Thermodynamic-Kinetic Decoupling Enables Stable Excitonic Emission in Defect-Tolerant Cu-Based Quantum Dots
Colloidal quantum dots that simultaneously offer room-temperature single-photon purity and high photoluminescence quantum yield are sought for quantum optics, but remain elusive in environmentally benign materials. We introduce a thermodynamic-kinetic decoupling strategy that transforms defect-tolerant CuInS2 quantum dots into bright, narrowband, and photostable single-photon emitters. Zn2+ alloying strains the lattice, thermodynamically suppressing native copper vacancies and narrowing the emission from a broad defect band of approximately 300 meV to an excitonic line of approximately 120 meV. Ga3+ incorporation then kinetically pins the cation sublattice against Cu+ migration, preventing defect regeneration during ZnS shell growth. The resulting Cd-free core/shell dots achieve near-unity quantum yield of approximately 98% while retaining narrow excitonic emission. Critically, room-temperature single-dot spectroscopy reveals homogeneous linewidths as low as approximately 58 meV, strongly suppressed blinking, and high-purity single-photon emission with g2(0) = 0.06. This stabilized excitonic emission directly reduces reabsorption losses in luminescent solar concentrators, yielding an external optical efficiency of 12.68%. Our work establishes a generalizable framework to unlock intrinsic excitonic photophysics in ion-mobile, defect-prone semiconductors, opening a viable path toward high-performance heavy-metal-free emitters for quantum light sources.