Deterministic nucleation of nanocrystal superlattices on 2D perovskites for light-funneling heterostructures

Abstract

Semiconductor heterostructures that combine components with different dimensionality provide an interesting way to manipulate the physical properties of the resulting material. Two-dimensional lead halide perovskites crystallize as flat microcrystals and have efficient in-plane exciton mobility, while perovskite nanocrystals are efficient emitters with a tunable bandgap that can self-assemble into microscopic superlattices. However, combining such intricate architectures into heterostructures has been challenging due to the mismatch in solubility properties and the challenging transfer procedures. Here we realize heterostructures where CsPbBr3 nanocrystal superlattices are deterministically grown along the faces of PEA2PbBr4 two-dimensional layered perovskite microcrystals. The growth can be limited to the lateral faces of the microcrystals and result in core-crown epitaxial heterostructures, or extended to the vertical direction leading to core-shell-like structures. The growth method is simple yet effective and versatile, and promises to be expanded to a large variety of other materials. We demonstrate that these heterostructures can be employed as efficient light-harvesting systems. In fact, energy can be transferred from the two-dimensional microcrystal domain to the superlattices, enabling switching between linear and non-linear carrier recombination regimes by tuning the excitation fluence. Moreover, by exploiting the lifetime shortening of CsPbBr3 nanocrystal emission upon sample cooling, we ensure that energy transfer occurs after the biexcitonic and single-excitonic decays of the nanocrystals, effectively extending the radiative recombination of superlattices.