Tailoring the Weight of Surface and Intralayer Edge States to Control LUMO Energies

The energies of the frontier molecular orbitals determine the optoelectronic properties in organic films, which are crucial for their application, and strongly depend on the morphology and supramolecular structure. The impact of the latter two properties on the electronic energy levels relies primarily on nearest-neighbor interactions, which are difficult to study due to their nanoscale nature and heterogeneity. Here, an automated method is presented for fabricating thin films with a tailored ratio of surface to bulk sites and a controlled extension of domain edges, both of which are used to control nearest-neighbor interactions. This method uses a Langmuir-Schaefer-type rolling transfer of Langmuir layers (rtLL) to minimize flow during the deposition of rigid Langmuir layers composed of π-conjugated molecules. Using UV-vis absorption spectroscopy, atomic force microscopy, and transmission electron microscopy, it is shown that the rtLL method advances the deposition of multi-Langmuir layers and enables the production of films with defined morphology. The variation in nearest-neighbor interactions is thus achieved and the resulting systematically tuned lowest unoccupied molecular orbital (LUMO) energies (determined via square-wave voltammetry) enable the establishment of a model that functionally relates the LUMO energies to a morphological descriptor, allowing for the prediction of the range of accessible LUMO energies.