Nano-thermodynamics of chemically induced graphene-diamond transformation

TL;DR

This paper combines thermodynamic theory and atomistic computations to predict the conditions and mechanisms for transforming graphene into ultrathin diamond-like films, revealing the influence of surface chemistry and stacking on the resulting diamond structure.

Contribution

It introduces a predictive framework for graphene-to-diamond transformation considering surface chemistry, pressure, and stacking, highlighting the role of adsorbents and initial stacking in determining diamond allotropes.

Findings

Reduced pressure threshold for diamond formation due to surface chemistry.

Optimal adsorbent patterns favor cubic or hexagonal diamond structures.

H and F facilitate diamond formation, Cl hinders it.

Abstract

Nearly two-dimensional diamond, or diamane, is coveted as ultrathin $sp^3$-carbon film with unique mechanics and electro-optics. The very thinness ($~h$) makes it possible for the surface chemistry, e.g. adsorbed atoms, to shift the bulk phase thermodynamics in favor of diamond, from multilayer graphene. Thermodynamic theory coupled with atomistic first principles computations predicts not only the reduction of required pressure ($p/p_{\infty}>1-h_0/h$), but also the nucleation barriers, definitive for the kinetic feasibility of diamane formation. Moreover, the optimal adsorbent chair-pattern on a bilayer graphene results in a cubic diamond lattice, while for thicker precursors the adsorbent boat-structure tends to produce hexagonal diamond (lonsdaleite), if graphene was in AA` stacking to start with. As adsorbents, H and F are conducive to diamond formation, while Cl appears sterically hindered.