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Organometal halide perovskites are promising materials for optoelectronic applications, whose commercial realization depends critically on their stability under multiple environmental factors. 

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. 

Abstract The energy level alignment that occurs at the interfaces in planar-hetero structured perovskite photovoltaic devices strongly influences the charge transport across the interface, and thus plays a crucial role in overall device performance. To directly observe the energy level alignment requires pristine homogeneous surfaces that are free of contamination including adventitious carbon. Co-evaporation offers the ability to grow perovskite thin films in-situ, and the method involves thermally evaporating the perovskite precursors such as PbI 2 and CH 3 NH 3 I. Early reports have shown that the perovskite film formation and stoichiometry are problematic at ultralow coverages. In particular, it was reported that there was excessive PbI 2 and a deficiency in CH 3 NH 3 I. Using photoemission spectroscopy, we investigated the perovskite precursor PbI 2 on gold and highly oriented pyrolytic graphite (HOPG) surfaces. Results show that the nature of the surface and the deposition conditions can strongly influence the film formation. Excessive iodine observed in the initial evaporation stages appears to be substrate dependent, and this may influence the overall energy level alignment.