Passivation-sensitive exciton finestructure produces excess Stokes   shifts in colloidal quantum dots
  The excitonic finestructure of colloidal quantum dots (CQDs) is comprised of a manifold of transitions, of which only the lowest are populated and contribute to photoluminescence. This leads to a Stokes shift in emission relative to absorption. Here we show experimentally that the Stokes shift in Pb and Cd-based chalcogenide CQDs is correlated with the degree of surface passivation, and develop a model that explains how coupling to the surface affects the core electronic states. Dark and bright transitions can reorder and split, increasing the Stokes shift even without the formation of deep traps. Our findings resolve the highly-debated topic of excess Stokes shifts in PbS nanocrystals as due to parity-forbidden transitions instead of traps. We predict that the Stokes shift in PbS can be eliminated via core stoichiometry control, a critical step towards enhancing the open circuit voltage in quantum dot solar cells. 
Oleksandr Voznyy, Fengjia Fan, Alexander Ip, Amirreza Kiani, Susanna   M. Thon, Kyle W. Kemp, Larissa Levina, Edward H. Sargent
cond-mat.mes-hall