The conductivity of graphite oxide films is modulated using reducing agents. It is found that the sheet resistance of graphite oxide film reduced using sodium borohydride (NaBH4) is much lower than that of films reduced using hydrazine (N2H4). This is attributed to the formation of CN groups in the N2H4 case, which may act as donors compensating the hole carriers in reduced graphite oxide. In the case of NaBH4 reduction, the interlayer distance is first slightly expanded by the formation of intermediate boron oxide complexes and then contracted by the gradual removal of carbonyl and hydroxyl groups along with the boron oxide complexes. The fabricated conducting film comprising a NaBH4‐reduced graphite oxide reveals a sheet resistance comparable to that of dispersed graphene.
We investigated the modulation of optical properties of single-walled carbon nanotubes (SWCNTs) by AuCl 3 doping. The van Hove singularity transitions (E 11 (S), E 22 (S), E 11 (M)) in absorption spectroscopy disappeared gradually with an increasing doping concentration and a new peak appeared at a high doping concentration. The work function was downshifted up to 0.42 eV by a strong charge transfer from the SWCNTs to AuCl 3 by a high level of p-doping. We propose that this large work function shift forces the Fermi level of the SWCNTs to be located deep in the valence band, i.e., highly degenerate, creating empty van Hove singularity states, and hence the work function shift invokes a new asymmetric transition in the absorption spectroscopy from a deeper level to newly generated empty states.
Various viologens have been used to control the doping of single-walled carbon nanotubes (SWCNTs) via direct redox reactions. A new method of extracting neutral viologen (V(0)) was introduced using a biphase of toluene and viologen-dissolved water. A reductant of sodium borohydride transferred positively charged viologen (V(2+)) into V(0), where the reduced V(0) was separated into toluene with high separation yield. This separated V(0) solution was dropped on carbon nanotube transistors to investigate the doping effect of CNTs. With a viologen concentration of 3 mM, all the p-type CNT transistors were converted to n-type with improved on/off ratios. This was achieved by donating electrons spontaneously to CNTs from neutral V(0), leaving energetically stable V(2+) on the nanotube surface again. The doped CNTs were stable in water due to the presence of hydrophobic V(0) at the outermost CNT transistors, which may act as a protecting layer to prevent further oxidation from water.
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