Resonant Multiple-Phonon Absorption Causes Efficient Anti-Stokes Photoluminescence in CsPbBr<sub>3</sub> Nanocrystals.

Zhang, Zhuoming; Ghonge, Sushrut; Ding, Yang; Zhang, Shubin; Berciu, Mona; Schaller, Richard D; Jankó, Boldizsár; Kuno, Masaru · ACS Nano · 2024

basic_science · Level V

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Abstract

Lead halide perovskite nanocrystals, such as CsPbBr<sub>3</sub>, exhibit efficient photoluminescence (PL) up-conversion, also referred to as anti-Stokes photoluminescence (ASPL). This is a phenomenon where irradiating nanocrystals up to 100 meV below gap results in higher energy band edge emission. Most surprising is that ASPL efficiencies approach unity and involve single-photon interactions with multiple phonons. This is unexpected given the statistically disfavored nature of multiple-phonon absorption. Here, we report and rationalize near-unity anti-Stokes photoluminescence efficiencies in CsPbBr<sub>3</sub> nanocrystals and attribute them to resonant multiple-phonon absorption by polarons. The theory explains paradoxically large efficiencies for intrinsically disfavored, multiple-phonon-assisted ASPL in nanocrystals. Moreover, the developed microscopic mechanism has immediate and important implications for applications of ASPL toward condensed phase optical refrigeration.