ABSTRACTElectrochemical tuning of single-wall carbon nanotubes has been investigated using in situ Raman spectroscopy. We built a linear actuator from single-wall carbon nanotube mat and studied in several alkali metal (Li, Na, and K) and alkaline earth (Ca) halide solutions. The variation of bonding with electrochemical biasing was monitored using in situ Raman. This is since Raman can detect changes in C-C bond length: the radial breathing mode (RBM) at ∼190 cm−1 varies inversely with the nanotube diameter and the G band at ∼1590 cm−1 varies with the axial bond length. In addition, the intensities of both the modes vary significantly in a nonmonotonic manner pointing at the emptying/depleting or filling of the bonding and anti-bonding states - electrochemical charge injection. We discuss the variation of spectroscopic observables (intensity/frequency) of these modes providing valuable information on the charge transfer dynamics on the single-wall carbon nanotubes mat surface. We found the in-plane compressive strain (∼ -0.25%) and the charge transfer per carbon atom (fc ∼ -0.005) as an upper bound for the electrolytes used i.e. CaCl2. These results can be quantitatively understood in terms of the changes in the energy gaps between the one-dimensional van Hove singularities in the electron density of states arising possibly due to the alterations in the overlap integral of π bonds between the p orbitals of the adjacent carbon atoms. Moreover, the extent of variation of the absolute potential of the Fermi level or alternatively modification of band gap is estimated from modeling Raman intensity to be around 0.1 eV as an upper bound for CaCl2.
