Metallic and Semiconducting Single-Walled Carbon Nanotubes: Differentiating Individual SWCNTs by Their Carbon 1s Spectra

The C 1s inner shell excitation spectra of individual metallic and semiconducting single-walled carbon nanotubes (SWCNTs) were measured using high-resolution electron energy loss spectroscopy in an aberration-corrected transmission electron microscope (TEM-EELS). On the basis of its diameter, the metallic SWCNT is most likely a (10,10) sample, whereas (11,12) and a number of other chiral vectors are consistent with the diameter of the semiconducting SWCNTs. The C 1s X-ray absorption spectra of the same electronically pure SWCNT materials were measured as individual bundles or agglomerations of bundles by scanning transmission X-ray microscopy. Spectral differences in the C 1s -> pi* transitions of metallic and semiconducting species, related to differences in the van Hove singularities in their unoccupied states, are observed by both methods. The fine structure of the C 1s -> pi* transitions is similar to that recently reported from nonspatially resolved X-ray absorption spectroscopy of ensemble samples of high-purity metallic and semiconducting SWCNTs. The quality of the TEM-EELS spectra of individual SWCNTs is such that the line shape can be used to identify if they are metallic or semiconducting, thereby opening up the possibility to interrogate the electronic state of single-SWCNT devices. A strong X-ray linear dichroism in the C 1s -> pi* band of both types of SWCNTs was observed.