Multiexciton generation (MEG) has been indirectly observed in colloidal quantum dots, both in solution and the solid state, but has not yet been shown to enhance photocurrent in an optoelectronic device. Here, we report a class of solution-processed photoconductive detectors, sensitive in the ultraviolet, visible, and the infrared, in which the internal gain is dramatically enhanced for photon energies Ephoton greater than 2.7 times the quantum-confined bandgap Ebandgap. Three thin-film devices with different quantum-confined bandgaps (set by the size of their constituent lead sulfide nanoparticles) show enhancement determined by the bandgap-normalized photon energy, Ephoton/Ebandgap, which is a clear signature of MEG. The findings point to a valuable role for MEG in enhancing the photocurrent in a solid-state optoelectronic device. We compare the conditions on carrier excitation, recombination, and transport for photoconductive versus photovoltaic devices to benefit from MEG.

We report colloidal quantum dot (CQDs) photovoltaics having a approximately 930 nm bandgap. The devices exhibit AM1.5G power conversion efficiencies in excess of 2%. Remarkably, the devices are stable in air under many tens of hours of solar illumination without the need for encapsulation. We explore herein the origins of this orders-of-magnitude improvement in air stability compared to larger PbS dots. We find that small and large dots form dramatically different oxidation products, with small dots forming lead sulfite primarily and large dots, lead sulfate. The lead sulfite produced on small dots results in shallow electron traps that are compatible with excellent device performance; whereas the sulfates formed on large dots lead to deep traps, midgap recombination, and consequent catastrophic loss of performance. We propose and offer evidence in support of an explanation based on the high rate of oxidation of sulfur-rich surfaces preponderant in highly faceted large-diameter PbS colloidal quantum dots.

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Colloidal quantum dot (CQD) photovoltaics offer a promising approach to harvest the near-IR region of the solar spectrum, where half of the sun's power reaching the earth resides. High external quantum efficiencies have been obtained in the visible region in lead chalcogenide CQD photovoltaics. However, the corresponding efficiencies for band gap radiation in the near-infrared lag behind because the thickness of CQD photovoltaic layers from which charge carriers can be extracted is limited by short carrier diffusion lengths. Here, we investigate, using a combination of electrical and optical characterization techniques, ligand passivation strategies aimed at tuning the density and energetic distribution of charge trap states at PbS nanocrystal surfaces. Electrical and optical measurements reveal a more than 7-fold enhancement of the mobility-lifetime product of PbS CQD films treated with 3-mercaptopropionic acid (MPA) in comparison to traditional organic passivation strategies that have been examined in the literature. We show by direct head-to-head comparison that the greater mobility-lifetime products of MPA-treated devices enable markedly greater short-circuit current and higher power conversion efficiency under AM1.5 illumination. Our findings highlight the importance of selecting ligand treatment strategies capable of passivating a diversity of surface states to enable shallower and lower density trap distributions for better transport and more efficient CQD solar cells.

The air stability and power conversion efficiency of solution‐processed PbS quantum dot solar cells is dramatically improved by the insertion of 0.8 nm LiF between the PbS nanoparticle film and the Al contact.