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.

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.

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.