A hot electron-hole pair breaks the symmetry of a semiconductor quantum dot.

The best-understood property of semiconductor quantum dots (QDs) is the size-dependent optical transition energies due to the quantization of charge carriers near the band edges. In contrast, much less is known about the nature of hot electron-hole pairs resulting from optical excitation significantly above the bandgap. Here, we show a transient Stark effect imposed by a hot electron-hole pair on optical transitions in PbSe QDs. The hot electron-hole pair does not behave as an exciton, but more bulk-like as independent carriers, resulting in a transient and varying dipole moment which breaks the symmetry of the QD. As a result, we observe redistribution of optical transition strength to dipole forbidden transitions and the broadening of dipole-allowed transitions during the picosecond lifetime of the hot carriers. The magnitude of symmetry breaking scales with the amount of excess energy of the hot carriers, diminishes as the hot carriers cool down and disappears as the hot electron-hole pair becomes an exciton. Such a transient Stark effect should be of general significance to the understanding of QD photophysics above the bandgap.