Influence of the Alkyl Chain Length of (Pentafluorophenylalkyl) Ammonium Salts on Inverted Perovskite Solar Cell Performance

We study the effect of (2,3,4,5,6-pentafluorophenyl)alkylamine additives with differing alkyl chain lengths (methyl, ethyl, and n-propyl) on the performance of methylammonium lead triiodide (MAPbI3) perovskite solar cells. The results show that the length of the alkyl chain between the 2,3,4,5,6-pentafluorophenyl group and ammonium moiety has a critical effect on the perovskite film structure and subsequent device performance. The 2,3,4,5,6-pentafluorophenyl ammonium additive with the shortest linking group (a methylene unit), namely (2,3,4,5,6-pentafluorophenyl)methylammonium iodide, was found to be distributed throughout the bulk of the perovskite film with a 2D phase only being observable at high concentrations (>30 mol%). In contrast, the additives with ethyl and n-propyl linking groups phase-separate during solution processing and are found to concentrate at the surface of the perovskite film. Photoluminescence measurements showed that the fluorinated additives passivated the surface defects on the perovskite grains. Of the three additives, inverted devices containing 0.32 mol% of the 2,3,4,5,6-pentafluorophenyl ammonium additive with the methylene linking group achieved a maximum power conversion efficiency of 22.0%, with the device efficiency decreasing with increasing additive concentration. In contrast, the devices composed of the additive with the longest alkyl linker, 3-(2,3,4,5,6-pentafluorophenyl)propylammonium iodide, had the poorest performance, with PCEs less than that of the neat MAPbI3 control and decreasing with increasing additive concentration.