The optical properties of single -walled carbon nanotubes: Separation, characterization, and measurement in suspension

The one dimensional structure of single-walled carbon nanotubes (SWNTs) gives rise to optical phenomena that differ from bulk materials. This dissertation studies the separation of SWNTs dissolved in aqueous media using surfactant molecules, and the measurement of their intrinsic optical properties including absorption and emission. The SWNTs were separated from the bundled form using mechanical processing techniques such as sonication and centrifugation. A processing study, which isolated the effects of sonication frequency, sonication power, and centrifugation speed, was performed to determine the factors that lead to the best separation. The results of this study suggest that the suspensions are a mixture of individual tubes and small bundles. Prior determinations of intrinsic nanotube properties based on the assumption of isolated nanotubes will have to be revisited. The transient absorption spectrum was measured for the S11 subband region using monochromatic pump excitation at wavelengths corresponding to S22 subband transitions, where the exciting pump fluence was sufficient to create many excitons on a single nanotube. The transient decay kinetics followed a linear dependence that was proportional to 1/[special characters omitted] on a log-log scale with a slope of -0.5, which is consistent with the diffusion limited recombination of excitons in one dimension. This result suggests that the decay of photoexcitations in nanotubes is initially governed by two-body kinetics, which becomes a one-body process only in the long time limit. Our work refutes the one-electron model for the excited state relaxation of nanotubes proposed by others. When the transient decay was studied as a function of the initial exciton population, the diffusion coefficient was found to be a different constant value at each initial population. Local thermalization of the surrounding medium may cause this difference, as thermal relaxation occurs on a time scale that is longer than that of exciton recombination in SWNTs. This work further elucidates the mechanism of excited state relaxation in SWNTs, and advances the understanding of one-dimensional nanostructures