Dimensionality of excitons in stacked van der Waals materials: The example of hexagonal boron nitride

With the example of hexagonal boron nitride, we demonstrate how the character of electron-hole (e−h) pairs in van der Waals bound low-dimensional systems is driven by layer stacking. Four types of excitons appear, with either a two- or three-dimensional spatial extension. Electron and hole distributions are either overlapping or exhibit a charge-transfer nature. We discuss under which structural and symmetry conditions they appear and they are either dark or bright. This analysis provides the key elements to identify, predict, and possibly tailor the character of e−h pairs in van der Waals materials.