Possessing excellent electronic and mechanical properties and great stability, single-walled carbon nanotubes (SWCNTs) are exceptionally attractive in fabricating flexible transparent conductive films. Doping is a key step to further enhance the conductivity of the SWCNT films and the reliable doping is highly needed. We developed a feasible strategy that uses solid acids such as phosphotungstic acid (PTA) to dope the SWCNT films stably relying on the nonvolatility of the dopants. The sheet resistance of the films was reduced to around a half of the original value meanwhile with no obvious change in transmittance. The doping effect maintained during a 700 days' observation. The excellent flexibility of the PTA-doped films was demonstrated by a bending test of 1000 cycles, during which the sheet resistance and transmittance was basically unaffected. The blue shifts of G band in the Raman spectra and the increase of work function measured by the Kelvin probe force microscopy both reveal the p-type doping of the films by PTA. The strong acidity of PTA plays a key role in the doping effect by increasing the redox potential of the ambient O2 and thus the Fermi level of the SWCNTs is brought down. The great feasibility and robustness of our doping strategy are desirable in the practical application of SWCNT-based flexible transparent conductive films. This strategy can be extended to the p-type doping of various CNT-based assemblies (such as sponges and forests) as well as other material families, expanding the application spectrum of polyacids.
Keywords: carbon nanotubes; doping; flexible device; phosphotungstic acid; solid acid; transparent conductive films.