Modulation of charge transfer exciton dynamics in organic semiconductors using different structural arrangements

In devices based on organic semiconductors, aggregation and inter-molecular interactions play a key role in affecting the photo-physical and dynamical carrier properties of the material, potentially becoming a limiting factor to achieving high efficiency. As a consequence, a detailed understanding of the interplay between the film molecular structure and the material properties is essential to properly design devices with optimized performance. Here we demonstrate how different molecular structural arrangements modulate the charge transfer (CT) dynamics in cobalt phthalocyanine (CoPc) thin films. By transient absorption spectroscopy and time-resolved photoemission spectroscopy, we study the influence of different CoPc structures on the dynamical electronic properties, the CoPc intra and intermolecular de-excitation pathways up to 7 ns. We rationalize the ultrafast formation of triplet states in the CoPc through an electron exchange process between the single-occupied Co3dz2 orbital and p orbitals of the macrocycle, which obviate for an energetically unfavourable spin-flip. We found enhanced CT exciton lifetime in the case of the herringbone structure with respect to the brickwork one, possibly explainable by a more efficient CT exciton delocalization along the stacking axis.

Automated summary

In devices based on organic semiconductors, the aggregation and inter-molecular interactions significantly affect the photo-physical and dynamical carrier properties. Understanding the interplay between the molecular structure and material properties is crucial for designing devices with optimized performance. This study investigates how different molecular structural arrangements modulate the charge transfer dynamics in cobalt phthalocyanine thin films.