Flowing versus Static Conditions for Measuring Multiple Exciton Generation in PbSe Quantum Dots

Recent reports question the validity of pulsed fs-laser experiments for measuring the photon-to-exciton quantum yields (QYs) that result from multiple exciton generation (MEG). The repetitive nature of these experiments opens up an alternative relaxation pathway that may produce artificially high results. We present transient-absorption (TA) data for 4.6 and 6.6 nm diameter PbSe quantum dots (QDs) at a variety of pump photon energies. The data are collected under laminar flow conditions with volumetric flow rates ranging from 0 to 150 mL/min (resulting in Reynolds numbers up to 460). The results are modeled with a spatially resolved population balance of generation, recombination, convective replacement, and accumulation of long-lived excited QDs. By comparing the simulations and experiments, the steady-state population of the long-lived QD-excited states and their kinetics are determined for different experimental conditions. We also improve upon reported photon-to-exciton QYs for PbSe QDs. We find differences in the observed TA dynamics between flowing and static conditions that depend upon photon fluence, pump photon energy, and quality of the QD surfaces. For excitation energies below 2 Eg, independent of QD size or photon fluence, we observe no flow rate dependence in the TA dynamics. At excitation energies of hν > 3 Eg, we observe differences between static and flowing conditions that are most pronounced for high photon fluences. At 3.7 Eg and for 4.6 nm PbSe QDs we find a QY of 1.2 ± 0.1 and at 4.5 Eg the QY is 1.55 ± 0.05. With 6.6 nm QDs excited at 4.7 Eg we observe no difference between static and flowing conditions and find a QY of 1.61 ± 0.05. We also find that by treating the surface of QDs, we can decrease the charging probability (Pg ≈ 5 × 10−5) by a factor of 3−4. The observed variations suggest that different QD samples vary regarding their susceptibility to the creation of long-lived states.