Singlet exciton fission, a process that generates two excitons from a single photon, is perhaps the most efficient of the various multiexciton-generation processes studied to date, offering the potential to increase the efficiency of solar devices. But its unique characteristic, splitting a photogenerated singlet exciton into two dark triplet states, means that the empty absorption region between the singlet and triplet excitons must be filled by adding another material that captures low-energy photons. This has required the development of specialized device architectures. In this Account, we review work to develop devices that harness the theoretical benefits of singlet exciton fission. First, we discuss singlet fission in the archetypal material, pentacene. Pentacene-based photovoltaic devices typically show high external and internal quantum efficiencies. They have enabled researchers to characterize fission, including yield and the impact of competing loss processes, within functional devices. We review in situ probes of singlet fission that modulate the photocurrent using a magnetic field. We also summarize studies of the dissociation of triplet excitons into charge at the pentacene-buckyball (C60) donor-acceptor interface. Multiple independent measurements confirm that pentacene triplet excitons can dissociate at the C60 interface despite their relatively low energy. Because triplet excitons produced by singlet fission each have no more than half the energy of the original photoexcitation, they limit the potential open circuit voltage within a solar cell. Thus, if singlet fission is to increase the overall efficiency of a solar cell and not just double the photocurrent at the cost of halving the voltage, it is necessary to also harvest photons in the absorption gap between the singlet and triplet energies of the singlet fission material. We review two device architectures that attempt this using long-wavelength materials: a three-layer structure that uses long- and short-wavelength donors and an acceptor and a simpler, two-layer combination of a singlet-fission donor and a long-wavelength acceptor. An example of the trilayer structure is singlet fission in tetracene with copper phthalocyanine inserted at the C60 interface. The bilayer approach includes pentacene photovoltaic cells with an acceptor of infrared-absorbing lead sulfide or lead selenide nanocrystals. Lead selenide nanocrystals appear to be the most promising acceptors, exhibiting efficient triplet exciton dissociation and high power conversion efficiency. Finally, we review architectures that use singlet fission materials to sensitize other absorbers, thereby effectively converting conventional donor materials to singlet fission dyes. In these devices, photoexcitation occurs in a particular molecule and then energy is transferred to a singlet fission dye where the fission occurs. For example, rubrene inserted between a donor and an acceptor decouples the ability to perform singlet fission from other major photovoltaic properties such as light absorption.

Singlet Exciton Fission Photovoltaics