Quantifying Organic Cation Ratios in Metal Halide Perovskites: Insights from X-ray Photoelectron Spectroscopy and Nuclear Magnetic Resonance Spectroscopy

The employment of metal halide perovskites (MHPs) in various optoelectronic applications requires the preparation of thin films whose composition plays a crucial role. Yet, the composition of the MHP films is rarely reported in the literature, partly because quantifying the actual organic cation composition cannot be done with conventional characterization methods. For MHPs, NMR has gained popularity, but for films, tedious processes like scratching several films are needed. Here, we use mechanochemical synthesis of MA_1-x FA _x PbI₃ powders with various MA⁺: FA⁺ ratios and combine solid-state NMR spectroscopy (ssNMR) and X-ray photoelectron spectroscopy (XPS) to provide a reference characterization protocol for the organic cations' quantification in either powder form or films. Following this, we demonstrate that organic cation ratio quantification on thin films with ssNMR can be done without scraping the film and using significantly less mass than typically needed, that is, employing a single ∼800 nm-thick MA_1-x FA _x PbI₃ film deposited by pulsed laser deposition (PLD) onto a 1 × 1 in.², 0.2 mm-thick quartz substrate. While background signals from the quartz substrate appear in the ¹H ssNMR spectra, the MA⁺ and FA⁺ signals are easily distinguishable and can be quantified. This study highlights the importance of calibrating and quantifying the source and the thin film organic cation ratio, as key for future optimization and scalability of physical vapor deposition processes.