Thermal evaporation is an important technique for fabricating methylammonium lead iodide (MAPbI₃), but the process is complicated by the need to co-evaporate methylammonium iodide (MAI) and PbI₂. In this work, the effect of water vapor during the thermal deposition of MAPbI₃ was investigated under high vacuum. The evaporation process was monitored with a residual gas analyzer (RGA), and the film quality was examined with X-ray photoelectron spectroscopy (XPS). The investigations showed that during evaporation, MAI decomposed while PbI₂ evaporated as a whole compound. It was found that the residual water vapor reacted with one of the MAI-dissociated products. The higher iodine ratio suggests that the real MAI flux was higher than the reading from the QCM. The XPS analysis demonstrated that the residual water vapor may alter the elemental ratios of C, N, and I in thermally deposited MAPbI₃. Morphologic properties were investigated with atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). It was observed that a sample grown with high water vapor pressure had a roughened surface and poor film quality. Therefore, an evaporation environment with water vapor pressure below 10⁻⁸ Torr is needed to fabricate high quality perovskite films.

Hybrid organic inorganic perovskites have been considered as a potential candidate for the next generational solar cell due to their outstanding optoelectronic properties and rapid development in recent years. However, the biggest challenge to prevent them from massive commercial use is their long-term stability. Photoemission spectroscopy has been widely used to investigate properties of the perovskites, which provide critical insights to better understand the degradation mechanisms. In this article, we review mainly our photoemission studies on the degradation processes of perovskite thin films and single crystals with different environmental factors, such as gases, water, and light by monitoring changes of chemical composition and electronic structure. These studies on the effects by different environmental parameters are discussed for the understanding of the stability issues and the possible solutions.

Angle-resolved photoemission spectroscopy (ARPES) is a vital technique, collecting data from both the energy and momentum of photoemitted electrons, and is indispensable for investigating the electronic band structure of solids. This article provides a review on ARPES studies of the electronic band structure of organic single crystals, including organic charge transfer conductors; organic semiconductors; and organo-metallic perovskites. In organic conductors and semiconductors, band dispersions are observed that are highly anisotropic. The Van der Waals crystal nature, the weak electron wavefunction overlap, as well as the strong electron-phonon coupling result in many organic crystals having indiscernible dispersion. In comparison, organo-metallic perovskite halides are characterized by strong s-p orbitals from the metal and halide at the top of the valence bands, with dispersions similar to those in inorganic materials.

In this study, a facile passivation for methylammonium lead bromide (MAPbBr₃) single crystals is reported. Stability against moisture and light remains the most critical demerit of perovskite materials, which is improved by depositing a 40 Å thick hydrophobic copper phthalocyanine (CuPc) layer on top of the cleaved perovskite surface. The water and light exposure processes were monitored with X-ray photoelectron spectroscopy with precise control of the exposure time and pressure. It is found that the CuPc top layer could protect the sample from moisture infiltration at a water exposure of 10¹³ L, while the nonpassivated sample started to degrade at 10⁸ L. During the light exposure, CuPc also slowed down the light-induced degradation, which is supported by the elemental ratio change of metallic lead and bromine. These results are further confirmed by the morphological comparison via scanning electron microscopy and focused ion beam.

Organometal halide perovskites are promising materials for optoelectronic applications, whose commercial realization depends critically on their stability under multiple environmental factors. In this study, a methylammonium lead bromide (MAPbBr₃) single crystal was cleaved and exposed to simultaneous oxygen and light illumination under ultrahigh vacuum (UHV). The exposure process was monitored using X-ray photoelectron spectroscopy (XPS) with precise control of the exposure time and oxygen pressure. It was found that the combination of oxygen and light accelerated the degradation of MAPbBr₃, which could not be viewed as a simple addition of that by oxygen-only and light-only exposures. The XPS spectra showed significant loss of carbon, bromine, and nitrogen at an oxygen exposure of 10¹⁰ Langmuir with light illumination, approximately 17 times of the additive effects of oxygen-only and light-only exposures. It was also found that the photoluminescence (PL) emission was much weakened by oxygen and light co-exposure, while previous reports had shown that PL was substantially enhanced by oxygen-only exposure. Measurements using a scanning electron microscope (SEM) and focused ion beam (FIB) demonstrated that the crystal surface was much roughened by the co-exposure. Density functional theory (DFT) calculations revealed the formation of superoxide and oxygen induced gap state, suggesting the creation of oxygen radicals by light illumination as a possible microscopic driving force for enhanced degradation.