Nanocrystal (NC) self-assembly is a versatile platform for materials engineering at the mesoscale. The NC shape anisotropy leads to structures not observed with spherical NCs. This work presents a broad structural diversity in multicomponent, long-range ordered superlattices (SLs) comprising highly luminescent cubic CsPbBr 3 NCs (and FAPbBr 3 NCs) coassembled with the spherical, truncated cuboid, and disk-shaped NC building blocks. CsPbBr 3 nanocubes combined with Fe 3 O 4 or NaGdF 4 spheres and truncated cuboid PbS NCs form binary SLs of six structure types with high packing density; namely, AB 2 , quasi-ternary ABO 3 , and ABO 6 types as well as previously known NaCl, AlB 2 , and CuAu types. In these structures, nanocubes preserve orientational coherence. Combining nanocubes with large and thick NaGdF 4 nanodisks results in the orthorhombic SL resembling CaC 2 structure with pairs of CsPbBr 3 NCs on one lattice site. Also, we implement two substrate-free methods of SL formation. Oil-in-oil templated assembly results in the formation of binary supraparticles. Self-assembly at the liquid–air interface from the drying solution cast over the glyceryl triacetate as subphase yields extended thin films of SLs. Collective electronic states arise at low temperatures from the dense, periodic packing of NCs, observed as sharp red-shifted bands at 6 K in the photoluminescence and absorption spectra and persisting up to 200 K.

Lead halide perovskite nanocrystals (NCs) were recently found to exhibit extraordinary optical amplification properties. The great majority of such studies implemented ultrashort photon pulses in the femtosecond regime to initiate the stimulated emission process. Yet the realization of practical lasing applications based on such materials is crucially dependent on their ability to sustain optical amplification at significantly longer time scales, at which major losses associated with spontaneous emission and nonradiative recombination occur. Herein we demonstrate highly efficient amplified spontaneous emission (ASE) from close-packed films of formamidinium lead iodide perovskite (FAPbI3) NCs under excitation in the nanosecond regime. Systematic optimization of the NC processing and thermal treatment yields solids that exhibit high ASE net modal gain up to 604 cm–1 and weakly temperature sensitive ASE thresholds with room-temperature values as low as 140 μJ cm–2. The efficient optical amplification using excitation pulses comparable to the exciton lifetime combined with the excellent chemical durability and air stability of FAPbI3 NCs renders them outstanding gain media for continuous-wave lasers in the red and near-infrared.

Advances in the technology and processing of flexible optical materials have paved the way toward the integration of semiconductor emitters and polymers into functional light emitting fabrics. Lead halide perovskite nanocrystals appear as highly suitable optical sensitizers for such polymer fiber emitters due to their ease of fabrication, versatile solution-processing and highly efficient, tunable, and narrow emission across the visible spectrum. A beneficial byproduct of the nanocrystal incorporation into the polymer matrix is that it provides a facile and low-cost method to chemically and structurally stabilize the perovskite nanocrystals under ambient conditions. Herein, we demonstrate two types of robust fiber composites based on electrospun hydrophobic poly(methyl methacrylate) (PMMA) or hydrophilic polyvinylpyrrolidone (PVP) fibrous membranes sensitized by green-emitting all-inorganic CsPbBr 3 or hybrid organic-inorganic FAPbBr 3 nanocrystals. We perform a systematic investigation on the influence of the nanocrystal-polymer relative content on the structural and optical properties of the fiber nanocomposites and we find that within a wide content range, the nanocrystals retain their narrow and high quantum yield emission upon incorporation into the polymer fibers. Quenching of the radiative recombination at the higher/lower bound of the nanocrystal:polymer mass ratio probed is discussed in terms of nanocrystal clustering/ligand desorption due to dilution effects, respectively. The nanocomposite's optical stability over an extended exposure in air and upon immersion in water is also discussed. The studies confirm the demonstration of robust and bright polymer-fiber emitters with promising applications in backlighting for LCD displays and textile-based light emitting devices.

Solution-processed lasers are cost-effective, compatible with a vast range of photonic resonators, and suited for a mass production of flexible, lightweight, and disposable devices. The emerging class of lead halide perovskite nanocrystals (LHP NCs) can serve as a highly suitable active medium for such lasers, owing to their outstanding optical gain properties and the suppressed optical nonradiative recombination losses stemming from their defect-tolerant nature. In this work, CsPbBr 3 NCs are embedded within polymeric Bragg reflectors to produce fully solution-processed microcavities. By a systematic parametric optimization of the polymer mirrors, resonators with Q-factors up to 110 can be produced in the green, supporting amplified spontaneous emission (ASE) under continuous wave excitation, with a threshold as low as 140 mW/cm 2 . Angle-dependent reflectivity and luminescence studies performed below the ASE threshold demonstrate the strong spectral and angular redistribution of the CsPbBr 3 NC spontaneous emission when coupled to the cavity mode. Under resonance, amplification of the output intensity by a factor of 9 in the vicinity of the cavity mode and by a factor of 5 in the whole integrated emission along with an increase of the radiative rate accounted by a Purcell factor of 2 is obtained with respect to NCs deposited in reference microcavity structures.

The primary obstacle to the use of lead halide perovskite nanocrystals (NCs) in optoelectronics is the inability of traditional ligand engineering approaches to provide robust surface passivation. The structural lability can be mitigated by employing different ligands such as long-chain quaternary ammonium and zwitterionic surfactants. Here, we report a comprehensive study that probes the impact of such surface passivation routes on the optoelectronic properties of weakly confined CsPbBr 3 NCs. Spectroscopy unravels clear correlations of various photophysical figures of merit with the ligand type used. Compared to NCs decorated by conventional oleic acid/oleylamine ligands, passivation with the quaternary ammonium or zwitterionic surfactants increases the NC solid-state emission yield by up to 40% by halving the average trap depth and increasing by 1.5 times the exciton binding energy. Furthermore, the aforementioned ligands better preserve the size of NCs in thin films, as shown by the absence of significant NC aggregation and the confinement-induced increase by a factor of 2 of the Froḧlich interaction between excitons and optical phonons. The suitability of ligands for photonics is finally assessed by probing metrics, such as the amplified spontaneous emission threshold, the moisture tolerance, and the photoconductivity and electroluminescent performance of lateral and vertical devices, respectively.

The slowdown of carrier cooling in lead halide perovskites (LHP) may allow the realization of efficient hot carrier solar cells. Much of the current effort focuses on the understanding of the mechanisms that retard the carrier relaxation, while proof-of-principle demonstrations of hot carrier harvesting have started to emerge. Less attention has been placed on the impact that the energy and momentum relaxation slowdown imparts on the spontaneous and stimulated light-emission process. LHP nanocrystals (NCs) provide an ideal testing ground for such studies as they exhibit bright emission and high optical gain, while the carrier cooling bottleneck is further pronounced compared to their bulk analogues due to confinement. Herein, the luminescent properties of CsPbBr3, FAPbBr3, and FAPbI3 NCs in the strong photoexcitation regime are investigated. In the former two NC systems, amplified spontaneous emission is found to dominate over the radiative recombination at average carrier occupancy per nanocrystal larger than 5–10. On the other hand, under the same photoexcitation conditions in the FAPbI3 NCs, a longer lived population of hot carriers results in a competition between hot luminescence, stimulated emission, and defect recombination. The dynamic interplay between the aforementioned three emissive channels appears to be influenced by various experimental and material parameters that include temperature, material purity, film morphology, and excitation pulse width and wavelength.

Lead halide perovskite nanocrystals (NCs) are highly suitable active media for solution-processed lasers in the visible spectrum, owing to the wide tunability of their emission from blue to red via facile ion-exchange reactions. Their outstanding optical gain properties and the suppressed nonradiative recombination losses stem from their defecttolerant nature. In this work, we demonstrate flexible waveguides combining the transparent, bioplastic, polymer cellulose acetate with green CsPbBr 3 or red-emitting CsPb(Br,I) 3 NCs in simple solutionprocessed architectures based on polymer-NC multilayers deposited on polymer micro-slabs. Experiments and simulations indicate that the employment of the thin, free-standing membranes results in confined electrical fields, enhanced by 2 orders of magnitude compared to identical multilayer stacks deposited on conventional, rigid quartz substrates. As a result, the polymer structures exhibit improved amplified emission characteristics under nanosecond excitation, with amplified spontaneous emission (ASE) thresholds down to ∼95 μJ cm −2 and ∼70 μJ cm −2 and high net modal gain up to ∼450 and ∼630 cm −1 in the green and red parts of the spectrum, respectively. The optimized gain properties are accompanied by a notable improvement of the ASE operational stability due to the low thermal resistance of the substrate-less membranes and the intimate thermal contact between the polymer and the NCs. Their application potential is further highlighted by the membrane's ability to sustain dual-color ASE in the green and red parts of the spectrum through excitation by a single UV source, activate underwater stimulated emission, and operate as efficient white light downconverters of commercial blue LEDs, producing high-quality white light emission, 115% of the NTSC color gamut.

Colloidal quantum dots (CQDs) are typically decorated with organic molecules that provide surface passivation and colloidal solubility. An alternate but less studied surface functionalization approach via inorganic complexes can produce stable CQDs with attractive transport and optical properties. Further development of such all-inorganic CQD solids is dependent on the deeper understanding of the energetic and dynamic interactions of the new ligands with the CQD excitons. Herein, a series of four metal chalcogenide (MCC) ligands of the K z XS 4 type were attached to PbS CQDs. Out of the four MCC complexes studied, we find that only K 4 GeS 4 ligands yield robust PbS CQD films with bright photoluminescence (PL) in the solid state. A systematic spectroscopic investigation of the K 4 GeS 4 -capped CQD films provides evidence of the temperature-dependent ligand-mediated exciton delocalization and trapping processes. At low temperatures, efficient trapping at ligand-induced states is found to occur within ∼6 ns after photoexcitation, followed by a considerably slower exciton back transfer to the CQD core. At elevated temperatures, the CQD films become photoconductive, providing evidence of exciton dissociation via carrier transfer within adjacent dots. The addition of a thin CdS shell suppresses the delocalization and trapping of excitons, resulting in brighter emission and significantly slower transient absorption and PL dynamics.