Quantum Optoelectronics

Abstract:

We demonstrate that semiconductor quantum dots can be excited efficiently in a resonant three-photon process, whilst resonant two-photon excitation is highly suppressed. Time-dependent Floquet theory is used to quantify the strength of the multi-photon processes and model the experimental results. The efficiency of these transitions can be drawn directly from parity considerations in the electron and hole wavefunctions in semiconductor quantum dots. Finally, we exploit this technique to probe intrinsic properties of InGaN quantum dots. In contrast to non-resonant excitation, slow relaxation of charge carriers is avoided which allows us to measure directly the radiative lifetime of the lowest energy exciton states. Since the emission energy is detuned far from the resonant driving laser field, polarization filtering is not required and emission with a greater degree of linear polarization is observed compared to non-resonant excitation.

Abstract:

The main challenges in the optical and morphological tuning of highly stable orange-emitting Mn-doped perovskite include achieving uniform dopant distribution, maintaining structural integrity under varying environmental conditions, and optimizing luminescent efficiency while minimizing non-radiative recombination pathways. This study presents a novel, one-step, water-induced ultrafast synthesis strategy for obtaining Mn-doped mixed-halide perovskites at room temperature. This technique offers morphological control by varying the amount of water-based precursor, allowing the tuning of resulting nanostructures to produce nanoplatelets, nanocubes, or nanowires. In the growth mechanism, Mn2+ dopants affect the crystal structure by promoting stable growth and uniform doping at higher concentrations, while water improves ion dispersion, reaction kinetics, and passivation, facilitating optimal crystal growth and the formation of desired nanostructure morphologies. The synthesized Mn:CsPbBr3−xClx NCs form a highly stable colloidal solution with approximately 100 % emission stability for up to one year under ambient conditions and retain 98.9 % of its photoluminescence after aging at 85 °C for 200 h. We also explore the PL mechanism in Mn:CsPbBr3-xClx NCs, where temperature-dependent PL analysis reveals energy transfer from CsPbBr3-xClx exciton states to Mn2+-doped levels, enhancing PL intensity, with both exciton and Mn2+ emissions exhibiting a blue shift as the temperature increased from 6 K to 300 K, attributed to lattice expansion and electron–phonon interactions. A warm white light emission is achieved with excellent stability and an exceptionally wide color gamut coverage. The proposed strategy has the potential to enable large-scale synthesis and fabrication of highly stable perovskite devices for high-quality display and lighting applications.

Abstract:

CsPbCl₃ perovskite nanocrystals (NCs) are promising violet emitters owing to their narrow emission and high color purity, but their low defect tolerance demands careful passivation to achieve high photoluminescence quantum yield (PLQY), and typically only for fresh CsPbCl₃ NCs. Here, we report a delayed dual-passivation pathway in CsPbCl₃ NCs induced by the halide-rich molecular reagent phosphorus oxychloride (POCl₃), which unexpectedly yields a strong time-dependent PLQY enhancement instead of the rapid degradation usually observed. POCl₃ gradually decomposes into P- and Cl-containing species, enabling a controlled release of excess halides that autonomously passivates halide vacancies in a self-regulated manner. This dynamic self-healing process boosts the PLQY of colloidal CsPbCl₃ NCs by over 40-fold relative to pristine samples and sustains high violet emission efficiencies for more than 2 months of storage under ambient conditions. Spectroscopic measurements and calculations indicate that both liberated Cl^- and in situ-formed phosphonic species passivate halide vacancies and Pb^{2 +} dangling bonds, suppressing mid-gap defect states. The resulting self-passivated NCs deliver a luminance of 409 cd m^{- 2}, the highest reported for CsPbCl₃-based violet emitters. These results establish halide-rich dual passivators such as POCl₃ as powerful tools for long-term defect control in chloride perovskite NCs and for robust, bright violet-LEDs.

Abstract:

Lead-halide perovskite nanocrystals (NCs) have gained attention for optoelectronics, but careful selection of the antisolvent used for purification is essential to achieve high monodispersity and yield while minimizing surface damage. Current understanding indicates that this requires lowering the relative polarity of the antisolvent, yet high-polarity antisolvents are widely used for purification, as we confirm through data mining. We show that polarity alone is insufficient for antisolvent selection by comparing ethyl acetate and acetonitrile for CsPbI3 NC purification. Despite its higher polarity, acetonitrile yields improved colloidal stability compared to ethyl acetate. Using 1H NMR, FTIR, and XPS measurements, alongside DFT calculations, we demonstrate that acetonitrile acts as a stronger Lewis base, binding to and passivating the NC surface. Coordination of acetonitrile to the perovskite NC surface enhances stability and improves their performance in light-emitting diodes. These findings establish a mechanistic framework for antisolvent selection to realize bright and stable halide perovskite NCs.