Modification of the electronic structure in single-walled carbon nanotubes with aromatic amines

We investigated the interactions of two aromatic amines, N,N,N′N′‐tetramethyl‐p‐phenylenediamine (TMPD) and tetramethylpyrazine (TMP) with single‐walled carbon nanotube (SWNT) networks. Adsorption and intercalation of amine molecules in bundled SWNTs is expected to modify the electronic structure of nanotubes in a similar way as has already been observed for alkali metals. Our ab initio density functional calculations demonstrate that TMPD donates electron to the nanotube and produces donor‐like states below the conduction band whereas the effect of the TMP treatment is very weak. The electron transfer to the nanotubes has been supported experimentally by the XPS valence band spectra which show strongly modified spectral features. Especially an increase of the electronic density at the Fermi level upon adsorption of TMPD and TMP is clearly demonstrated. Rather intensive features between π* and σ* transitions in the NEXAFS spectrum of the pristine SWNTs attributed to the oxidized carbon functional groups are chemically modified upon adsorption of amines on the networks. This fact suggests that the aromatic amines evidently react with the defects, remove or replace oxygen species responsible for the p‐type doping of SWNTs, and therefore are acting as a de‐doping agent for the naturally p‐type doped semiconducting SWNTs.