Molecular Precursors-Induced Surface Reconstruction at Graphene/Pt(111) Interfaces

TL;DR

This study uses advanced computational methods to reveal how molecular precursors induce surface reconstruction at graphene/Pt(111) interfaces, highlighting the role of precursor chemistry and temperature in the process.

Contribution

It identifies a more stable reconstructed surface structure and elucidates the mechanism by which molecular precursors trigger surface reconstruction during early graphene formation.

Findings

Reconstructed structure is more stable than previous reports.

Surface reconstruction occurs during early stages of precursor adsorption.

Pt-C covalent bonds significantly alter graphene's electronic structure.

Abstract

Inspired by experimental observations of Pt(111) surfaces reconstruction at the Pt/graphene (Gr) interfaces with ordered vacancy networks in the outermost Pt layer, the mechanism of the surface reconstruction is investigated by van-der-Waals-corrected density functional theory in combination with particle-swarm optimization algorithm and ab initio atomistic thermodynamics. Our global structural search finds a more stable reconstructed (Rec) structure than that was reported before. With correction for vacancy formation energy, we demonstrate that the experimental observed surface reconstruction occurred at the earlier stages of graphene formation: 1) reconstruction occurred when C60 adsorption (before decomposition to form graphene) for C60 as a molecular precursor, or 2) reconstruction occurred when there were (partial) hydrogens retain in the adsorbed carbon structures for C2H4 and C60H30 as precursors. The reason can be attributed to that the energy gain, from the strengthened Pt-C bonding for C of C60 or for C with partial H, compensates the energy cost of formation surface vacancies and makes the reconstruction feasible, especially at elevated temperatures. In the Rec structure, two Pt-C covalent bonds are formed per unit cell, which have a great impact on the adsorbed Gr electronic structures.