Synthesis and Properties of Strongly Quantum-Confined Cesium Lead Halide Perovskite Nanocrystals.

ConspectusSemiconducting metal halide perovskite (MHP) nanocrystals have emerged as an important new class of materials as the source of photons and charges for various applications that can outperform many other semiconductor nanocrystals utilized for the same purposes. However, the majority of the studies of MHP nanocrystals focused on weakly or nonconfined systems, where the quantum confinement giving rise to various size-dependent and confinement-enhanced photophysical properties cannot be explored readily. This was partially due to the challenge in producing strongly quantum-confined MHP nanocrystals, since the traditional kinetic control approach was less effective for the size control. Recent synthetic progress in MHP nanocrystals utilizing the equilibrium-based size control achieved the precise control of quantum confinement with high ensemble uniformity, enabling the exploration of the unique properties of MHP nanocrystals under strong quantum confinement. In this Account, we review the recent progress made in the synthesis of strongly quantum-confined cesium lead halide nanocrystals and investigation of the properties of exciton modified by strong quantum confinement. The main body of this Account discusses the key results of the research in this field in two separate sections. Section 2 describes the thermodynamic equilibrium-based synthesis method to control the size of cesium lead halide perovskite quantum dots in strongly confined regime. Size control in anisotropic nanocrystals with one- and two-dimensional quantum confinement is also discussed. Section 3 covers the following three topics that highlight the effects of quantum confinement on various spectroscopic properties of excitons in cesium lead halide perovskite nanocrystals: (1) Size-dependent absorption cross section of cesium lead halide quantum dots; (2) confinement effect on exciton fine structure and access to the dark exciton exhibiting intense and long-lived photoluminescence; (3) activation of forbidden exciton transition via dynamic lattice distortion by the photoexcited charge carriers enhanced by quantum confinement. The impact of strong quantum confinement goes beyond the properties of excitons covered in this Account and is expected to expand the functionality of MHP nanocrystals as the source of photons and charges. For instance, realization of the possible enhancement of photon down- and upconversion and hot carrier generation via quantum confinement will further increase the usefulness of strongly confined MHP nanocrystals in their applications.