Quantifying Mn diffusion through transferred versus directly-grown graphene barriers

We quantify the mechanisms for manganese (Mn) diffusion through graphene in Mn/graphene/Ge (001) and Mn/graphene/GaAs (001) heterostructures, for samples prepared by graphene layer transfer versus graphene growth directly on the semiconductor substrate. These heterostructures are important for applications in spintronics; however, challenges in synthesizing graphene directly on technologically important substrates such as GaAs necessitate layer transfer steps, which can introduce defects into the graphene. \textit{In-situ} photoemission spectroscopy measurements reveal that Mn diffusion through graphene grown directly on a Ge (001) substrate is 1000 times lower than Mn diffusion into samples without graphene ($D_{gr,direct} \sim 4\times10^{-18}$cm$^2$/s, $D_{no-gr} \sim 5 \times 10^{-15}$ cm$^2$/s at 500$^\circ$C). Transferred graphene on Ge suppresses the Mn in Ge diffusion by a factor of 10 compared to no graphene ($D_{gr,transfer} \sim 4\times10^{-16}cm^2/s$). For both transferred and directly-grown graphene, the low activation energy ($E_a \sim 0.1-0.5$ eV) suggests that Mn diffusion through graphene occurs primarily at graphene defects. The diffusivity prefactor $D_0$ scales with the defect density. Similar diffusion barrier performance is found on GaAs substrates; however, it is not currently possible to grow graphene directly on GaAs. Our results highlight the importance of developing graphene growth directly on functional substrates, to avoid the damage induced by layer transfer.