below the continuum band threshold. In the S-SWCNTs PA_1 occurs from both the optical exciton and the dark exciton, to final states which are close in energy and again below the continuum band threshold. PA_1 therefore gives the lower limit of the binding energy of the lowest optical exciton in both π-conjugated polymers and S-SWCNTs. The binding energy of lowest exciton that belongs to the widest S-SWCNTs with diameters ≥1 nm in films is 0.3-0.4 eV, as determined by both experimental and theoretical methods.