Systematic Study on the Morphological Development of Blade-Coated Conjugated Polymer Thin Films via In Situ Measurements

The morphology of conjugated polymer thin films, determined by the kinetics of film drying, is closely correlated with their electrical properties. Herein, we focused on dramatic changes in the thin-film morphology of blade-coated poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} caused by the effect of solvent and coating temperature. Through in situ measurements, the evolution of polymer aggregates and crystallites, which plays a decisive role in the formation of the charge-transport pathway, was observed in real time. By combining in situ ultraviolet–visible spectroscopy and in situ grazing-incidence wide-angle X-ray scattering analysis, we could identify five distinct stages during the blade-coating process; these stages were observed irrespective of the solvent and coating temperature used. The five stages are described in detail with a proposed model of film formation. This insight is an important step in understanding the relationship between the morphology of thin polymer films and their charge-transport properties as well as in optimizing the structural evolution of thin films.