Doping-dependent charge injection and band alignment in organic field-effect transistors

We have studied metal/organic semiconductor charge injection in poly(3-hexylthiophene) (P3HT) field-effect transistors with Pt and Au electrodes as a function of annealing in a vacuum. At low impurity dopant densities, Au/P3HT contact resistances increase and become nonohmic. In contrast, Pt/P3HT contacts remain ohmic even at far lower doping. Ultraviolet photoemission spectroscopy (UPS) reveals that metal/P3HT band alignment shifts dramatically as samples are dedoped, leading to an increased injection barrier for holes, with a greater shift for Au/P3HT. These results demonstrate that doping can drastically alter band alignment and the charge injection process at metal/organic interfaces.