Stabilization of electronic properties of (1R)-(−)-10-camphorsulfonic acid doped polyaniline by UV irradiation

Stability of electronic parameters of conducting polymers affects the overall performance of organic electronics. We show that UV light (254 nm) treatment of polyaniline (PANI) films, containing camphorsulfonic acid (CSA) as a dopant and cast from formic acid, decreases the film resistance and keeps their improved resistance stable for at least 4 months. It has been found that due to the different origins of these electronic properties, the resistance and work function of the PANI·CSA films are affected differently by the UV treatment. The long-term stability of the resistance is governed by morphological changes of the material. On the other hand the stability of the threshold voltage of the field-effect transistor (FET) which is an indirect measure of the work function, originates from the charge density equilibration at the PANI·CSA film/insulator interface. The FT-IR, UV–vis and circular dichroism data provide the evidence that after the UV treatment the polymer molecular structure remains intact, but some secondary structural re-arrangements of the PANI·CSA take place. These re-arrangements are resulting from the strong donor–acceptor interactions between the imine and/or amine groups of the PANI chains and the CO and SO₃⁻ groups of the doping CSA-anion. These interactions enhance significantly the mechanical rigidity of the PANI matrix. The increasing broad absorption band of the “free-carrier tail” in the FT-IR spectra correlates with the conductivity increase of the UV treated PANI·CSA film.