This study provides new evidence on a long postulated mechanism of phase separation in a polymer/fullerene mixture during spin coating for controlled nanodomains of oriented crystallization and heterojunctions that favor applications in polymer solar cells (PSCs). The simultaneous nanoscale phase separation and crystallization during spin coating of the mixture are traced using in situ grazing‐incidence small‐ and wide‐angle X‐ray scattering. Combined with the complimentary results from time‐resolved optical reflectance spectroscopy, transient stratification of the liquid film during the transition from the flow‐ to evaporation‐dominated stage of spin coating is disclosed; the vertical liquid–liquid phase separation incubates a supersaturated skin layer where fullerene aggregation and polymer crystallization occur and develop concomitantly. Shortly after the transition, the near‐surface structural development is largely pinned, leaving the solvent‐rich bottom layer to diminish via solvent diffusion and evaporation through the thickened skin layer that finally condenses into the spin‐coated film upon solvent depletion. The shear‐enhanced surface layering and supersaturation for the surface‐down nanostructural development are unexpected in all the existing structural models for PSCs. The mechanistic understanding of coupled vertical phase separation and local nanosegregation provides new insights and alternative strategy to the morphology control of spin‐cast PSC active layers in particular and various solution‐processed polymeric films in general.
A model for oil-in-water emulsion has been developed in this paper. A group of viscosity coefficients transiting smoothly and incessantly from the thick film region to the thin film region is defined. The contributions from disperse and continuous phases to the total lubricant pressure and pressure gradient are functions of the oil concentration and the film thickness. The parameters used in these functions are determined by a series of computational fluid dynamics simulations. The onset of inversion and the viscosity after inversion are also investigated. It is found that the critical volume fraction of oil in the inception of inversion is dependent on the oil viscosity and a factor regarding the combined effects from the emulsifier, pH value, droplet size, and the shear rate. A series of simulations using the proposed model has been carried out and compared with the experimental results, such as the film thickness and the extension of oil pool for various rolling speeds and supply oil concentrations. The numerical outputs are basically in agreement with the experiments.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.