Morphology, Energy Level Alignment, and Charge Transfer at the Protoporphyrin IX-Semiconductor Interface

The combination of molecular catalysts and semiconductor substrates in hybrid heterogeneous photo- or electrocatalytic devices could yield synergistic effects that result in enhanced activity and long-term stability. The extent of synergy strongly depends on the electronic interactions and energy level alignment between the molecular states and the valence and conduction band of the substrate. These properties of hybrid interfaces are investigated for a model system composed of protoporphyrin IX (PPIX) as a stand-in for molecular catalysts and a variety of semiconductor substrates. Monolayers of PPIX are deposited using Langmuir-Blodgett deposition. Their morphology is studied in dependence of the deposition surface pressure to achieve a high-quality, dense coverage. By making use of ultraviolet-visible spectroscopy and ultraviolet photoelectron spectroscopy, the band alignment is determined by the vacuum level and incorporates an interface dipole of 0.4 eV independent of the substrate. The HOMO, LUMO, and LUMO+1 levels were determined to be at 5.6, 3.7, and 2.7 eV below the vacuum level, respectively. The quenching of PPIX photoluminescence in dependence of the potential gradient between excited state and electron affinity of the semiconductor substrates is overall in good agreement with electron transfer processes occurring at very fast time scales on the order of femtoseconds. Nevertheless, deviations from this model become apparent for narrower band gap semiconductors, which points to an additional relevance of other processes, such as energy transfer. These findings highlight the importance of matching the semiconductor to the molecular catalyst to prevent undesirable deactivation pathways.