We measured the electronic local density of states (LDOS) of graphite surfaces near monoatomic step edges, which consist of either the zigzag or armchair edge, with the scanning tunneling microscopy (STM) and spectroscopy (STS) techniques. The STM data reveal that the (and honeycomb superstructures coexist over a length scale of 3−4 nm from both the edges. By comparing with density-functional derived nonorthogonal tight-binding calculations, we show that the coexistence is due to a slight admixing of the two types of edges at the graphite surfaces. In the STS measurements, a clear peak in the LDOS at negative bias voltages from −100 to −20 mV was observed near the zigzag edges, while such a peak was not observed near the armchair edges. We concluded that this peak corresponds to the graphite "edge state" theoretically predicted by Fujita et al. [J. Phys. Soc. Jpn. 65, 1920] with a tight-binding model for graphene ribbons. The existence of the edge state only at the zigzag type edge was also confirmed by our first-principles calculations with different edge terminations.

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