Metal Halide Perovskite/Electrode Contacts in Charge‐Transporting‐Layer‐Free Devices

Abstract Metal halide perovskites have drawn substantial interest in optoelectronic devices in the past decade. Perovskite/electrode contacts are crucial for constructing high‐performance charge‐transporting‐layer‐free perovskite devices, such as solar cells, field‐effect transistors, artificial synapses, memories, etc. Many studies have evidenced that the perovskite layer can directly contact the electrodes, showing abundant physicochemical, electronic, and photoelectric properties in charge‐transporting‐layer‐free perovskite devices. Meanwhile, for perovskite/metal contacts, some critical interfacial physical and chemical processes are reported, including band bending, interface dipoles, metal halogenation, and perovskite decomposition induced by metal electrodes. Thus, a systematic summary of the role of metal halide perovskite/electrode contacts on device performance is essential. This review summarizes and discusses charge carrier dynamics, electronic band engineering, electrode corrosion, electrochemical metallization and dissolution, perovskite decomposition, and interface engineering in perovskite/electrode contacts‐based electronic devices for a comprehensive understanding of the contacts. The physicochemical, electronic, and morphological properties of various perovskite/electrode contacts, as well as relevant engineering techniques, are presented. Finally, the current challenges are analyzed, and appropriate recommendations are put forward. It can be expected that further research will lead to significant breakthroughs in their application and promote reforms and innovations in future solid‐state physics and materials science.