Ligand Directed Self-Assembly of Bulk Organic-Semiconductor/Quantum-Dot Blend Films Enables Near Quantitative Harvesting of Triplet Excitons

Abstract: Singlet fission (SF), an exciton multiplication process occurring in organic semiconductors, offers a way to break the Shockley-Queisser limit in single-bandgap photovoltaics (PV). If the triplet excitons generated by SF can be transferred to inorganic quantum dots (QDs), where they radiatively recombine, SF based photon multiplication is achieved, converting a single high-energy photon into two low-energy photons. Such a SF photon multiplication film (SF-PMF) could raise the efficiency of the best Si-PV from 26.7% to 32.5%. But a precise nanoscale morphology is required within such a film consisting of the appropriate morphology for the organic phase, allowing for efficient SF, within which the QD emitters are well dispersed on a tens of nm length scale to enable efficient harvesting of the triplets. However, it has been a long-standing problem that the individual components in organic-QD blends have a tendency to aggregate and phase separate, due to a mismatch of their size, shape and surface energies. Here, we demonstrate a QD surface engineering approach using an electronically active, highly soluble semiconductor ligand that is matched to the SF material, which allows us to direct the self-assembly process yielding solution processed films with well-dispersed QDs and minimal aggregation, as characterised by X-ray and neutron scattering and electron microscopy. Steady state and time-resolved optical spectroscopy show that the films support efficient SF (190% yield) in the organic phase and quantitative triplet energy transfer across the organic-QD interface, resulting in 95% of the triplet excitons being harvested by the QDs. Our results establish the SF-PMF as a highly promising architecture to harness the SF process to enhance PV efficiencies, and also provide a highly versatile approach to overcome challenges in the blending of organic semiconductors with QDs.