Colloidal Quantum Dots (QDs) are heavily investigated for their applications in light emission such as light emitting diodes and, more challenging, lasers due to their appealing processing conditions, compared to e.g. epitaxy, lowering cost and enabling patterning, and tunable optical properties. Using quantum confined Cd-based QDs, several groups have shown light amplification and ensuing lasing action in the red part of the spectrum. Although impressive milestones were achieved, there is to date no single material that can provide the demanding combination of gain metrics to be truly competitive with existing epitaxial growth approaches. In this work, we take a look at CdS/Se nanocrystals in the regime of vanishing quantum confinement, so-called ‘bulk nanocrystals’. We show that these unique materials display disruptive optical gain metrics in the green optical region. Indeed, while showing similar gain thresholds compared to state-of-the-art QD materials, the gain window (440-600 nm, … ), amplitude (up to 50.000/cm) and gain lifetime (up to 3 ns) vastly outpace other QD materials. Using these novel gain materials, we demonstrate lasing in the highly demanded green spectral region (480 – 530 nm) and in the red (650 – 740 nm) both with pulsed and quasi-CW optical excitation. These lasers are made using a Photonic Crystal Surface Emitting Laser (PCSEL) type cavity. As a final step, we attempt to further optimize the lasing properties, be it either narrow linewidth lasers, or high-power output, based on in-depth understanding of the hybrid QD-PCSEL laser system.
Colloidal quantum dots (QDs) are heavily investigated for their applications in light emission such as light emitting diodes and, more challenging, lasers. This is due to their appealing processing conditions, compared to e.g. epitaxy, resulting in lowering cost. They can also be patterned and their optical properties can be tuned. Using quantum confined Cd-based QDs, several groups have shown light amplification and ensuing lasing action in the red part of the spectrum. Although impressive milestones were achieved, there is to date no single material that can provide the demanding combination of gain metrics to be truly competitive with existing epitaxial growth approaches. In this talk, we take a look at material properties of CdS/Se nanocrystals in the regime of vanishing quantum confinement, so-called ‘bulk nanocrystals’. We show that these unique materials display disruptive optical gain metrics in the green optical region. Indeed, while showing similar gain thresholds compared to state-of-the-art QD materials, the gain window (440-600 nm, 640-750 nm), amplitude (up to 50.000/cm) and gain lifetime (up to 3 ns) vastly outpace other solution processible materials. These results, while very impressive, are also puzzling. In the solution processible community a material system without quantum confinement does not exactly inspire confidence to have good emission metrics. We attempt to explain the physics behind these huge gain coefficients, by using a bulk semiconductor model which includes a strong band-gap renormalization effect, and argue why going to a bulk semiconductor can be advantageous compared to confined systems for making integrated lasers.
InP colloidal quantum dots have become widespread in luminescent colour conversion however further studies are necessary to understand the origin of the emitting state. Additionally, reports on optical gain are scarce and lack follow-up research. In this paper, we study the properties of InP/ZnSe and InP/ZnSe/ZnS quantum dots with Transient Absorption Spectroscopy. We propose a state-filling model were the band-edge bleach can be interpreted as the filling of the conduction and valence band edge states by delocalized holes and electrons. According to this interpretation, optical gain should be observed once the average exciton density is larger than
1. We explain this lower than expected threshold and the properties of the observed stimulated emission band by acknowledging that Stokes shift is the main spectral shift. The proposed exciton-phonon coupling leads to a unique mechanism where the stimulated emission band results from the counteraction between the absorption and photoluminescence bands. To fully take advantage of this mechanism, we propose that InP-based QDs with narrower emission lines and slower Auger recombination at higher pump intensities are needed.
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+.
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