Photophysics of quasi-one-dimensional excitons in pi-conjugated polymers and semiconducting single-walled carbon nanotubes.

摘要

In this work we studied the ultrafast dynamics of photoexcitations in pi-conjugated organic semiconductors and semiconducting single-walled carbon nanotubes (S-NTs), using a low-intensity high-repetition rate laser system in the spectral range from 0.13 to 1.05 eV, and high-intensity low-repletion rate laser system in the spectral range from 1.2 to 2.5 eV, in the time domain from 100 fs to 1 ns. We also measured cw photomodulation (PM) spectroscopy of pi-conjugated polymers and photoluminescence (PL) spectra of both polymers and isolated nanotubes.; In polymers, we found that excitons are the primary photoexcitations in single polymer chains. However, polarons and polaron pairs may also be photogenerated at early time in films. We consider this process to be extrinsic in nature, namely, dependent on materials properties, temperatures, excitation photon energies, as well as the quality of films.; Both annealed and unannealed thin NT films and D2O solutions of isolated NTs were investigated. Various transient photoinduced bleaching (PB) and photoinduced absorption (PA) bands were observed, which also showed photoinduced dichroism and decay together after taking into account the PB spectral shift. The PL emission shows polarization degree. We therefore conclude that the primary photoexcitations in S-NT are excitons that are confined along the NTs. Prom the average PL polarization degree and the transient polarization memory decay, we estimate the PL lifetime in isolated NTs in solution to be of the order of 500 ps, coupling with the minute PL emission quantum efficiency, which indicates weak radiative transition strength.; In S-NTs and pi-polymers, the emission spectra relative to the absorption bands are very similar, as well as transient photoinduced absorption bands (PA) with a low-energy PA1 and a higher-energy PA2 in all cases. Theoretical calculations of excited state absorptions within a correlated pi-electron Hamiltonian show the same excitonic energy spectrum, illustrating the universal features of quasi-one-dimensional excitons in carbon-based pi-conjugated systems. In both cases PA1 gives the lower limit of the binding energy of the lowest optical exciton. The binding energy of lowest exciton belonging to the widest S-NTs with diameters ≥ 1 nm in films is 0.3-0.4 eV, as well as ∼ 0.9 eV in PPV polymers.