Conduction band structure of high-mobility organic semiconductors and partially dressed polaron formation.

The energy band structure provides crucial information on charge transport behaviour in organic semiconductors, such as effective mass, transfer integrals and electron-phonon coupling. Despite the discovery of the valence (the highest occupied molecular orbital (HOMO)) band structure in the 1990s, the conduction band (the lowest unoccupied molecular orbital (LUMO)) has not been experimentally observed. Here we employ angle-resolved low-energy inverse photoelectron spectroscopy to reveal the LUMO band structure of pentacene, a prototypical high-mobility organic semiconductor. The derived transfer integrals and bandwidths from the LUMO are substantially smaller than those predicted by density functional theory calculations. To reproduce this bandwidth reduction, we propose an improved (partially dressed) polaron model that accounts for the electron-intramolecular vibrational interaction with frequency-dependent coupling constants based on Debye relaxation. This model quantitatively reproduces not only the transfer integrals, but also the temperature-dependent HOMO and LUMO bandwidths, and the hole and electron mobilities. The present results demonstrate that electron mobility in high-mobility organic semiconductors is indeed limited by polaron formation.

Surface Termination of Solution-Processed CH3NH3PbI3 Perovskite Film Examined using Electron Spectroscopies.

The interfaces of a perovskite solar cell significantly influence the charge processes in the cell, which contributes to the device performance with direct implication for surface potential, electronic structure, and chemical reactivity. The properties of the interface are strongly affected by the surface termination. In this work, the combination of ultraviolet photoelectron spectroscopy (UPS) and metastable-atom electron spectroscopy is demonstrated, to examine the surface termination of a solution-processed CH3NH3PbI3 perovskite film. The results show that the surface of the CH3NH3PbI3 perovskite film is terminated with a layer consisting of CH3NH3 and I. The interface energy level alignment for both occupied and unoccupied levels between CH3NH3PbI3 and C60 is also examined using UPS and low-energy inverse photoelectron spectroscopy. It turns out that an ideal energy level alignment is established for the electron collection and hole block at the perovskite and C60 interface.