Aging of Self-Assembled Lead Halide Perovskite Nanocrystal Superlattices: Effects on Photoluminescence and Energy Transfer

Abstract

Excitonic coupling, electronic coupling, and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a red-shifted collective 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 studying CsPbBr3 nanocrystal superlattices over time with room-temperature and cryogenic micro-photoluminescence spectroscopy, X-ray diffraction, and electron microscopy. It is shown that a gradual contraction of the superlattices and subsequent coalescence of the nanocrystals occurs over several days of keeping such structures under vacuum. 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. Overall, the aging of CsPbBr3 nanocrystal assemblies dramatically alters their emission properties and that should not be overlooked when studying collective optoelectronic phenomena nor confused with superfluorescence effects. ; The work of D.B. was supported by the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie Grant Agreement No. 794560 (RETAIN). R.X.Y. and L.Z.T. were supported by the Molecular Foundry, a DOE Office of Science User Facility of the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. D.S. acknowledges support from the project PRIN Interacting Photons in Polariton Circuits—INPhoPOL (Ministry of University and Scientific Research, MIUR, 2017P9FJBS_001). We thank P. Cazzato, L. De Marco, D. Ballarini, D. G. Suárez-Forero, V. Ardizzone, L. ...