Plasma–graphene interactions: combined effects of positive ions, vacuum-ultraviolet photons, and metastable species

This study compares the impact of different plasma environments on the damage formation dynamics of polycrystalline monolayer graphene films on SiO 2 /Si substrates and investigates the combined effects often observed in low-pressure argon plasmas. After careful characterization of the discharge properties by Langmuir probes and optical absorption spectroscopy, three operating conditions were selected to promote graphene irradiation by either positive ions, metastable species, or vacuum-ultraviolet (VUV) photons. In all cases, hyperspectral Raman imaging of graphene reveals plasma-induced damage. In addition, defect generation is systematically slower at grain boundaries (GBs) than within the grains, a behavior ascribed to a preferential self-healing of plasma-induced defects at GBs. The evolution of selected Raman band parameters is also correlated with the energy fluence provided to the graphene lattice by very-low-energy ions. From such correlation, it is shown that the presence of VUV photons enhances the defect formation dynamics through additional energy transfer. On the other hand, the presence of metastable species first impedes the defect generation and then promotes it for higher lattice disorder. While this impediment can be linked to an enhanced defect migration and self-healing at nanocrystallite boundaries in graphene, such effect vanishes in more heavily-damaged films.