Band Alignment and the Built-in Potential of Solids.

The built-in potential is of central importance to the understanding of many interfacial phenomena because it determines the band alignment at the interface. Despite its importance, its exact sign and magnitude have generally been recognized as ill-defined quantities for more than half a century. Here, we provide a common energy reference of bulk matter which leads to an unambiguous definition of the built-in potential and innate (i.e., bulk) band alignment. Further, we find that the built-in potential is explicitly determined by the bulk properties of the constituent materials when the system is in electronic equilibrium, while the interface plays a role only in the absence of equilibrium. Our quantitative theory enables a unified description of a variety of important properties of interfaces, ranging from work functions to Schottky barriers in electronic devices.