We present an extensive experimental study of the conditions under which Cu forms encapsulated islands under the top surface layers of graphite, as a result of physical vapor deposition of Cu on argon-ionbombarded graphite. When the substrate is held at 800 K during deposition, conditions are optimal for formation of encapsulated multilayer Cu islands. Deposition temperatures below 600 K favor adsorbed Cu clusters, while deposition temperatures above 800 K favor a different type of feature that is probably a singlelayer intercalated Cu island. The multilayer Cu islands are characterized with respect to size and shape, thickness and continuity of the graphitic overlayer, relationship to graphite steps, and stability in air. The experimental techniques are scanning tunneling microscopy and X-ray photoelectron spectroscopy. We also present an extensive study using density functional theory to compare stabilities of a wide variety of configurations of Cu atoms, Cu clusters, and Cu layers on/under the graphite surface. The only configuration that is significantly more stable under the graphite surface than on top of it, is a single Cu atom. This analysis leads us to conclude that formation of encapsulated Cu islands is kinetically driven, rather than thermodynamically driven.

Using scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy, we show that Ru forms metallic nanoislands on graphite, covered by a graphene monolayer. These islands are air-stable, contain 2-4 layers of Ru, and have diameters on the order of 10 nm. To produce these nanoislands two conditions must be met during synthesis. The graphite surface must be ion-bombarded, and subsequently held at an elevated temperature (1000-1180 K) during Ru deposition. A coincidence lattice forms between the graphene overlayer and the Ru island top. Its characteristics-coincidence lattice constant, corrugation amplitude, and variation of carbon lattice appearance within the unit cell-closely resemble the well-established characteristics of single-layer graphene on the (0001) surface of bulk Ru. Quantitative analysis of the graphene lattice in relation to the coincidence lattice on the island tops show that the two-dimensional lattice constant of the underlying metal equals that of bulk Ru(0001), within experimental error. The embedded Ru islands are energetically favored over on-top (adsorbed) islands, based on density-functional-theory calculations for Ru films with 1-3 Ru layers. We propose a formation mechanism in which Ru atoms intercalate via defects that act as entry portals to the carbon galleries, followed by nucleation and growth in the galleries. In this model, high deposition temperature is necessary to prevent blockage of entry portals.

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