Influence of Halides on the Interactions of Ammonium Acids with Metal Halide Perovskites

Additive engineering is a common strategy to improve the performance and stability of metal halide perovskite through the modulation of crystallization kinetics and passivation of surface defects. However, much of this work has lacked a systematic approach necessary to understand how the functionality and molecular structure of the additives influence perovskite performance and stability. This paper describes the inclusion of low concentrations of 5-aminovaleric acid (5-AVA) and its ammonium acid derivatives, 5-ammoniumvaleric acid iodide (5-AVAI) and 5-ammoniumvaleric acid chloride (5-AVACl), into the precursor inks for methylammonium lead triiodide (MAPbI₃) perovskite and highlights the important role of halides in affecting the interactions of additives with perovskite and film properties. The film quality, as determined by X-ray diffraction (XRD) and photoluminescence (PL) spectrophotometry, is shown to improve with the inclusion of all additives, but an increase in annealing time from 5 to 30 min is necessary. We observe an increase in grain size and a decrease in film roughness with the incorporation of 5-AVAI and 5-AVACl with scanning electron microscopy (SEM) and atomic force microscopy (AFM). Critically, X-ray photoelectron spectroscopy (XPS) measurements and density functional theory (DFT) calculations show that 5-AVAI and 5-AVACl preferentially interact with MAPbI₃ surfaces via the ammonium functional group, while 5-AVA will interact with either amino or carboxylic acid functional groups. Charge localization analysis shows the surprising result that HCl dissociates from 5-AVACl in vacuum, resulting in the decomposition of the ammonium acid to 5-AVA. We show that device repeatability is improved with the inclusion of all additives and that 5-AVACl increases the power conversion efficiency of devices from 17.61 ± 1.07 to 18.07 ± 0.42%. Finally, we show stability improvements for unencapsulated devices exposed to 50% relative humidity, with devices incorporating 5-AVAI and 5-AVACl exhibiting the greatest improvements.