Stokes shift, an energy difference between the excitonic absorption and emission, is a property of colloidal quantum dots (CQDs) typically ascribed to splitting between dark and bright excitons. In some materials, e.g., PbS, CuInS2, CdHgTe, a Stokes shift of up to 200 meV is observed, substantially larger than the estimates of dark-bright state splitting or vibronic relaxations. The shift origin remains highly debated, as contradictory signatures of both surface and bulk character were reported for the Stokes-shifted electronic state. Here we show that the energy transfer among CQDs in a polydispersed ensemble in solution suffices to explain the excess Stokes shift. This energy transfer is primarily due to CQD aggregation, and can be substantially eliminated by extreme dilution, higher-viscosity solvent, or better-dispersed colloids. Our findings highlight that ensemble polydispersity remains the primary source of the Stokes shift in CQDs in solution, propagating into the Stokes shift in films and the open-circuit voltage deficit in CQD solar cells. Improved synthetic control can bring notable advancements in CQD photovoltaics, and the Stokes shift continues to provide a sensitive and significant metric to monitor ensemble size distribution.
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUS-11-009-21
Acknowledgements: We thank Kyle Kemp, Janet Macdonald, Chih-Shan Tan and Kemar Reid for fruitful discussions. This publication is based in part on work supported by Award KUS-11-009-21, made by King Abdullah University of Science and Technology (KAUST), by the Ontario Research Fund Research Excellence Program, and by the Natural Sciences and Engineering Research Council (NSERC) of Canada Strategic Partnership Grant 478954-15.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.