Characterization and electrolytic cleaning of poly(methyl methacrylate) residues on transferred chemical vapor deposited graphene

Poly(methyl methacrylate) (PMMA) residue has long been a critical challenge for practical applications of the transferred chemical vapor deposited (CVD) graphene. Thermal annealing is empirically used for the removal of the PMMA residue; however experiments imply that there are still small amounts of residues left after thermal annealing which are hard to remove with conventional methods. In this paper, the thermal degradation of the PMMA residue upon annealing was studied by Raman spectroscopy. The study reveals that post-annealing residues are generated by the elimination of methoxycarbonyl side chains in PMMA and are believed to be absorbed on graphene via the pi-pi interaction between the conjugated unsaturated carbon segments and graphene. The post-annealing residues are difficult to remove by further annealing in a non-oxidative atmosphere due to their thermal and chemical stability. An electrolytic cleaning method was shown to be effective in removing these post-annealing residues while preserving the underlying graphene lattice based on Raman spectroscopy and atomic force microscopy studies. Additionally, a solution-gated field effect transistor was used to study the transport properties of the transferred CVD graphene before thermal annealing, after thermal annealing, and after electrolytic cleaning, respectively. The results show that the carrier mobility was significantly improved, and that the p-doping was reduced by removing PMMA residues and post-annealing residues. These studies provide a more in-depth understanding on the thermal annealing process for the removal of the PMMA residues from transferred CVD graphene and a new approach to remove the post-annealing residues, resulting in a residue-free graphene.