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Revealing the Influences of Solvent Boiling Point and Alkyl Chains on the Adlayer Crystallinity of Furan-Diketopyrrolopyrrole-Thienylene Copolymer at Molecular Level.

Surface crystallinity of the polymer poly(3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-altthieylenevinylene (PDVF) adlayers casted from low- boiling point (L-bp), medium-bp (M-bp) and high-bp (H-bp) solvents were investigated through scanning tunneling microscopy (STM) and analyzed in the assistance of Hansen solubility parameter (HSP) theory and molecular dynamics (MD) simulations. Crystallinity of PDVF adlayers increase evidently from the L- to H-bp solvent and the solvent with alkyl chain such as ethylbenzene (EB) facilitates improving crystallinity also than the one without alkyl chain such as chlorobenzene (CB) if the solvent bp locates in the same group. HSP space discloses that EB is a marginal solvent for PDVF in contrast to CB. Quasi-isolate PDVF in EB solution revealed by MD simulations facilitates forming crystallized domains through surface assembling mechanism. Whereas in CB, interconnected PDVF molecules through intermolecular overlapping tend to generate amorphous structures through direct deposition of pre-formed structures in solution.