Anion Exchange and the Quantum-Cutting Energy Threshold in Ytterbium-Doped CsPb(Cl1- xBr x)3 Perovskite Nanocrystals.

ABSTRACT

Colloidal halide perovskite nanocrystals of CsPbCl3 doped with Yb3+ have demonstrated remarkably high sensitized photoluminescence quantum yields (PLQYs), approaching 200%, attributed to a picosecond quantum-cutting process in which one photon absorbed by the nanocrystal generates two photons emitted by the Yb3+ dopants. This quantum-cutting process is thought to involve a charge-neutral defect cluster within the nanocrystal's internal volume. We demonstrate that Yb3+-doped CsPbCl3 nanocrystals can be converted postsynthetically to Yb3+-doped CsPb(Cl1- xBr x)3 nanocrystals without compromising the desired high PLQYs. Nanocrystal energy gaps can be tuned continuously from Eg ≈ 3.06 eV (405 nm) in CsPbCl3 down to Eg ≈ 2.53 eV (∼490 nm) in CsPb(Cl0.25Br0.75)3 while retaining a constant PLQY above 100%. Reducing Eg further causes a rapid drop in PLQY, interpreted as reflecting an energy threshold for quantum cutting at approximately twice the energy of the Yb3+2F7/2 → 2F5/2 absorption threshold. These data demonstrate that very high quantum-cutting energy efficiencies can be achieved in Yb3+-doped CsPb(Cl1- xBr x)3 nanocrystals, offering the possibility to circumvent thermalization losses in conventional solar technologies. The presence of water during anion exchange is found to have a deleterious effect on the Yb3+ PLQYs but does not affect the nanocrystal shapes or morphologies, or even reduce the excitonic PLQYs of analogous undoped CsPb(Cl1- xBr x)3 nanocrystals. These results provide valuable information relevant to the development and application of these unique materials for spectral-shifting solar energy conversion technologies.