Vacancy clusters as entry ports for cesium intercalation in graphite

Abstract

Graphite has been subjected to surface damage by Ar + ion bombardment. It has been found by scanning tunneling microscopy (STM) that deposited Cs atoms preferentially cluster at the artificially-produced vacancy clusters in the basal plane at 300 K. Density functional theory calculations show that Cs is more strongly bound at these defect sites than at basal plane step edges, providing a plausible explanation for the experimental observation. STM reveals that Cs intercalation into graphite occurs by diffusion through these vacancy clusters, acting as entry ports to the interior, at 700 K. DFT calculations show that these defects must consist of more than four contiguous atoms in order for Cs intercalation to be energetically easy. Experimentally, Cs atom nucleation at defect sites seems to culminate at Cs cluster heights near 1 nm and cluster diameters near 5 nm. Intercalated Cs produces coherent single Cs islands in the galleries as well as layered structures caused by superposition of overlapping individual islands. Oxygen exposure to graphite containing Ar +-produced defects does not influence Cs clustering at the defects or Cs entry into galleries beneath the defect. However, large oxygen exposures these clusters results in diminution of Cs intercalation, probably due to surface oxidation of Cs clusters.