Third Generation Photovoltaics based on Multiple Exciton Generation in Quantum Confined Semiconductors

Improving the primary photoconversion process in a photovoltaic cell 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 (SO) limit of similar to 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 similar to 4E(g) 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.