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Phys Rev Lett. 2006 Mar 3;96(8):086601. Epub 2006 Mar 3.

Charge-transport regime of crystalline organic semiconductors: diffusion limited by thermal off-diagonal electronic disorder.

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  • 1Department of Chemistry, University of Warwick, CV4 7AL Coventry, United Kingdom.

Abstract

We propose that the electron transport in crystalline organic semiconductors at room temperature (RT) is neither polaronic nor a combination of thermally activated hopping and polaronic transport, as previously thought. Thermal molecular motions cause large fluctuations in the intermolecular transfer integrals that, in turn, localize the charge carrier. This effect destroys the translational symmetry of the electronic Hamiltonian and makes the band description inadequate for RT organic crystals. We used a one-dimensional semiclassical model to compute the (temperature dependent) charge carrier mobility in the presence of thermal fluctuations of the electronic Hamiltonian. This transport mechanism explains several contrasting experimental observations pointing sometimes to a delocalized "bandlike" transport and sometimes to the existence of strongly localized charge carriers.

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