Colloidal lead halide perovskite (LHP) nanocrystals are of interest as photoluminescent quantum dots (QDs) whose properties depend on the size and shape. They are normally synthesized on subsecond time scales through hard-to-control ionic metathesis reactions. We report a room-temperature synthesis of monodisperse, isolable spheroidal APbBr 3 QDs (A=Cs, formamidinium, methylammonium) that are size-tunable from 3 to over 13 nanometers. The kinetics of both nucleation and growth are temporally separated and drastically slowed down by the intricate equilibrium between the precursor (PbBr 2 ) and the A[PbBr 3 ] solute, with the latter serving as a monomer. QDs of all these compositions exhibit up to four excitonic transitions in their linear absorption spectra, and we demonstrate that the size-dependent confinement energy for all transitions is independent of the A-site cation.

All‐inorganic lead‐halide perovskite (LHP) (CsPbX3, X = Cl, Br, I) quantum dots (QDs) have emerged as a competitive platform for classical light‐emitting devices (in the weak light–matter interaction regime, e.g., LEDs and laser), as well as for devices exploiting strong light–matter interaction at room temperature. Many‐body interactions and quantum correlations among photogenerated exciton complexes play an essential role, for example, by determining the laser threshold, the overall brightness of LEDs, and the single‐photon purity in quantum light sources. Here, by combining cryogenic single‐QD photoluminescence spectroscopy with configuration‐interaction (CI) calculations, the size‐dependent trion and biexciton binding energies are addressed. Trion binding energies increase from 7 to 17 meV for QD sizes decreasing from 30 to 9 nm, while the biexciton binding energies increase from 15 to 30 meV, respectively. CI calculations quantitatively corroborate the experimental results and suggest that the effective dielectric constant for biexcitons slightly deviates from the one of the single excitons, potentially as a result of coupling to the lattice in the multiexciton regime. The findings here provide a deep insight into the multiexciton properties in all‐inorganic LHP QDs, essential for classical and quantum optoelectronic devices.

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