We correlate spatially resolved fluorescence (-lifetime) measurements with X-ray nanodiffraction to reveal surface defects in supercrystals of self-assembled cesium lead halide perovskite nanocrystals and study their effect on the fluorescence properties. Upon comparison with density functional modeling, we show that a loss in structural coherence, an increasing atomic misalignment between adjacent nanocrystals, and growing compressive strain near the surface of the supercrystal are responsible for the observed fluorescence blueshift and decreased fluorescence lifetimes. Such surface defect-related optical properties extend the frequently assumed analogy between atoms and nanocrystals as so-called quasi-atoms. Our results emphasize the importance of minimizing strain during the self-assembly of perovskite nanocrystals into supercrystals for lighting application such as superfluorescent emitters.

Surface-defect passivation is key to achieving a high photoluminescence quantum yield in lead halide perovskite nanocrystals. However, in perovskite light-emitting diodes, these surface ligands also have to enable balanced charge injection into the nanocrystals to yield high efficiency and operational lifetime. In this respect, alkaline halides have been reported to passivate surface trap states and increase the overall stability of perovskite light emitters. On the one side, the incorporation of alkaline ions into the lead halide perovskite crystal structure is considered to counterbalance cation vacancies, whereas on the other side, the excess halides are believed to stabilize the colloids. Here, we report an organic lithium salt, viz. LiTFSI, as a halide-free surface passivation on perovskite nanocrystals. We show that treatment with LiTFSI has multiple beneficial effects on lead halide perovskite nanocrystals and LEDs derived from them. We obtain a higher photoluminescence quantum yield and a longer exciton lifetime and a radiation pattern that is more favorable for light outcoupling. The ligand-induced dipoles on the nanocrystal surface shift their energy levels toward a lower hole-injection barrier. Overall, these effects add up to a 4-to 7-fold boost of the external quantum efficiency in proof-of-concept LED structures, depending on the color of the used lead halide perovskite nanocrystal emitters.

Surface ligand exchange on all‐inorganic perovskite nanocrystals of composition CsPbBrI2 reveals improved optoelectronic properties due to strong interactions of the nanocrystal with mono‐functionalized porphyrin derivatives. The interaction is verified experimentally with an array of spectroscopic measurements as well as computationally by exploiting density functional theory calculations. The enhanced current efficiency is attributed to a lowering of the charging energy by a factor of 2–3, which is determined by combining electronic and optical measurements on a selection of ligands. The coupled organic–inorganic nanostructures are successfully deployed in a light‐emitting device with higher current efficacy and improved charge carrier balance, magnifying the efficiency almost fivefold compared to the native ligand.

We show that the decomposition of caesium lead halide perovskite nanocrystals under continuous X-ray illumination depends on the surface ligand. For oleic acid/oleylamine, we observe a fast decay accompanied by...

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