Water-induced polaron formation at the pentacene surface: Quantum mechanical molecular mechanics simulations

Water is an omnipresent polar impurity that is expected to be the origin of many electric degradation phenomena observed in organic semiconductors. Here, we describe a microscopic model for polaron formation in the outermost layer of a pentacene crystal due to the polarization of a nearby water layer. The efficient coupling of a classical force field that describes the liquid with a tight-binding model that represents the system of the organic layer permits the calculation of nanosecond length trajectories. The model predicts that the reorientation of water dipoles stabilizes positive charge carriers on average by 0.6 eV and thus leads to a polaron trap state at the liquid interface. Thermal fluctuations of the water molecules provoke two-dimensional diffusive hopping of the charge carrier parallel to the interface with mobilities of up to 0.6 cm2 s−1 V−1 and lead to an amorphous broadening of the valence-band tail. As a consequence, water-filled nanocavities act as trapping sites in pentacene transistors. Instead, a complete wetting of the organic film is expected to result in fast thermally activated hopping transport. Polaron trapping is thus not expected to be a limiting factor for transistor-based sensors that operate under water.