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

• Published in: Nano letters Vol. 19; no. 3; pp. 1931 - 1937
• Main Authors: Milstein, Tyler J, Kluherz, Kyle T, Kroupa, Daniel M, Erickson, Christian S, De Yoreo, James J, Gamelin, Daniel R
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.03.2019
• Subjects: ytterbium doping; anion exchange; Perovskite nanocrystals; quantum cutting
• ISSN: 1530-6984; 1530-6992
• DOI: 10.1021/acs.nanolett.8b05104

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–x Br x )3 nanocrystals without compromising the desired high PLQYs. Nanocrystal energy gaps can be tuned continuously from E g ≈ 3.06 eV (405 nm) in CsPbCl3 down to E g ≈ 2.53 eV (∼490 nm) in CsPb­(Cl0.25Br0.75)3 while retaining a constant PLQY above 100%. Reducing E g 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–x Br 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–x Br 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.