In this study, graphene oxide (GO) based hybrid materials with poly(3-butylthiophene) (P3BT) having various morphologies and crystal structures are fabricated through different approaches. The first kind of GO/P3BT hybrid material was prepared by aging GO/P3BT mixture in o-dichlorobenzene (ODCB) solvent, in which the P3BT molecules grow on GO surface and crystallize into semi-spherulites composed of nanoribbons. In this GO/P3BT hybrid material, P3BT crystals are in From II structure with a π-stacking distance of 0.47 nm and the P3BT nanoribbons with maximum width of 200 nm preferentially grow along the π-stacking direction. After thermal treatment, the GO/Form II P3BT hybrid material could be easily transformed into GO/Form I P3BT hybrid material with unchanged nanoribbon morphology but a modified π-stacking distance of 0.38 nm. If anisole is added to the fresh GO/P3BT solution in ODCB solvent, a third hybrid material, i.e., GO/P3BT nanowhiskers in Form I structure, was obtained. This work would be of benefit for the further understanding of P3BT crystallization behavior in the presence of GO and these hybrid materials would also provide potential platforms for further morphology-property study and crystal structure-property study on GO/conjugated polymer hybrid materials.
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