Excitonic/electronic coupling and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a collective low energy emission peak with accelerated dynamics. Here we report that similar spectroscopic features could appear as a result of the nanocrystal reactivity within the self-assembled superlattices. This is demonstrated by using CsPbBr3 nanocrystal superlattices under room temperature and cryogenic micro-photoluminescence spectroscopy. It is shown that keeping such structures under vacuum, a gradual contraction of the superlattices and subsequent coalescence of the nanocrystals occurs over several days. As a result, a narrow, low energy emission peak is observed at 4 K with a concomitant shortening of the photoluminescence lifetime due to the energy transfer between nanocrystals. When exposed to air, self-assembled CsPbBr3 nanocrystals develop bulk-like CsPbBr3 particles on top of the superlattices. At 4 K, these particles produce a distribution of narrow, low energy emission peaks with short lifetimes and excitation fluence-dependent, oscillatory decays, resembling the features of superfluorescence. Overall, the reactivity of CsPbBr3 nanocrystals dramatically alters the emission of their assemblies, which should not be overlooked when studying collective optoelectronic properties nor confused with superfluorescence effects.
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