Solution processed quantum dot (QD) lasers are one of the holy-grails of nanoscience. They are not yet commercialized because the lasing threshold is too high: one needs < 1 exciton per QD, which is hard to achieve due to fast non-radiative Auger recombination. The threshold can however be reduced by electronic doping of the QDs, which decreases the absorption near the band-edge, such that the stimulated emission (SE) can easily outcompete absorption. Here, we show that by electrochemically doping films of CdSe/CdS/ZnS QDs we achieve quantitative control over the gain threshold. We obtain stable and reversible doping more than two electrons per QD. We quantify the gain threshold and the charge carrier dynamics using ultrafast spectroelectrochemistry and achieve quantitative agreement between experiments and theory, including a vanishingly low gain threshold for doubly doped QDs. Over a range of wavelengths with appreciable gain coefficients, the gain thresholds reach record-low values of ~10-5 excitons per QD. These results demonstrate an unprecedented level of control over the gain threshold in doped QD solids, paving the way for the creation of cheap, solution-processable low-threshold QD-lasers.
Near-infrared luminescent lanthanide (Ln)-doped nanomaterials are currently attracting high interest in view of their sharp f-f emission peaks and long luminescence lifetimes, which establish a unique value for the development of optical amplifiers, lasers and biosensors. To improve the optical pumping of the weakly absorbing lanthanide ions (Ln3+), the doped nanoparticles are coupled with an organic dye sensitizer able to efficiently harvest light and subsequently transfer the absorbed energy to the emitter. However, this through-space “remote” sensitization is severely subjected to energy losses due to competitive energy migration or deactivation routes limiting the overall luminescence quantum yields. The implementation of the Förster’s model of resonance energy transfer on the basis of advanced ultra-fast transient absorption and photoluminescence spectroscopy with the support of density functional theory calculations demonstrate that the sensitization efficiency from the dye to the doped nanoparticle is strictly regulated by the geometry and localization of the transition dipole moment of the dye molecule. Within the nanoparticle, the energy transfer pathways can be harnessed through the spatial confinement of ‘energy bridges’, accepting energy from the surface dyes and donating to core emitters. We show that the FITC (fluorescein-isothiocyanate) dye allows reaching exceptional sensitization efficiency close to unity for the NIR-emitting triad Nd3+, Er3+ and Yb3+.