Publication date: 15th December 2025
Energy level alignment between organic semiconductors delicately depends on the interfacial morphology between donor and acceptor. Specifically, crystallization or aggregation, as well as amorphous blend phases, impact on the molecular energy levels and interfacial transitions through charge-transfer states. This has been already shown using a conventional polymer-fullerene bulk heterojunction. On the other hand, fluorination can modify both, the energy levels as well as the tendency of pristine phases for aggregation and crystallization. While fluorination may generally lead through increased electrostatic interaction to more tightly packed single phases, not all molecular sites are suitable to reach proper aggregation. Fluorination can thus also cause non-covalent conformational blocking instead of locking. We have investigated the impact of fluorination on single material energy levels – including the study of their optical and electronic properties. Comparison of the two allows us to detect exciton binding energies quantitatively – an otherwise hidden but important property of organic semiconductors. The influence of fluorination of polymeric donors or non-fullerene acceptors was investigated in more detail for model mixtures. Even though not directly detectable, energy level adjustments that occur in this process can be plausibly linked in particular to the influence of local electric fields due to quadrupolar molecular properties.
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