Polaron and bipolaronlike states inn-doped bithiophene

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Abstract
Bithiophene is studied with varying Cs dosing as a model for the n-doping of thiophene-based conducting polymers. The evolution of the electronic structure with increasing Cs concentration is followed both indirectly, by electron-energy-loss spectroscopy (EELS), and directly by ultraviolet-photoemission spectroscopy (UPS). In both spectroscopies the behavior of the states formed in the gap indicates two doping regimes. The EELS results parallel the optical-absorption results for the p-doping of longer thiophene oligomers and polythiophene, and suggest a polaron (anion) to bipolaronlike (dianion) transformation. The UPS results are consistent with this interpretation, showing first in the low-doping regime the appearance of two states in the band gap which move closer together in the higher-doping regime. This constitutes direct observation of a transition from polaron to bipolaron states, albeit in a model system. Consideration of the photoionization cross sections indicates that the deeper (bi)polaron level has C 2p character while the shallow level, filled by donation from the Cs, has significant S 3p character.