Dark exciton as the lowest-energy (ground) exciton state in metal halide perovskite nanocrystals is a subject of much interest. This is because the superior performance of perovskites as the photon source combined with long lifetime of dark exciton is very attractive for the applications such as quantum information processing. However, the direct observation of the long-lived dark exciton emission confirming the accessibility to dark ground exciton state has remained elusive. Here, we report the intense photoluminescence from dark exciton with microsecond lifetime in strongly confined CsPbBr3 nanocrystals and reveal the crucial role of confinement in accessing the dark ground exciton state. This study establishes the potential of strongly quantum confined perovskite nanostructures as the excellent platform to harvest the benefits of extremely long-lived dark exciton.

The fine structure of the band edge exciton and the dark exciton photoluminescence (PL) are topics of significant interest in the research of semiconducting metal halide perovskite nanocrystals, with several conflicting reports on the level ordering of the bright and dark states and the accessibility of the emitting dark states. Recently, we observed the intense dark exciton PL in strongly confined CsPbBr3 nanocrystals at cryogenic temperatures, in contrast to weakly confined nanocrystals lacking dark exciton PL, which was explained by the confinement enhanced bright–dark exciton splitting. In this work, we investigated the size-dependence of the dark exciton photoluminescence properties in CsPbBr3 and CsPbI3 quantum dots in the strongly confined regime, showing the clear role of confinement in determining the bright–dark energy splitting (ΔEBD) and the dark exciton lifetime (τD). We observe the increase in both ΔEBD and τD with increasing quantum confinement in CsPbBr3 and CsPbI3 QDs, consistent with the earlier predictions on the size-dependence of ΔEBD and τD. Our results show that quantum confinement plays a crucial role in determining the accessibility to the dark exciton PL and its characteristics in metal halide perovskite nanocrystals.

Hot electrons play a crucial role in enhancing the efficiency of photon-to-current conversion or photocatalytic reactions. In semiconductor nanocrystals, energetic hot electrons capable of photoemission can be generated via the upconversion process involving the dopant-originated intermediate state, currently known only in Mn-doped cadmium chalcogenide quantum dots. Here, we report that Mn-doped CsPbBr 3 nanocrystals are an excellent platform for generating hot electrons via upconversion that can benefit from various desirable exciton properties and the structural diversity of metal halide perovskites (MHPs). Two-dimensional Mn-doped CsPbBr 3 nanoplatelets are particularly advantageous for hot electron upconversion due to the strong exciton−dopant interaction mediating the upconversion process. Furthermore, nanoplatelets reveal evidence for the hot electron upconversion via long-lived dark excitons in addition to bright excitons that may enhance the upconversion efficiency. This study establishes the feasibility of hot electron upconversion in MHP hosts and demonstrates the potential merits of twodimensional MHP nanocrystals in the upconversion process.

We investigated the magnetic effect of Mn 2+ ions on an exciton of Mndoped CsPbI 3 quantum dots (QDs), where we looked for the signatures of an exciton magnetic polaron known to produce a large effective magnetic field in Mn-doped CdSe QDs. In contrast to Mn-doped CdSe QDs that can produce ∼100 T of magnetic field upon photoexcitation, manifested as a large change in the energy and relaxation dynamics of a bright exciton, Mn-doped CsPbI 3 QDs exhibited little influence of a magnetic dopant on the behavior of a bright exciton. However, a μs-lived dark exciton in CsPbI 3 QDs showed 40% faster decay in the presence of Mn 2+ , equivalent to the effect of ∼3 T of an external magnetic field. While further study is necessary to fully understand the origin of the large difference in the magneto-optic property of an exciton in two systems, we consider that the difference in antiferromagnetic coupling of the dopants is an important contributing factor.

Synthesis conditions for the anionic polymerization of PTMA, PTFEMA and PTMA-b-PTFEMA are reported, long-range ordering of the block copolymers is characterized.