Vanishing Quantum Confinement Enables Bright and Thermally Excited Multicarrier Emission from Semiconductor Nanocrystals.

Recently, nanocrystals in the regime of vanishing quantum confinement─termed bulk nanocrystals (BNCs)─have demonstrated optical gain characteristics. While their high-power lasing performance was demonstrated convincingly, the photophysics at low and intermediate powers─where charge-carrier populations are discrete─remain unexplored. Using single-photon avalanche diode (SPAD) array technology, we resolve the dynamics and energetics of six multicarrier excited states in individual CdSe/CdS core/shell BNCs, containing up to four electrons and two holes. Each state exhibits bimodal emission, indicative of thermal equilibrium between closely spaced electron and hole levels, confirmed via temperature-dependent single-particle measurements. Quantification of radiative and nonradiative decay channels reveals strongly suppressed Auger recombination through both the negative- and positive-trion pathways. We present a model that combines statistical scaling of rate constants with Fermi-Dirac thermal occupations of electron and hole levels, bridging the transitional regime between quantum-confined and bulk nanocrystals, and providing a comprehensive framework for understanding this emerging class of materials.