Theoretical investigation on graphene induced self-alignment of donor-acceptor structures

Non-covalent functionalization of graphene (Gr) with conducting polymers (CPs) improves the electrical and mechanical properties of both materials owing to the noncovalent 7C-7C stacking interaction between the surface and the aromatic rings in CPs. However, a comprehensive understanding of the self-organization and chain orientation of CPs on the Gr surface remains lacking, which may limit the engineering of CP-Gr complexes with optimized morphology for optoelectronic applications. This study focuses on the Density Functional Theory (DFT) calculations and homemade Python programming code to investigate the self-organization of donor (D)acceptor (A) type molecules on the Gr surface, aiming to elucidate factors governing the direction of selfalignment. Specifically, basic structural parameters characterizing the aromatic D-A molecules, such as the intramolecular aromatic ring distances, are explored to determine the rules for the preferred alignment direction of the CP monomers on the Gr surface, either in armchair or zigzag paths. Additionally, the influence of Gr on the morphological properties of aromatic molecules, variations in interaction energies between Gr and D-A-D systems with changing A units, and the impact of Gr size on molecular fitting characteristics are examined. The accurate determination of chain alignment direction, which can be applied for all conjugated small molecules and polymers at 2D material interfaces is crucial for guiding experimental studies aimed at tailoring structures and enhanced properties, such as promoting the crystalline domains with high electrical conductivity.