Photoemission Spectroscopy Characterization of Halide Perovskites

Controlling the surface and interface properties of halide perovskites (HaPs) materials is key to improve performance and stability of HaP‐based optoelectronic devices such as solar cells. Here, an overview is given on the use of different photoemission spectroscopy (PES) techniques as a tool kit to investigate chemical and electronic properties of surfaces and interfaces in research on HaP compounds. The primary focus of the article is X‐ray photoelectron spectroscopy (XPS), hard X‐ray photoemission spectroscopy (HAXPES), ultraviolet photoemission spectroscopy (UPS), and inverse photoemission spectroscopy (IPES), highlighting the importance of good practices during PES measurements. Starting from the working principles of PES, critical measurement conditions are discussed. In particular, the exposure of the HaP surface to vacuum and high energy radiation can cause accelerated ageing, degradation, and also ionic migration in the sample. The impact of these changes on the electronic and chemical properties is discussed, followed by an analysis of the specific challenges encountered when performing PES measurements of HaPs. These include the deviation from pristine surface conditions, determination of “soft” band edges, and assessment of band bending. The review concludes by emphasizing good practices for PES measurements of HaP samples and outlining the scope of operando type measurements to capture the transient behavior of HaPs in the experiment.