Band-Edge Energy Levels of Dynamic Excitons in Cube-Shaped CdSe/CdS Core/Shell Nanocrystals.

An electron-hole pair in a cube-shaped CdSe/CdS core/shell nanocrystal exists in the form of dynamic excitons across the strongly and weakly confined regimes under ambient temperatures. Photochemical doping is applied to distinguish the band-edge electron and hole levels, confirming an effective mass model with universal constants. Reduction of the optical bandgap upon epitaxy of the CdS shells is caused by lowering the band-edge electron level and barely affecting the band-edge hole level. Similar shifts of the electron levels, yet retaining the hole levels, can switch the order in energy of the three lowest-energy transitions. Thermal distribution of 1-4 electrons among the two thermally accessible electron levels follows number-counting statistics, instead of Fermi-Dirac distribution.