Theories of the Charge Transport Mechanism in Ordered Organic Semiconductors英文教材.pdfVIP

Adv Polym Sci (2010) 223: 259–300 DOI:10.1007/12 2009 10 c Springer-Verlag Berlin Heidelberg 2009 Published online: 19 June 2009 Theories of the Charge Transport Mechanism in Ordered Organic Semiconductors Alessandro Troisi Abstract The traditional theories of charge transport in ordered organic semiconductors are reviewed and their limitations discussed. The recent contri- butions of computational chemistry to the understanding of the parameters that determine the charge mobility in bulk semiconductors are analyzed in detail. The effect of thermal motions on the electronic wavefunction and the effect of strong off-diagonal electron–phonon coupling are identified as essential ingredients for the proper description of the charge dynamics. The development of suitable methods to compute the charge mobility taking into account these new computational results is reviewed, with special emphasis on the models that allow the prediction of the structure–property relationship. The available experimental evidence is compared with the predictions made by the most recent models. Keywords Molecular crystal · Polaron · Electron transport · Quantum chemistry · Pentacene · Disorder Contents 1 The Role of Theory in Organic Semiconductor Research 260 2 Traditional Views on Charge Transport Mechanism in Molecular Crystals and their Limitations 264 2.1 Delocalized Transport in Simple Electronic Band 265 2.2 Delocalized Transport in Polaronic Band 266 2.3 Hopping Transport 268 2.4 Experimental Evidence . 269 2.5 A More General Hamiltonian 269 A. Troisi Department of Chemistry and Centre of Scientific Computing, University of Warwick, CV4 7AL, Coventry, UK e-mail:a.troisi@warwick.ac.uk 260 A. Troisi 3 The Contribution of Computational Che