Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund's rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the 'dark exciton'. Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX, with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin-orbit coupling in the conduction band of a perovskite is combined with the Rashba effect. We then apply our model to CsPbX nanocrystals, and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster than any other semiconductor nanocrystal at room and cryogenic temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting, lasers and displays, these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices.

The bright emission observed in cesium lead halide perovskite nanocrystals (NCs) has recently been explained in terms of a bright exciton ground state [Becker et al. Nature 2018, 553, 189−193], a claim that would make these materials the first known examples in which the exciton ground state is not an optically forbidden dark exciton. This unprecedented claim has been the subject of intense experimental investigation that has so far failed to detect the dark ground-state exciton. Here, we review the effective-mass/electron−hole exchange theory for the exciton fine structure in cubic and tetragonal CsPbBr 3 NCs. In our calculations, the crystal field and the short-range electron−hole exchange constant were calculated using density functional theory together with hybrid functionals and spin−orbit coupling. Corrections associated with long-range exchange and surface image charges were calculated using measured bulk effective mass and dielectric parameters. As expected, within the context of the exchange model, we find an optically inactive ground exciton level. However, in this model, the level order for the optically active excitons in tetragonal CsPbBr 3 NCs is opposite to what has been observed experimentally. An alternate explanation for the observed bright exciton level order in CsPbBr 3 NCs is offered in terms of the Rashba effect, which supports the existence of a bright ground-state exciton in these NCs. The size dependence of the exciton fine structure calculated for perovskite NCs shows that the bright−dark level inversion caused by the Rashba effect is suppressed by the enhanced electron−hole exchange interaction in small NCs.

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(FA-acetate, 99%) were purchased from Sigma-Aldrich and used as received unless otherwise specified. CsPbI3 QD synthesis. The synthesis was performed following the method reported in our previous publications with slight modification. 1,2 First, 20 mL of ODE is mixed with 1.25 mL of OA containing 0.407 g of Cs2CO3. This was degassed at 120°C for 20 min under vacuum in a three-neck flask to form Cs-oleate. The Cs-oleate precursor was kept under N2 instead of vacuum after Cs2CO3 was completely dissolved in the solution. Then the PbI2 precursor was formed by mixing 0.5 g of PbI2 and 25 mL of ODE in a three-neck flask and heated at 120°C for 20 min under vacuum. A preheated mixture of OA and OAm (135°C, 2.5 mL each) was transferred into the PbI2 solution that was kept at 120°C under vacuum. After the PbI2 completely dissolved in the solution, the reaction flask was heated to the desired temperature (140, 160, or 180°C) under flowing N2. Then 2 mL of the Cs-oleate precursor was swiftly injected into the reaction flask. In general, smaller nanocrystals are obtained with lower growth and larger are obtained with higher temperature, but some sizes overlap this trend when using the size selective precipitation. Immediately after the reaction, the mixture was quenched by submerging the flask into an ice bath within 3 s after the injection. After cooling to room temperature, 70 mL of MeOAc was added into the colloidal solution and the mixed solution was centrifuged at 7500 rpm for 5 min.

We demonstrate a 1.5-mm-wavelength fiber laser formed by placement of glass microsphere resonators along a fiber taper. The fiber taper serves the dual purpose of transporting optical pump power into the spheres and extracting the resulting laser emission. A highly doped erbium:ytterbium phosphate glass was used to form microsphere resonant cavities with large gain at 1.5 mm. Laser threshold pump powers of 60 mW and fiber-coupled output powers as high as 3 mW with single-mode operation were obtained. A bisphere laser system consisting of two microspheres attached to a single fiber taper is also demonstrated.

Ligand-capped nanocrystals (NCs) of lead halide perovskites, foremost fully inorganic CsPbX3 NCs, are the latest generation of colloidal semiconductor quantum dots. They offer a set of compelling characteristicslarge absorption cross section, as well as narrow, fast, and efficient photoluminescence with long exciton coherence timesrendering them attractive for applications in light-emitting devices and quantum optics. Monodisperse and shape-uniform, broadly size-tunable, scalable, and robust NC samples are paramount for unveiling their basic photophysics, as well as for putting them into use. Thus far, no synthesis method fulfilling all these requirements has been reported. For instance, long-chain zwitterionic ligands impart the most durable surface coating, but at the expense of reduced size uniformity of the as-synthesized colloid. In this work, we demonstrate that size-selective precipitation of CsPbBr3 NCs coated with a long-chain sulfobetaine ligand, namely, 3-(N,N-dimethyloctadecylammonio)-propanesulfonate, yields monodisperse and sizable fractions (>100 mg inorganic mass) with the mean NC size adjustable in the range between 3.5 and 16 nm and emission peak wavelength between 479 and 518 nm. We find that all NCs exhibit an oblate cuboidal shape with the aspect ratio of 1.2 × 1.2 × 1. We present a theoretical model (effective mass/k·p) that accounts for the anisotropic NC shape and describes the size dependence of the first and second excitonic transition in absorption spectra and explains room-temperature exciton lifetimes. We also show that uniform zwitterion-capped NCs readily form long-range ordered superlattices upon solvent evaporation. In comparison to more conventional ligand systems (oleic acid and oleylamine), supercrystals of zwitterion-capped NCs exhibit larger domain sizes and lower mosaicity. Both kinds of supercrystals exhibit superfluorescence at cryogenic temperaturesaccelerated collective emission arising from the coherent coupling of the emitting dipoles.

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In this Mini Review, we summarize major corrections to the dark-bright exciton theory [ Efros et al. Phys. Rev B 1996 , 54 , 4843 - 4856 ], which should be used for quantitative description of the band edge exciton in II-VI and III-V compound quantum-dot nanocrystals (NCs). The theory previously did not take into account the long-range exchange interaction, resulting in the under-estimation of the splitting between the upper bright and lower dark or quasi-dark exciton, as reported by several experimental groups. Another type of correction originates from the closeness in energy of the ground, 1S, and the first excited, 1P, hole levels in a spherical NC, resulting in significant energetic overlap of the levels from the 1S1S and 1P1S exciton manifolds connected with the ground 1S electron level. The thermal occupation of the optically forbidden 1P1S exciton levels changes the radiative decay time of the NCs at both helium and room temperatures. We demonstrate the role of both effects in CdSe NCs and compare our predictions with available experimental data.