Nanoscale infrared and microwave imaging of stacking faults in multilayer graphene

Abstract

Graphite occurs in a range of metastable stacking orders characterized by both the number and direction of shifts between adjacent layers by the length of a single carbon-carbon bond. At the extremes are Bernal (or ``ABAB...'') stacking, where the direction of the interlayer shift alternates with each layer, and rhombohedral (or ``ABCABC...'') stacking order where the shifts are always in the same direction. However, for an N-layer system, there are in principle $N-1$ unique metastable stacking orders of this type. Recently, it has become clear that stacking order has a strong effect on the low energy electronic band structure with single-layer shifts completely altering the electronic properties. Most experimental work has focused on the extremal stacking orders in large part due to the difficulty of isolating and identifying intermediate orders. Motivated by this challenge, here we describe two atomic force microscopy (AFM) based techniques to unambiguously distinguish stacking orders and defects in graphite flakes. Photo-thermal infrared atomic force microscope (AFM-IR) is able to distinguish stacking orders across multiple IR wavelengths and readily provides absolute contrast via IR spectral analysis. Scanning microwave impedance microscopy (sMIM) can distinguish the relative contrast between Bernal, intermediate and rhombohedral domains. We show that both techniques are well suited to characterizing graphite van der Waals devices, providing high contrast determination of stacking order, subsurface imaging of graphene flakes buried under a hexagonal boron nitride (hBN) dielectric layer, and identifying nanoscale domain walls. Our results pave the way for the reliable fabrication of graphene multilayer devices of definite interlayer registry.