The energetic driving force required to drive charge separation across donor/acceptor heterojunctions is a key consideration for organic optoelectronic devices. Herein we report a series of transient absorption and photocurrent experiments as a function of excitation wavelength and temperature for two low-band-gap polymer/fullerene blends to study the mechanism of charge separation at the donor/acceptor interface. For the blend that exhibits the smallest donor/acceptor LUMO energy level offset, the photocurrent quantum yield falls as the photon excitation energy is reduced toward the band gap, but the yield of bound, interfacial charge transfer states rises. This interplay between bound and free charge generation as a function of initial exciton energy provides key evidence for the role of excess energy in driving charge separation of direct relevance to the development of low-band-gap polymers for enhanced solar light harvesting.

J. Am. Chem. Soc.
Ultrafast Spectroscopy

Dimitrov, S. D., Bakulin, A., Nielsen, C. B., Schroeder, B. C., Du, J., Bronstein, H., … Dupuis, R. D. (2012). On the energetic dependence of charge separation in low-band-gap polymer/fullerene blends. J. Am. Chem. Soc., 134(44), 18189–18192. doi:10.1021/ja308177d