DOI: https://doi.org/10.29363/nanoge.emlem.2024.021
Publication date: 13th July 2024
Halide perovskite nanocrystal superlattices exhibit collective superfluorescent emission, due to collective interactions between multiple simultaneously excited nanocrystals [1,2]. This coupling, enabled below a critical temperature of 180-200K, changes both the transition energy and emission rate compared with the emission of individual uncoupled nanocrystals. According to the superradiance model, first described by Dicke in the 1950s, when of several identical emitters are located within a small volume, coherent collective coupling through common vacuum modes of the electromagnetic field result in a faster emission rate [3]. The ensemble of emitters behaves as one large transition dipole with an oscillator strength proportional to the number of coupled emitters. Although Dicke superradiance is commonly observed in dense atomic gases, recent observation of superfluorescent emission in solid state semiconductor systems is nontrivial as they deviate from the ideal superradiance model framework due to strong dipole-dipole interactions between the emitters [2]. We demonstrate how quantum confinement governs the type of coupling through synthetical control over nanocrystal size, and by compositional control over the Bohr radius via anion exchange. Superlattices made of weakly confined nanocrystals, showed a red-shifted collective photon bunching emission bursts with a faster emission rate, showcasing key characteristics of superfluorescence. In contrast, superlattices made of strongly confined nanocrystals showed a blue-shifted collective photon bunching emission bursts, despite having a slower radiative rate. We explain these different modes of collective behavior by suggesting a critical role for exciton dipole-dipole interactions between neighboring nanocrystals in the superlattice. We utilize the exciton interaction theory, which was developed by Kasha in the 1960s to explain attractive (J-type) and repulsive (H-type) dipole-dipole interactions in molecular aggregates [4]. The H/J aggregate behavior switching in perovskite nanocrystals, is the result of modified exciton orientation, due to the quantum confinement. The confinement changes the preferred alignment of transition dipoles in the nanocrystals, shown by analysis of angular-dependent emission patterns, thereby changing the relative dipole orientation between neighbouring nanocrystals, and dictating the resulting optical behavior of the ensemble. Merging Kasha exciton interaction theory with Dicke superradiance model, provides new understanding of exciton interactions and collective emission phenomena at the solid state.
We thank our collaborators: Alexey Gorlach , Einav Scharf , Yonatan Ossia , Rotem Liran , Kobi Cohen , Rotem Strassberg , Ido Kaminer , and Uri Banin
We thank Dr. Maria Koifman for the SEM imaging, and to Dr. Inna Popov, and Dr. Ilya Torchinsky for their help in the angular emission measurements.
This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 949682- ERC.