Experimental observation of ABCB stacked tetralayer graphene

In tetralayer graphene, three inequivalent layer stackings should exist, however, only rhombohedral (ABCA) and Bernal (ABAB) stacking have so far been observed. The three stacking sequences differ in their electronic structure, with the elusive third stacking (ABCB) being unique as it is predicted to exhibit an intrinsic bandgap as well as locally flat bands around the K points. Here, we use scattering-type scanning near-field optical microscopy and confocal Raman microscopy to identify and characterize domains of ABCB stacked tetralayer graphene. We differentiate between the three stacking sequences by addressing characteristic interband contributions in the optical conductivity between 0.28 and 0.56 eV with amplitude and phase-resolved near-field nano-spectroscopy. By normalizing adjacent flakes to each other, we achieve good agreement between theory and experiment, allowing for the unambiguous assignment of ABCB domains in tetralayer graphene. These results establish near-field spectroscopy at the interband transitions as a semi-quantitative tool, enabling the recognition of ABCB domains in tetralyer graphene flakes and therefore, providing a basis to study correlation physics of this exciting phase.