Multiple exciton generation (MEG) is a process that can occur in semiconductor nanocrystals, or quantum dots (QDs), whereby absorption of a photon bearing at least twice the bandgap energy produces two or more electron-hole pairs. Here, we report on photocurrent enhancement arising from MEG in lead selenide (PbSe) QD-based solar cells, as manifested by an external quantum efficiency (the spectrally resolved ratio of collected charge carriers to incident photons) that peaked at 114 ± 1% in the best device measured. The associated internal quantum efficiency (corrected for reflection and absorption losses) was 130%. We compare our results with transient absorption measurements of MEG in isolated PbSe QDs and find reasonable agreement. Our findings demonstrate that MEG charge carriers can be collected in suitably designed QD solar cells, providing ample incentive to better understand MEG within isolated and coupled QDs as a research path to enhancing the efficiency of solar light harvesting technologies.

The organic cation and its interplay with the inorganic lattice underlie the exceptional optoelectronic properties of organo-metallic halide perovskites. Herein we report high-quality infrared spectroscopic measurements of methylammonium lead halide perovskite (CH3NH3Pb(I/Br/Cl)3) films and single crystals at room temperature, from which the dielectric function in the investigated spectral range is derived. Comparison with electronic structure calculations in vacuum of the free methylammonium cation allows for a detailed peak assignment. We analyze the shifts of the vibrational peak positions between the different halides and infer the extent of interaction between organic moiety and the surrounding inorganic cage. The positions of the NH3(+) stretching vibrations point to significant hydrogen bonding between the methylammonium and the halides for all three perovskites.

Lead halide perovskites such as methylammonium lead triiodide (CH 3 NH 3 PbI 3 ) have outstanding optical and electronic properties for photovoltaic applications, yet a full understanding of how this solution processable material works so well is currently missing. Previous

Improving the primary photoconversion process in a photovoltaiccell by utilizing the excess energy that is otherwise lost as heat can lead to an increase in the overall power conversion efficiency (PCE). Semiconductor nanocrystals (NCs) with at least one dimension small enough to produce quantum confinement effects provide new ways of controlling energy flow not achievable in thin film or bulk semiconductors. Researchers have developed various strategies to incorporate these novel structures into suitable solar conversion systems. Some of these methods could increase the PCE past the Shockley-Queisser (SQ) limit of ∼33%, making them viable "third generation photovoltaic" (TGPV) cell architectures. Surpassing the SQ limit for single junction solar cells presents both a scientific and a technological challenge, and the use of semiconductor NCs to enhance the primary photoconversion process offers a promising potential solution. The NCs are synthesized via solution phase chemical reactions producing stable colloidal solutions, where the reaction conditions can be modified to produce a variety of shapes, compositions, and structures. The confinement of the semiconductor NC in one dimension produces quantum films, wells, or discs. Two-dimensional confinement leads to quantum wires or rods (QRs), and quantum dots (QDs) are three-dimensionally confined NCs. The process of multiple exciton generation (MEG) converts a high-energy photon into multiple electron-hole pairs. Although many studies have demonstrated that MEG is enhanced in QDs compared with bulk semiconductors, these studies have either used ultrafast spectroscopy to measure the photon-to-exciton quantum yields (QYs) or theoretical calculations. Implementing MEG in a working solar cell has been an ongoing challenge. In this Account, we discuss the status of MEG research and strategies towards implementing MEG in working solar cells. Recently we showed an external quantum efficiency for photocurrent of greater than 100% (reaching 114%) at ∼4Eg in a PbSe QD solar cell. The internal quantum efficiency reached 130%. These results compare favorably with ultrafast transient spectroscopic measurements. Thus, we have shown that one of the tenets of the SQ limit, that photons only produce one electron-hole pair at the electrodes of a solar cell, can be overcome. Further challenges include increasing the MEG efficiency and improving the QD device structure and operation.