Analytical investigation of the composition of plasma-induced functional groups on carbon nanotube sheets

To increase the applicability of carbon nanotubes (CNTs) oxygen-containing functional groups were generated on their widely inert surface by using glow-discharge plasmas. CNT-sheets (bucky papers) produced from the powder-like raw material were used as substrates allowing for a more defined characterization of one and the same surface by different analytical techniques. The plasma composition was analyzed by optical emission spectroscopy. Since the actual composition of the plasma-induced functional groups has still not been completely resolved, we performed an in-depth characterization of the treated samples by X-ray photoelectron (XPS) and Raman spectroscopy as well as electron spin resonance measurements. To overcome limitations of the XPS-analysis in distinguishing between groups featuring nearby binding energies, alcohol-, keto-/aldehyde-, and carboxyl-groups were tagged by derivatization techniques using fluorine-containing reagents (trifluoroaceticanhydride, trifluoromethylphenylhydrazine, and trifluoroethanol). Differential spectra were calculated to enhance the accuracy of the deconvolution of the XPS-spectra. This enabled us to determine dependencies of the plasma parameters, i.e. treatment time, process pressure, and gas composition (mixtures of Ar, O2, H2O, and H2), on the composition of the generated functional groups as well as an up to 6-fold enhancement in derivatizable groups for switching process gas from Ar/O2 to Ar/H2O.