Using Raman spectroscopy to elucidate the aggregation state of single-walled carbon nanotubes

Raman spectroscopy can be used to probe the aggregation state of single-walled carbon nanotubes in solution or as solids with a range of varying morphologies. Carbon nanotubes experience an orthogonal electronic dispersion when in electrical contact that broadens (from 40 meV to roughly 80 meV) and shifts the interband transition to lower energy (by 60 meV). We show that the magnitude of this shift is dependent on the extent of bundle organization and the inter-nanotube contact area. In the Raman spectrum, aggregation shifts the effective excitation profile and causes peaks to increase or decrease, depending on where the transition lies, relative to the excitation wavelength. The results are modeled using a simplified delta-function representation of nanotube electronic structure. The findings are particularly relevant for evaluating nanotube separation processes, where relative peak changes in the Raman spectrum can be confused for selective enrichment.