Auger-Mediated Electron Relaxation Is Robust to Deep Hole Traps: Time-Domain Ab Initio Study of CdSe Quantum Dots

By slowing down electronphonon relaxation in nanoscale materials, one can increase efficiencies of solar energy conversion via hot electron extraction, multiple exciton generation, and elimination of exciton trapping. The elusive phonon bottleneck is hard to achieve, in particular, due to Auger-type energy exchange between electrons and holes. The Auger channel can be suppressed by hole trapping. Using time-domain ab initio simulation, we show that deep hole traps cannot fully eliminate the Auger channel. The simulations show that the hole-mediated electron relaxation is slowed down only by about 30%, which is in agreement with the recent experiments. The Auger energy exchange and hole relaxation to the trap state occur on similar time scales. Hole trapping is slow, because holes themselves experience a weak bottleneck effect. The study establishes the fundamental mechanisms of the electron and hole relaxation processes with and without hole traps. It shows that more sophisticated hole trapping strategies, for example, involving shell layers, are required in order to achieve the phonon bottleneck and to reduce electronic energy losses.