Acoustic-optical phonon up-conversion and hot-phonon bottleneck in lead-halide perovskites.

Yang, Jianfeng; Wen, Xiaoming; Xia, Hongze; Sheng, Rui; Ma, Qingshan; Kim, Jincheol; Tapping, Patrick; Harada, Takaaki et al. · Nat Commun · 2017

basic_science · Level V

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Abstract

The hot-phonon bottleneck effect in lead-halide perovskites (APbX<sub>3</sub>) prolongs the cooling period of hot charge carriers, an effect that could be used in the next-generation photovoltaics devices. Using ultrafast optical characterization and first-principle calculations, four kinds of lead-halide perovskites (A=FA<sup>+</sup>/MA<sup>+</sup>/Cs<sup>+</sup>, X=I<sup>-</sup>/Br<sup>-</sup>) are compared in this study to reveal the carrier-phonon dynamics within. Here we show a stronger phonon bottleneck effect in hybrid perovskites than in their inorganic counterparts. Compared with the caesium-based system, a 10 times slower carrier-phonon relaxation rate is observed in FAPbI<sub>3</sub>. The up-conversion of low-energy phonons is proposed to be responsible for the bottleneck effect. The presence of organic cations introduces overlapping phonon branches and facilitates the up-transition of low-energy modes. The blocking of phonon propagation associated with an ultralow thermal conductivity of the material also increases the overall up-conversion efficiency. This result also suggests a new and general method for achieving long-lived hot carriers in materials.