Evolution of the Ionization Energy in Two- and Three-Dimensional Thin Films of Pentacene Grown on Silicon Oxide Surfaces

The ionization energy (IE) of pentacene in two- and three-dimensional (2D and 3D) thin films and its evolution with coverage were studied via photoelectron yield spectroscopy in ambient conditions. In the 2D thin films, the IE of pentacene was found to be nearly constant at 4.91 eV, irrespective of its island size, for an average island size exceeding 1.6 × 10⁴ nm². In the 3D thin films, however, a reduction in IE by 0.04 eV was clearly observed upon stacking an additional molecular layer on top of the monolayer film, and the IE decreased to 4.73 eV at 20 monolayers. These experimental findings demonstrate the IE evolution in the buried layers of the 3D thin films and the significant impact of the neighboring molecular layers on the IE in layered systems with molecular aggregation.