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
A method for enhancing the moisture barrier property of polydimethylsiloxane (PDMS) polymer films is proposed. This is achieved by filling the PDMS free volume with aluminum oxide (AlOx). To deposit AlOx inside PDMS, thermal atomic layer deposition (ALD) is employed. The PDMS/AlOx film thus produced has a 30 nm AlOx layer on the surface. Its water vapor transmission rate (WVTR) is 5.1 × 10−3 g m−2 d−1 at 45 °C and 65% relative humidity (RH). The activation energy of permeability with the PDMS/AlOx film for moisture permeation is determined to be 35.5 kJ mol−1. To investigate the moisture barrier capability of the PDMS/AlOx layer, (FAPbI3)0.85(MAPbBr3)0.15/spiro-OMeTAD/Au perovskite solar cells are fabricated, and encapsulated by the PDMS/AlOx film. To minimize the thermal damage to solar cells during ALD, AlOx deposition is performed at 95 °C. The solar cells exposed to 45 °C-65% RH for 300 h demonstrate less than a 5% drop in the power-conversion efficiency.
In this study, we developed the universal encapsulation method using poly(vinyl alcohol-co-ethylene) (EVOH) to improve the water stability of perovskite solar cells. In order to enhance the moisture barrier property, we utilized SiO2 and graphene oxide (GO) fillers in the EVOH matrix. First, UV-treated SiO2 increased the dispersibility in the EVOH matrix and made the penetrating path more complicated, which led to a better moisture barrier property. The water vapor transmission ratio (WVTR) is enhanced from 4.72 × 10–2 (EVOH only) to 1.55 × 10–2 (EVOH with SiO2 filler) g/m2 day. Second, we found that GO reduce the unreacted hydroxyl groups that could attract water molecules at the surface of EVOH. The addition of GO increased the WVTR up to 3.34 × 10–3 g/m2 day. Finally, our EVOH-based film successfully encapsulated without the efficiency drop. The encapsulated devices surprisingly maintained 86% of their performance even under direct contact with water for 5 h.