Kouki Akaike

Energy-level alignment at organic heterointerfaces

Quantitative modeling demystifies the complex and diverse energetics observed at interfaces between organic semiconductors. Today’s champion organic (opto-)electronic devices comprise an ever-increasing number of different organic-semiconductor layers. The functionality of these complex heterostructures largely derives from the relative alignment of the frontier molecular-orbital energies in each layer with respect to those in all others. Despite the technological relevance of the energy-level alignment at organic heterointerfaces, and despite continued scientific interest, a reliable model that can quantitatively predict the full range of phenomena observed at such interfaces is notably absent. We identify the limitations of previous attempts to formulate such a model and highlight inconsistencies in the interpretation of the experimental data they were based on. We then develop a theoretical framework, which we demonstrate to accurately reproduce experiment. Applying this theory, a comprehensive overview of all possible energy-level alignment scenarios that can be encountered at organic heterojunctions is finally given. These results will help focus future efforts on developing functional organic interfaces for superior device performance.

Fermi level pinning induced electrostatic fields and band bending at organic heterojunctions

The energy level alignment at interfaces between organic semiconductors is of direct relevance to understand charge carrier generation and recombination in organic electronic devices. Commonly, work function changes observed upon interface formation are interpreted as interface dipoles. In this study, using ultraviolet and X-ray photoelectron spectroscopy, complemented by electrostatic calculations, we find a huge work function decrease of up to 1.4 eV at the C60 (bottom layer)/zinc phthalocyanine (ZnPc, top layer) interface prepared on a molybdenum trioxide (MoO3) substrate. However, detailed measurements of the energy level shifts and electrostatic calculations reveal that no interface dipole occurs. Instead, upon ZnPc deposition, a linear electrostatic potential gradient is generated across the C60 layer due to Fermi level pinning of ZnPc on the high work function C60/MoO3 substrate, and associated band-bending within the ZnPc layer. This finding is generally of importance for understanding organic het...

Impact on electronic structure of donor/acceptor blend in organic photovoltaics by decontamination of molybdenum-oxide surface

Molybdenum oxide (MoOx) is widely used as the hole-transport layer in bulk-heterojunction organic photovoltaics (BHJ-OPVs). During the fabrication of solution-processed BHJ-OPVs on vacuum-deposited MoOx film, the film must be exposed to N2 atmosphere in a glove box, where the donor/acceptor blends are spin-coated from a mixed solution. Employing photoelectron spectroscopy, we reveal that the exposure of the MoOx film to such atmosphere contaminates the MoOx surface. Annealing the contaminated MoOx film at 160 °C for 5 min, prior to spin-coating the blend film, can partially remove the carbon and oxygen adsorbed on the MoOx surface during the exposure of MoOx. However, the contamination layer on the MoOx surface does not affect the energy-level alignment at the interface between MoOx and the donor/acceptor blend. Hence, significant improvement in the performance of BHJ-OPVs by mildly annealing the MoOx layer, which was previously reported, can be explained by the reduction of undesired contamination.