In situ optical spectroelectrochemistry of single-walled carbon nanotube thin films

A detailed study is presented on the optical absorption of thin films of single-walled carbon nanotubes (SWNT) under electrochemical conditions. The procedure for the preparation of free-standing semitransparent films of SWNT is used for the fabrication of a working electrode for transmission optical spectroelectrochemistry. The analysis of the potential dependent spectroscopic response of the SWNT film benefits from the widest possible electrochemical window, in which the charging of SWNT can safely be investigated. This electrochemical window is not limited by parasitic electrochemistry and/or galvanic breakdown reactions occurring at supporting electrode materials such as indium–tin oxide conducting glass or semitransparent Pt film, which were employed in earlier studies. Electrochemical doping of SWNT is observable at the optical absorptions, which are assigned to allowed electronic transitions between van Hove singularities in the density of states of SWNT. Furthermore, the spectral response of counterions, balancing the charging of the nanotube skeleton, is traceable at certain conditions. The latter effect is monitored here through the overtones of C–H stretching vibrations from tetrabutylammonium cations.