Title screen

[References: 68 tit.]

Highly-oriented pyrolytic graphite (HOPG), i.e., the 3D stack of sp2-hybridized carbon sheets, is an attractive material thanks to its high electrical conductivity, chemical inertness, thermal stability, atomic-scale flatness, and ease of exfoliation. Despite an apparently ideal and uniform material, freshly cleaved HOPG shows domains in Kelvin probe force microscopy (KPFM) with surface potential contrast over 30 mV. We systematically investigated these domains using an integrated approach, including time-dependent KPFM and hyperspectral Raman imaging. The observed time-evolving domains are attributed to locally different hydrocarbon adsorption from the environment, driven by structural defects likely related to rotational mismatch, i.e., twisted layers. These defects affect the interlayer coupling between topmost graphene and the underlying layers. Our hypothesis was supported by Raman spectroscopy results, showing domains with G peak shifts and 2D line shape compatible with bilayer graphene. We attribute the selective sensitivity of our Raman spectroscopy results to the top graphene layers as resonances due to van Hove singularities. Our results show that the chemical and electrical properties of HOPG are far more complex than what is generally believed due to the broken symmetry at the top surface, giving rise to graphene bilayer-like behavior.