Enhanced photostability of multication lead halide perovskites through the use of azaadamantane-based modifiers

Abstract

Complex lead halides incorporating simultaneously a few univalent cations such as cesium (Cs+), methylammonium (MA+) and formamidinium (FA+) represent highly promising materials for perovskite solar cells, delivering record-high power conversion efficiencies. Unfortunately, these materials demonstrate insufficient stability, which limits their practical implementation; therefore, improving the photochemical and thermal stability of multication lead halide perovskites is an urgent task that needs to be addressed to achieve sufficiently long operational lifetimes of perovskite solar cells to facilitate their commercial real-life applications. Herein, we present a comparative study of two azaadamantane-based molecular modifiers as stabilizing additives for Cs0.10MA0.15FA0.75PbI3 and Cs0.12FA0.88PbI3 perovskite formulations. An iodide of N-methylated 1,3,5,7-tetraazaadamantane known as urotropine (MAdI) showed a modest stabilizing effect in Cs0.10MA0.15FA0.75PbI3, though it stabilized effectively Cs0.12FA0.88PbI3. On the contrary, 4,6,10-trihydroxy-3,5,7-trimethyl-1,4,6,10-tetraazaadamantane hydrochloride (NAdCl) strongly enhanced the stability of both lead halide perovskites and prevented the formation of metallic lead Pb0 as a photolysis product. Different stabilizing effects caused by MAdI and NAdCl were related to their different localization within the perovskite films, as evidenced by nanoscale infrared (IR) s-SNOM microscopy. Density functional theory (DFT) calculations confirmed the enhanced stability granted by NAdCl by demonstrating a much higher adsorption energy towards undercoordinated lead atoms on the surface of the perovskite. Finally, the optimal molecular modification of Cs0.10MA0.15FA0.75PbI3 and Cs0.12FA0.88PbI3 films with azaadamantanes made them completely tolerant to light and heat within at least 5000 and 16 000 h of aging, thus setting new perovskite stability records and presenting the newly-developed material formulations as highly promising absorbers for efficient and stable perovskite solar cells.