Adsorption and decomposition steps on Cu(111) of liquid aromatic hydrocarbon precursors for low-temperature CVD of graphene: A DFT study

Low-temperature chemical vapor deposition (LT-CVD) of graphene using liquid aromatic hydrocarbons holds technological advantages over conventional growth from methane. However, the nature of decomposition mechanisms of such precursors and their effectiveness in a LT-CVD process is still debated. We investigate by means of density functional theory adsorption energies and decomposition first steps on Cu(111) of single-ring aromatic hydrocarbons, such as benzene and toluene. Our results confirm the stronger stability with respect to methane of aromatic adsorbates, due to exchange of London dispersion forces with Cu surface; however, toluene exhibits improved bindings with respect to benzene. The adsorption energy slightly improves if additional methyl groups are substituted in benzene, as in o-xylene and 1,2,3-trimethylbenzene. Among decomposition reactions, dehydrogenation of the methyl group in toluene is energetically more favored (1.20 eV) than that of methane (1.52 eV) or aromatic C-rings (1.67 eV and 1.72 eV for benzene and toluene), while demethylation of toluene remains negligible due to the prohibitive energy barrier (2.49 eV). Methyl dehydrogenation in toluene leads to the abundant formation of adsorbed benzyl radicals onto Cu in an almost parallel-to-surface configuration, as active species for graphene nucleation. Toluene (and to a lesser extent o-xylene and 1,2,3-trimethylbenzene) should be thus preferred to benzene in LT-CVD of graphene.