2D/3D hybrid Cs${}_2$AgBiBr${}_6$ double perovskite solar cells. Improved energy level alignment for higher contact-selectivity and large open circuit voltage

Since their introduction in 2017, the efficiency of lead-free halide perovskite solar cells based on Cs${}_2$AgBiBr${}_6$ has not exceeded 3%. The limiting bottlenecks are attributed to a low electron diffusion length, self-trapping events and poor selectivity of the contacts, leading to large non-radiative V${}_{OC}$ losses. Here, 2D/3D hybrid double perovskites are introduced for the first time, using phenethyl ammonium as the constituting cation. The resulting solar cells show an increased efficiency of up to 2.5% for the champion cells and 2.03% on average, marking an improvement by 10% compared to the 3D reference on mesoporous TiO${}_2$. The effect is mainly due to a V${}_{OC}$ improvement by up to 70 mV on average, yielding a maximum V${}_{OC}$ of 1.18 V using different concentrations of phenethylammonium bromide. While these are among the highest reported V${}_{OC}$ values for Cs${}_2$AgBiBr${}_6$ solar cells, the effect is attributed to a change in recombination behavior within the full device and a better selectivity at the interface toward the hole transporting material (HTM). This explanation is supported by voltage-dependent external quantum efficiency, as well as photoelectron spectroscopy, revealing a better energy level alignment and thus a better hole-extraction and improved electron blocking at the HTM interface. (© 2022 The Authors. Advanced Energy Materials published by Wiley‐VCH GmbH)