Intercalated structures formed by platinum on epitaxial graphene on SiC(0001)

TL;DR

This study investigates the structure, mechanism, and effects of platinum intercalation in epitaxial graphene on SiC(0001), revealing a layered intercalated phase that alters morphology and electronic properties, with implications for spintronics and catalysis.

Contribution

It provides detailed atomic-scale insights into Pt intercalation mechanisms and resulting structures in epitaxial graphene on SiC(0001), which were previously unclear.

Findings

Intercalated Pt forms a single layer removing buffer layer corrugation.

Pt intercalation creates a two-level structure with superstructure in graphene.

Intercalation leads to silicide formation and emergence of quasi-free-standing graphene.

Abstract

Graphene on SiC intercalated with two-dimensional metal layers, such as Pt, offers a versatile platform for applications in spintronics, catalysis, and beyond. Recent studies have demonstrated that Pt atoms can intercalate at the heterointerface between SiC(0001) and the C-rich $(6\sqrt{3}\times6\sqrt{3})$R30{\deg} reconstructed surface (hereafter referred as the buffer layer). However, key aspects such as intercalated phase structure and intercalation mechanisms remain unclear. In this work, we investigate changes in morphology, chemistry, and electronic structure for both buffer layer and monolayer graphene grown on SiC(0001) following Pt deposition and annealing cycles, which eventually led to Pt intercalation at temperatures above 500{\deg}C. Atomic-resolution imaging of the buffer layer reveals a single intercalated Pt layer that removes the periodic corrugation of the buffer layer, arising from partial bonding of C-atoms with Si-atoms of the substrate. In monolayer graphene, the Pt-intercalated regions exhibit a two-level structure: the first level corresponds to a Pt layer intercalated below the buffer layer, while the second level contains a second Pt layer, giving rise to a $(12\times12)$ superstructure relative to graphene. Upon intercalation, Pt atoms appear as silicides, indicating a reaction with Si atoms from the substrate. Additionally, charge neutral $\pi$-bands corresponding to quasi-free-standing monolayer and bilayer graphene emerge. Analysis of multiple samples, coupled with a temperature-dependent study of the intercalation rate, demonstrates the pivotal role of buffer layer regions in facilitating the Pt intercalation in monolayer graphene. These findings provide valuable insight into Pt intercalation, advancing the potential for applications.