Impact of concentration self-quenching on the charge generation yield of fullerene based donor-bridge-acceptor compounds in the solid state

A fullerene based Donor-Bridge-Acceptor (DBA) compound, incorporating a pi-extended tetrathiafulvalene electron donor, is investigated with respect to its photophysics in solution versus solid state. Solid films of neat DBA are compared with blend films where the DBA compound is diluted in the inert, low dielectric, polymer poly(styrene). It is found that the moderate intermolecular electronic coupling and donor-acceptor separation (22 angstrom) in this case leads to the generation of more dissociated, intermolecular charges than a mixture of the donor and acceptor reference compounds. However, the increased intermolecular interactions in the solid state lead to the excited state of the fullerene suffering from concentration self-quenching. This is found to severely affect the charge generation yield in solid films. The impact of competing intra and intermolecular interactions in the solid state upon the film photophysics is analysed in terms of a kinetic model which includes both the effects of concentration self-quenching and the impact of film composition upon the dielectric stabilisation of charge separated states. We conclude that both concentration self-quenching and dielectric stabilisation are critical in determining the photophysics of the blend films, and discuss strategies based upon our observations to enhance the charge photogeneration properties of organic films and photovoltaic devices based upon DBA compounds