Generalization of Einstein relation for doped organic semiconductors

Under the assumption of Gaussian energy distributions of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO), analytical expressions of generalized Einstein relation for electron and hole transport in doped organic semiconductor thin films are developed. Numerical calculations show that, although traditional Einstein relation still holds for low carrier concentrations, that is, the diffusion-coefficient-to-mobility ratio in units of k_BT/q, with k_B the Boltzmann’s constant, T the temperature and q the elementary charge, equals 1. But when the electron (hole) concentration is high, the diffusion-coefficient-to-mobility ratio for electrons (holes) changes strongly with the electron (hole) concentration, the doping level, the mean energy of LUMOs (HOMOs) of the dopant E_Ld (E_Hd) and the host E_L (E_H), as well as their variances. Dopants with E_Ld<E_L (E_Hd>E_H) affect the diffusion-coefficient-to-mobility ratio mainly in the range of low and middle carrier concentrations, while those with E_Ld>E_L (E_Hd<E_H) have significant effect only in the range of high carrier concentrations. It was found that there can be a maximum in the dependence of the diffusion-coefficient-to-mobility ratio on the quasi-Fermi energy or carrier concentration exist, for appropriate values of the doping level, the mean energy and variance of LUMO or HOMO states of the dopant. PACS 71.20.Rv; 72.90.+y; 73.50.-h