The hot-phonon bottleneck effect in lead-halide perovskites (APbX₃) 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⁺/MA⁺/Cs⁺, X=I⁻/Br⁻) 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 FAPbI₃. 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.

Perovskite decomposition in detail: Solar cells are subject to heating when operating in sunlight, and the organic components of hybrid perovskite solar cells, especially the commonly used methylammonium cation, can undergo thermal decomposition. Encapsulation can limit decomposition by bringing such reactions to equilibrium and can prevent exposure to damaging ambient moisture. Shi et al. examined several encapsulation schemes for perovskite films and devices by probing volatile products with gas chromatography–mass spectrometry (see the Perspective by Juarez-Perez and Haro). Pressure-tight polymer/glass stack encapsulation was effective in suppressing gas transfer and allowed solar cells containing methylammonium to pass harsh moisture and thermal cycling tests. Science , this issue p. eaba2412 ; see also p. 1309