We calculate the maximum power conversion efficiency for conversion of solar radiation to electrical power or to a flux of chemical free energy for the case of hydrogen production from water photoelectrolysis. We consider several types of ideal absorbers where absorption of one photon can produce more than one electron-hole pair that are based on semiconductor quantum dots with efficient multiple exciton generation ͑MEG͒ or molecules that undergo efficient singlet fission ͑SF͒.Using a detailed balance model with 1 sun AM1.5G illumination, we find that for single gap photovoltaic ͑PV͒ devices the maximum efficiency increases from 33.7% for cells with no carrier multiplication to 44.4% for cells with carrier multiplication. We also find that the maximum efficiency of an ideal two gap tandem PV device increases from 45.7% to 47.7% when carrier multiplication absorbers are used in the top and bottom cells. For an ideal water electrolysis two gap tandem device, the maximum conversion efficiency is 46.0% using a SF top cell and a MEG bottom cell versus 40.0% for top and bottom cell absorbers with no carrier multiplication. We also consider absorbers with less than ideal MEG quantum yields as are observed experimentally.

Charge carriers are photogenerated with very different spatial distributions in conventional inorganic photovoltaic (IPV) cells and in organic photovoltaic (OPV or excitonic) cells. This leads to a fundamental, and often overlooked, mechanistic difference between them. Carriers are generated primarily at the exciton-dissociating heterointerface in OPV cells, resulting in the production of electrons in one phase and holes in the other—the two carrier types are thus already separated across the interface upon photogeneration in OPV cells, giving rise to a powerful chemical potential energy gradient ∇μhv that promotes the photovoltaic effect. This occurs also in high-surface-area OPV cells, although their description is more complex. In contrast, both carrier types are photogenerated together throughout the bulk in IPV cells: ∇μhv then drives both electrons and holes in the same direction through the same phase; efficient carrier separation therefore requires a built-in equilibrium electrical potential energy difference ∅bi across the cell. The open-circuit photovoltage Voc is thus limited to ∅bi in IPV cells, but it is often greater than ∅bi in OPVs. The basic theory necessary to compare IPVs to OPVs is reviewed. Relevant experiments are described, and numerical simulations that compare semiconductor devices differing only in the spatial distribution of photogenerated carriers are presented to demonstrate this fundamental distinction between the photoconversion mechanisms of IPV and OPV devices.

Multiple exciton generation (MEG) in quantum dots (QDs) and impact ionization (II) in bulk semiconductors are processes that describe producing more than one electron-hole pair per absorbed photon. We derive expressions for the proper way to compare MEG in QDs with II in bulk semiconductors and argue that there are important differences in the photophysics between bulk semiconductors and QDs. Our analysis demonstrates that the fundamental unit of energy required to produce each electron-hole pair in a given QD is the band gap energy. We find that the efficiency of the multiplication process increases by at least 2 in PbSe QDs compared to bulk PbSe, while the competition between cooling and multiplication favors multiplication by a factor of 3 in QDs. We also demonstrate that power conversion efficiencies in QD solar cells exhibiting MEG can greatly exceed conversion efficiencies of their bulk counterparts, especially if the MEG threshold energy can be reduced toward twice the QD band gap energy, which requires a further increase in the MEG efficiency. Finally, we discuss the research challenges associated with achieving the maximum benefit of MEG in solar energy conversion since we show the threshold and efficiency are mathematically related.

The n-type transition metal oxides (TMO) consisting of molybdenum oxide (MoO(x)) and vanadium oxide (V(2)O(x)) are used as an efficient hole extraction layer (HEL) in heterojunction ZnO/PbS quantum dot solar cells (QDSC). A 4.4% NREL-certified device based on the MoO(x) HEL is reported with Al as the back contact material, representing a more than 65% efficiency improvement compared with the case of Au contacting the PbS quantum dot (QD) layer directly. We find the acting mechanism of the hole extraction layer to be a dipole formed at the MoO(x) and PbS interface enhancing band bending to allow efficient hole extraction from the valence band of the PbS layer by MoO(x). The carrier transport to the metal anode is likely enhanced through shallow gap states in the MoO(x) layer.

The intermediate-band solar cell ͑IBSC͒ concept has been recently proposed to enhance the current gain from the solar spectrum whilst maintaining a large open-circuit voltage. Its main idea is to introduce a partially occupied intermediate band ͑IB͒ between the valence band ͑VB͒ and conduction band ͑CB͒ of the semiconductor absorber, thereby increasing the photocurrent by the additional VB→ IB and IB→ CB absorptions. The confined electron levels of self-assembled quantum dots ͑QDs͒ were proposed as potential candidates for the implementation of such an IB. Here we report experimental and theoretical investigations on In y Ga 1−y As dots in a GaAs 1−x P x matrix, examining its suitability for acting as IBSCs. The system has the advantage of allowing strain symmetrization within the structure, thus enabling the growth of a large number of defect-free QD layers, despite the significant size mismatch between the dot material and the surrounding matrix. We examine the various conditions related to the optimum functionality of the IBSC, in particular those connected to the optical and electronic properties of the system. We find that the intensity of absorption between QD-confined electron states and host CB is weak because of their localized-to-delocalized character. Regarding the position of the IB within the matrix band gap, we find that, whereas strain symmetrization can indeed permit growth of multiple dot layers, the current repertoire of GaAs 1−x P x barrier materials, as well as In y Ga 1−y As dot materials, does not satisfy the ideal energetic locations for the IB. We conclude that other QD systems must be considered for QD-IBSC implementations.