Solid State Spectroelectrochemistry of Redox Reactions in Polypyrrole/Oxide Molecular Heterojunctions

To understand the mechanism of bias-induced resistance switching observed in polypyrrole (PPy) based solid state junctions, in situ UV-vis absorption spectroscopy was employed to monitor oxidation states within PPy layers in solution and in PPy/metal oxide junctions. For PPy layers in acetonitrile, oxidation led primarily to cationic polaron formation, while oxidation in 0.1 M NaOH in H2O resulted in imine formation, caused by deprotonation of polarons. On the basis of these results in solution, spectroelectrochemistry was used to monitor bias-induced formation of polarons and imines in PPy layers incorporated into solid state carbon/PPy/Al2O3/Pt junctions. A positive bias on the carbon electrode caused PPy oxidation, with the formation of polaron and imine species strongly dependent on the surrounding environment. The spectral changes associated with polarons or imines were stable for at least several hours after the applied bias, while a negative bias reversed the absorbance changes back to the initial PPy spectrum. These results indicate that PPy can be oxidized in nominally solid state devices, and the formation of stable polarons is dependent on the tendency for deprotonation of the polaron to the imine. Since PPy conductivity depends strongly on the polaron concentration, monitoring its concentration is critical to determining resistance switching mechanisms. Furthermore, the importance of ion mobility and OH- generation through H2O reduction at the Pt contact are discussed.