Spontaneous Formation of Lead-Free Cs₃ Cu₂ I₅  Quantum Dots in Metal-Organic-Frameworks with Deep-Blue Emission

All-inorganic lead-free Cs₃ Cu₂ I₅  perovskite-derivant quantum dots (QDs) have attracted tremendous attention due to their nontoxicity and unique optoelectronic properties. However, the traditional hot-injection method requires high temperatures and multiple ligands to confine the growth of QDs. Herein, a strategy is reported to spontaneously synthesize ultrasmall Cs₃ Cu₂ I₅  QDs within metal-organic-frameworks (MOFs) MOF-74 at room temperature (RT) with an average diameter of 4.33 nm. The obtained Cs₃ Cu₂ I₅  QDs exhibit an evident deep-blue emission with Commission Internationale de L'Eclairage coordinates of (0.17, 0.07), owing to the strong quantum confinement effect. Due to the protection of MOF-74, the Cs₃ Cu₂ I₅  QDs demonstrate superior stability, and the photoluminescence quantum yield retains 89% of the initial value after the storage of 1440 h under the environment with relative humidity exceeding 70%. Besides, triplet-triplet annihilation upconversion emission is observed within the composite of Cs₃ Cu₂ I₅ @MOF-74, which brings out apparent temperature-dependent photoluminescence. This study reveals a facile method for fabricating ultrasmall lead-free perovskite-derivant QDs at RT without multiple ligands. Besides, the temperature-dependent photoluminescence of Cs₃ Cu₂ I₅ @MOF-74 may open up a new way to develop the applications of temperature sensors or other related optoelectronic devices.