Ionic and electronic energy diagrams for hybrid perovskite solar cells

The development of photoelectrochemical devices based on mixed ionic-electronic conductors requires knowledge of transport, generation and reaction of electronic and ionic charge carriers. Thermodynamic representations can significantly help the understanding of these processes. They should be simple and reflect the necessity of dealing with ions and electrons. In this work, we discuss the extension of energy diagrams commonly used to describe electronic properties of semiconductors to the defect chemical treatment of electronic and ionic charge carriers in mixed conducting materials as introduced in the context of nanoionics. We focus on hybrid perovskites in relation to their use as the active layer material of solar cells. Owing to the presence of at least two ion types, a variety of native ionic disorder processes have to be dealt with in addition to the single fundamental electronic disorder process as well as potential frozen-in defects. Various situations are discussed that show how such generalized level diagrams can be usefully applied and appropriately simplified in the determination of the equilibrium behavior of bulk and interfaces in solar cell devices. This approach can serve as a basis for investigating the behavior of perovskite solar cells, but also other mixed-conducting devices operating under bias.