Vanishing quantum confinement enables bright and thermally excited multi-carrier emission from semiconductor nanocrystals

TL;DR

This paper investigates the photophysics of bulk nanocrystals, revealing their multi-carrier emission properties, suppressed Auger recombination, and thermal equilibrium behavior, thus bridging the understanding between quantum-confined and bulk nanocrystals.

Contribution

It provides the first detailed single-particle analysis of multi-carrier states in bulk nanocrystals and introduces a model explaining their unique emission characteristics.

Findings

Multi-carrier states exhibit bimodal emission.

Strong suppression of Auger recombination observed.

Thermal equilibrium confirmed between electron and hole levels.

Abstract

Recently, nanocrystals in the regime of vanishing quantum confinement-termed bulk nanocrystals (BNCs)-have demonstrated remarkable 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 multi-carrier 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.