Ultrafast spectroscopy of excitons in semiconducting carbon nanotubes

Abstract

Ultrafast relaxation dynamics of photoexcitations in semiconducting single walled carbon nanotubes (S-NTs) were investigated using polarized pump-probe photomodulation (with 150 fs time resolution) and cw polarized photoluminescence (PL). Both annealed and unannealed NT films and D₂O solutions of isolated NTs were investigated. Various transient photoinduced bleaching (PB) and photoinduced absorption (PA) bands, which show photoinduced dichroism, were observed in the ultrafast photomodulation spectra of <i>all</i> NT forms. Taking into account the PB spectral shift observed for NTs in solution, the PA and PB bands are seen to decay together by following a power law in time of the form (t)^-&alpha;, with &alpha; in the range of 0.7 to 1. The PL emission of S-NTs in D₂O solution shows a polarization degree that agrees with that of the transient photoinduced dichroism. We conclude that the primary photoexcitations in <i>S</i>-NTs are excitons that are confined along the NTs. From the average PL polarization degree and the transient polarization memory decay, we estimate the PL lifetime of isolated NTs in solution is of order 500ps. This relatively long PL lifetime is dominated by non-radiative decay processes, which when coupled with the tiny PL emission quantum efficiency indicates a very small radiative recombination rate, in good agreement with recent theories that include electron correlation.