Commonly observed variations in photoluminescence (PL) spectra of crystalline organic semiconductors, including the appearance or enhancement of certain PL bands, are shown to originate from a small amount of structural disorder (e.g., amorphous inclusions embedded in a crystal), rather than be necessarily related to chemical impurities or material oxidation. For instance, in rubrene, a minute amount of such disorder can lead to the appearance of a dominant PL band at 650 nm as a result of triplet excitons captured and fused at these sites, with a subsequent emission from the amorphous phase.
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