Humidity-Induced Degradation Processes of Halide Perovskites Unveiled by Correlative Analytical Electron Microscopy.

Improving the stability of lead halide perovskite solar cells (PSCs) for industrialization is currently a major challenge. It is shown that moisture induces changes in global PSC performance, altering the nature of the absorber through phase transition or segregation. Understanding how the material evolves in a wet environment is crucial for optimizing device performance and stability. Here, the chemical and structural evolution of state-of-the-art hybrid perovskite thin-film Cs0.05 (MA0.15 FA0.85 )0.95 Pb(I0.84 Br0.16 )3 (CsMAFA) is investigated after aging under controlled humidity with analytical characterization techniques. The analysis is performed at different scales through Photoluminescence, X-ray Diffraction Spectroscopy, Cathodoluminescence, Selected Area Electron Diffraction, and Energy Dispersive X-ray Spectroscopy. From the analysis of the degradation products from the perovskite layer and by the correlation of their optical and chemical properties at a microscopic level, different phases such as lead-iodide (PbI2 ), inorganic mixed halide CsPb(I0.9 Br0.1 )3 and lead-rich CsPb2 (I0.74 Br0.26 )5 perovskite are evidenced. These phases demonstrate a high degree of crystallinity that induces unique geometrical shapes and drastically affects the optoelectronic properties of the thin film. By identifying the precise nature of these specific species, the multi-scale approach provides insights into the degradation mechanisms of hybrid perovskite materials, which can be used to improve PSC stability.

Influence of X-Ray Irradiation During Photoemission Studies on Halide Perovskite-Based Devices.

Metal halide perovskites (MHPs) are semiconductors with promising application in optoelectronic devices, particularly, in solar cell technologies. The chemical and electronic properties of MHPs at the surface and interfaces with adjacent layers dictate charge transfer within stacked devices and ultimately the efficiency of the latter. X-ray photoelectron spectroscopy is a powerful tool to characterize these material properties. However, the X-ray radiation itself can potentially affect the MHP and therefore jeopardize the reliability of the obtained information. In this work, the effect of X-ray irradiation is assessed on Cs0.05 MA0.15 FA0.8 Pb(I0.85 Br0.15 )3  (MA for CH3 NH3 , and FA for CH2 (NH2 )2 ) MHP thin-film samples in a half-cell device. There is a comparison of measurements acquired with synchrotron radiation and a conventional laboratory source for different times. Changes in composition and core levels binding energies are observed in both cases, indicating a modification of the chemical and electronic properties. The results suggest that changes observed over minutes with highly brilliant synchrotron radiation are likely occurring over hours when working with a lab-based source providing a lower photon flux. The possible degradation pathways are discussed, supported by steady-state photoluminescence analysis. The work stresses the importance of beam effect assessment at the beginning of XPS experiments of MHP samples.

Light-Induced Passivation in Triple Cation Mixed Halide Perovskites: Interplay between Transport Properties and Surface Chemistry.

Mixed halide perovskites have attracted a strong interest in the photovoltaic community as a result of their high power conversion efficiency and the solid opportunity to realize low-cost and industry-scalable technology. Light soaking represents one of the most promising approaches to reduce non-radiative recombination processes and thus to optimize device performances. Here, we investigate the effects of 1 sun illumination on state-of-the-art triple cation halide perovskite thin films Cs0.05(MA0.14, FA0.86)0.95 Pb (I0.84, Br0.16)3 by a combined optical and chemical characterization. Competitive passivation and degradation effects on perovskite transport properties have been analyzed by spectrally and time-resolved quantitative imaging luminescence analysis and by X-ray photoemission spectroscopy (XPS). We notice a clear improvement of the optoelectronic properties of the material, with a increase of the quasi fermi level splitting and a corresponding decrease of methylammonium MA+ for short (up to 1 h) light soaking time. However, after 5 h of light soaking, phase segregation and in-depth oxygen penetration lead to a decrease of the charge mobility.