Influence of NiCr/Au electrodes and multilayer thickness on the electrical properties of PANI/PVS ultrathin film grown by Lbl deposition

In the present work, we concentrate on the study of effects of metallic electrodes, multilayer thickness and temperature in ac and dc electrical conductivity of polyaniline/poly(vinyl sulfonic acid) (PANI/PVS) ultrathin films. The polymer system was obtained from layer-by-layer (Lbl) self-assembly technique on a glass substrate with an electrode array of adhesion layer of NiCr (20 nm) covered with Au (180 nm). We observed a significant and abrupt increase in the value of dc conductivity and a change of ac conductivity behavior of NiCr/Au–PANI/PVS–NiCr/Au structure when the thickness of PANI/PVS system reaches the Au layer. These effects were ascribed to the ideal contact of Au–PANI/PVS and the relative high interfacial contact resistance between PANI/PVS and NiCr, thus reducing the parallel resistance of NiCr/Au–PANI/PVS interfacial layer in an ideal parallel plate capacitor structure. Atomic Force Microscopy images confirm this assumption. Furthermore, the ac conductivity of Au–PANI/PVS–Au structure was typical of solid disordered materials. A model based on carrier hopping in a medium with randomly varying energy barriers was presented for the ac conductivity of the polymer system, which also encompasses the high dielectric constant of PANI/PVS blended films, the neutral contact Au–PANI/PVS, and the electrical resistance of NiCr–PANI/PVS interfacial layer. The model allowed separating the interface and the bulk effects in the electrical response of NiCr/Au–PANI/PVS–NiCr/Au structure and in addition the highest activation energy (35 MeV) correlated with an optimization of hopping distance (30 nm) for carriers jumps in PANI/PVS system.