Oligothiophene-g-oligo(D,L-lactide) “Rod-Graft-Coil” Co-Oligomer: Self-Assembly Modulation by Processing and Formed Films Surface Morphological Diversity Characterization †

In the field of advanced functional materials, π-conjugated, electrically conductive polymers (CPs) represent a highly specialized class, intensively studied as essential in contemporary optoelectronic and biointerfaced technologies. The solution-processability of CPs represents a significant advantage; however, the interactions occurring in this state make it difficult to establish suitable strategies for controlling the resulting solid-state microstructures and the charge transport. In this context, the main aim of this paper was to analyze how the polymer architecture and other deliberately chosen design criteria, can be harnessed and easily combined with a versatile processing toward self-assembled thin films of varying surface properties. Thus, a “rod-graft-coil” polymacromonomer, denoted OTh-PDLLA,—previously synthesized via metal-free-photoinduced oxidative polymerization, yielding an oligomeric structure comprising a π-conjugated thiophene backbone with densely grafted oligo(D,L-lactide) side chains—was processed into thin films by drop-casting, in native and also in its LiClO4-treated form, on rigid glass slides and on flexible polylactide (PLA) sheets, using solvents of differing quality, at various concentrations. The influence of these processing parameters on the shape and size of the formed self-assembled supramolecular structures on films surface was analyzed, and the processing-dependent surfaces wettability changes were also discussed.