Surface electronic structure of nitrogen-doped semiconducting single-walled carbon nanotube networks

We investigated the effects of vacuum annealing on the surface electronic structure and the work function of single-walled carbon nanotubes (SWCNTs). We changed the doping type of semiconducting single-walled carbon nanotubes (semi-SWCNTs) from p-type to n-type, and investigated their optical properties. The HNO₃ treated p-type SWCNT network was converted to n-type after vacuum annealing due to formation of C-N bond. The C 1s sp² binding energy of the vacuum annealed semi-SWCNTs was shifted toward a higher binding energy about 0.42 eV, which indicates a raising Fermi level as much as 0.42 eV compared with the intrinsic semi-SWCNTs. In addition, the work function of the vacuum annealed semi-SWCNT was observed towards lower energies. It is considered that the C-N bonding of semi-SWCNTs creates a donor level near the bottom of the conduction band, thus raising the Fermi level. The ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy revealed that the increased binding energy of C 1s sp² and the decreased work function of semi-SWCNTs are caused by n-type doping after vacuum annealing.