Broadening of van Hove Singularities Measured by Photoemission Spectroscopy of Single- and Mixed-Chirality Single-Walled Carbon Nanotubes

The occupied valence electronic states of single-walled carbon nanotubes (SWCNTs) are responsible for their optoelectronic properties and are unique for each SWCNT chirality. Photoemission spectroscopy (PES) is one of the few methods capable of directly measuring the electron density in the valence states of materials, but there are only a few reports which have observed the valence states of SWCNTs and no examples for single-chirality SWCNTs. Here, we prepare single- and mixed-chirality SWCNT films and characterize their valence states using PES. Chirality-pure SWCNTs were isolated using both gel permeation chromatography and single-stranded DNA-facilitated aqueous two-phase extraction from starting materials consisting of mixed-chirality species. Chirality separation and purity was confirmed with UV-vis-NIR absorption spectroscopy. SWCNT films were prepared for the single-chirality species (10,3), (7,6), (7,3), (6,5), (8,3), (9,1) along with SWCNT chirality mixture of metallic and semiconducting SWCNTs, and as-synthesized mixtures possessing a range of SWCNT diameter. PES using synchrotron radiation was completed for all samples with survey and C 1s core-level spectra obtained to confirm SWCNT coverage, defect level, and purity. Valence band PES was obtained to characterize the valence electronic states and showed significant broadening of the signal, in comparison to calculated density of states, which could not be accounted for by instrument resolution. An inverse diameter dependence of the broadening was observed with greater broadening for smaller-diameter SWCNTs. The broadening is hypothesized to be related to the photohole lifetime, which was found to be significantly longer for wide-diameter SWCNTs. The diameter dependence of the broadening and photohole lifetimes is discussed in terms of both Tomonaga-Luttinger and Landau theories of Fermi liquids.