In this article, we have reviewed the recent progress of the experimental studies on ultra-thin films of graphite and hexagonal boron nitride (h-BN) by using angle-resolved electron spectroscopy together with other techniques. The fundamental properties of these high-quality films are discussed on the basis of the data on dispersion relations of valence electrons, phonon dispersion etc. The interfacial orbital mixing of the π-state of the monolayer graphite (MG) with the d states of the reactive substrates is the origin for the phonon softening, expansion of the nearest-neighbour C-C distance, modification of the π-band, low work function, and two-dimensional plasmons with high electron density, etc. In the cases of weak mixing at the interface between the MG and relatively inert substrates, the observed properties of the MG are very close to the bulk ones. In contract to the case for MG, the interfacial interaction between the h-BN monolayer and the substrate is weak.
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