Delayed electron–hole recombination in a pseudo-direct semiconductor

Abstract Kirchhoff demonstrated the reciprocity between absorptivity and emissivity for blackbody radiation in 1860 (ref. 1 ), thereby establishing the general principle that a good absorber must also be a good emitter. This principle underpins the generalized Planck’s law 2 and, when applied to semiconductors—in the form of the van Roosbroeck–Shockley equation 3 —results in substantial limitations to solar energy conversion. Here we demonstrate how this reciprocity can be circumvented in semiconductors, such as bismuth sulfide, showing a pseudo-direct bandgap character—that is, featuring a lower-energy indirect transition paired with a direct transition placed a few k B T above. After determining the pseudo-direct bandgap nature of bismuth sulfide, we reveal how this feature substantially retards bimolecular electron–hole recombination in this material with respect to classic direct semiconductors 4 . The resulting combination of a high absorption coefficient and delayed recombination offers the unprecedented possibility of overcoming limitations associated with Planck’s law, with far-reaching potential for solar energy conversion.