Hot Exciton Relaxation Dynamics in Semiconductor Quantum Dots: Radiationless Transitions on the Nanoscale

Abstract

The ability to confine electrons and holes in semiconductor quantum dots (QDs) in the form of excitons creates an electronic structure which is both novel and potentially useful for a variety of applications. Upon optical excitation of the dot, the initial excitonic state may be electronically hot. The relaxation dynamics of this hot exciton is the primary event which controls key processes such as optical gain, hot carrier extraction, and multiple exciton generation. Here, we describe femtosecond state-resolved pump/probe experiments on colloidal CdSe quantum dots that provide the first quantitative measure of excitonic state-to-state transition rates. The measurements and modeling here reveal that there are multiple paths by which hot electrons and hot holes relax. The immediate result is that there is no phonon bottleneck for electrons or holes for excitons in quantum dots. This absence of phonon-based relaxation is confirmed by independent measurements of weak exciton–phonon coupling between the vario...