Swift heavy ion irradiation induced modifications in the optical band gap and Urbach's tail in polyaniline nanofibers

Optical band gap and Urbach tail width of HCl and CSA doped polyaniline (PAni) nanofibers and the ion beam induced modifications in the band gap and Urbach's tail of the samples have been studied employing UV-Vis absorption spectroscopy. All the major bands appearing in the FTIR spectra exhibit a decrease in intensity and broadening in their band widths upon interaction with the highly energetic ion beams. This suggests that SHI irradiation induces chain-scissioning events in the PAni nanofibers. An interesting result that comes out from the FTIR analysis is a transition from the benzenoid to quinoid states in the PAni chains, which reveals that there is a decrease in the degree of conjugation in the polymer upon irradiation. Optical absorption studies indicate three direct allowed transitions at ∼2.64, 3.61 and 4.08 eV for HCl doped PAni nanofibers and at ∼2.62, 3.49 and 4.02 eV for the CSA doped PAni nanofibers. The optical band gap is found to increase with increasing ion fluence which may be attributed to the reduction in the fiber diameters upon irradiation, which is corroborated by TEM analysis. Increase in the optical band gap also points out to a decrease in the conjugation length due to the larger torsion angles between the adjacent phenyl rings of the polymer with respect to the plane of the nitrogen atoms, which is also supported by FTIR results. The Urbach tail width decreases with increasing ion fluence indicating that structural disorders are annealed out of the PAni nanofibers which is also observed from the plots of (αhν)2 against photon energy (hν) for HCl doped PAni nanofibers. The quantum confinement effect is confirmed by fact that a band gap exhibits a linear dependence on the inverse of the square of the radius of the PAni nanofibers. Infact, the increase in the optical band gap may be a combined effect of the decrease in the Urbach band width and the quantum confinement effect.