Negative Thermal Quenching in Quantum-Cutting Yb<sup>3+</sup>-Doped CsPb(Cl<sub>1–</sub><i><sub>x</sub></i>Br<i><sub>x</sub></i>)<sub>3</sub> Perovskite Nanocrystals
Joo Yeon D. Roh, Tyler J. Milstein, Daniel R. Gamelin
Abstract
Ytterbium-doped all-inorganic lead-halide perovskites (Yb 3+:CsPb(Cl 1– x Br x ) 3 ) show broadband absorption and exceptionally high near-infrared photoluminescence quantum yields, providing opportunities for solar spectral shaping to improve photovoltaic power conversion efficiencies. Here, we report that Yb 3+:CsPb(Cl 1– x Br x ) 3 NCs also show extremely strong negative thermal quenching of the Yb 3+ luminescence, with intensities at room temperature >100 times those at 5 K for some compositions. Analysis of this temperature dependence as a function of x shows that it stems from thermally activated quantum cutting related to the temperature dependence of the spectral overlap between the PL of the perovskite (donor) and the simultaneous-pair absorption of two Yb 3+ ions (acceptor). In the Yb 3+:CsPbBr 3 limit, this spectral overlap goes to zero at 5 K, such that only single-Yb 3+ sensitization requiring massive phonon emission occurs. At room temperature, Yb 3+ PL in this composition is enhanced ∼135-fold by thermally activated quantum cutting, highlighting the extreme efficiency of quantum cutting relative to single-Yb 3+ sensitization. These results advance the fundamental mechanistic understanding of quantum cutting in doped perovskites, with potential ramifications for solar and photonics technologies.