Modulating charge density and inelastic optical response in graphene by atmospheric pressure localized intercalation through wrinkles

The intercalation of an oxide barrier between graphene and its metallic substrate for chemical vapor deposition is a contamination-free alternative to the transfer of graphene to dielectric supports, usually needed for the realization of electronic devices. Low-cost processes, especially at atmospheric pressure, are desirable but whether they are achievable remains an open question. Combining complementary microscopic analysis, providing structural, electronic, vibrational, and chemical information, we demonstrate the spontaneous reactive intercalation of 1.5 nm-thick oxide ribbons between graphene and an iridium substrate, at atmospheric pressure and room temperature. We discover that oxygen-containing molecules needed for forming the ribbons are supplied through the graphene wrinkles, which act as tunnels for the efficient diffusion of molecules entering their free end. The intercalated oxide ribbons are found to modify the graphene–support interaction, leading to the formation of quasi-free-standing high quality graphene whose charge density is modulated in few 10–100 nm-wide ribbons by a few 1012 cm−2, where the inelastic optical response is changed, due to a softening of vibrational modes – shifts of Raman G and 2D bands by 6 and 10 cm−1, respectively.