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Phys Rev Lett. 2007 May 18;98(20):206406. Epub 2007 May 17.

Role of intermolecular coupling in the photophysics of disordered organic semiconductors: aggregate emission in regioregular polythiophene.

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  • 1Cavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge, CB3 0HE, United Kingdom.


We address the role of excitonic coupling on the nature of photoexcitations in the conjugated polymer regioregular poly(3-hexylthiophene). By means of temperature-dependent absorption and photoluminescence spectroscopy, we show that optical emission is overwhelmingly dominated by weakly coupled H aggregates. The relative absorbance of the 0-0 and 0-1 vibronic peaks provides a powerfully simple means to extract the magnitude of the intermolecular coupling energy, of approximately 5 and 30 meV for films spun from isodurene and chloroform solutions, respectively.

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