We studied the microscopic dependence of poly(9,9-dioctylfluorene) photoluminescence (PL) on the deposition conditions. We show that in films spin coated from chloroform phase separation of β and glassy phases is present, with micrometric β phase clusters covering about 6% of the sample surface. The exposure to toluene vapors leads to the disappearance of the β phase clusters, but increases the β phase content in the films due to swelling induced polyfluorene chain planarization. The deposition from toluene solution leads to nonuniform PL intensity, dominated by the β phase emission, attributed to an interplay between aggregation during the solvent evaporation and solvent swelling induced chain planarization.
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