We have investigated the chemical nature and the electronic structure of the interface between a low work function metal, aluminum, and a conjugated polymer semiconductor, polythiophene. We have studied the initial stages of the interface formation by depositing the metal onto the surface of a polymer film. Charge transfer processes between the metal and the polymer are analyzed using core-level x-ray photoelectron spectroscopy (XPS); the evolution upon metallization of the valence electronic levels directly related to the polymer electronic structure is followed with ultraviolet photoelectron spectroscopy (UPS). With these techniques, we investigate the deposition of aluminum on two polythiophene systems (i) the alkyl-substituted poly-3-octylthiophene and (ii) the α-sexithiophene oligomer. The experimental data are compared to the results of a recent quantum chemical study on model systems consisting of thiophene oligomers (up to sexithiophene) interacting with a few Al atoms. The interaction of polythiophene with Al atoms is found to modify dramatically the structure of the conjugated backbone, as strong carbon-aluminum bonds are formed in the α positions of the thiophene rings. A large charge transfer takes place from the Al atoms to the polymer chain, and the upper π levels of the polymer are strongly affected. The metallization is contrasted to the doping of conjugated polymers with alkali metals.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry