Monte Carlo simulations are used to investigate the dissociation of a Coulomb correlated charge pair at an idealized interface between an electron accepting and an electron donating molecular material. In the simulations the materials are represented by cubic lattices of sites, with site the energies spread according to Gaussian distributions. The influence of temperature, applied external fields, and the width of the Gaussian densities of states distribution for both the electron and the hole transporting material are investigated. The results show that the dissociation of geminate charge pairs is assisted by disorder. When the rate for geminate recombination at the interface is very low (<1 ns<sup>-1</sup>) the simulations predict a high yield for carrier collection, as observed experimentally. Comparison of the simulated and experimentally observed temperature dependence of the collection efficiency indicates that at low temperature dissociation of the geminate charge pairs may be one of the factors limiting the device performance. Furthermore, the simulations show that excess exciton energy liberated in the photoinduced charge transfer process enhances dissociation of the geminate pair and can thereby allow for high yields for carrier collection.
The photophysical properties of a solution processed blend of two semiconducting polymers with electron donating and electron accepting properties, respectively, as used in polymer photovoltaic devices have been investigated. In the binary mixture of poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and poly[oxa-1,4-phenylene-(1-cyano-1,2-vinylene)-(2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene)-1,2-(2-cyanovinylene)-1,4-phenylene] (PCNEPV) photoexcitation of either one of the polymers results in formation of a luminescent exciplex at the interface of the two materials. The high energy of this correlated charge-separated state is consistent with the high open-circuit voltage of the corresponding solar cells (1.36 eV). Application of an electric field results in dissociation of the marginally stable exciplex into charge carriers, which provides the basis for the photovoltaic effect of this combination of materials.