Researchers must learn how to tune the electronic properties of graphene — not an easy feat, given a major challenge intrinsic to the material. Unlike semiconductors such as silicon, pure graphene is a zero band-gap material, making it difficult to electrically “turn off” the flow of current through it. Therefore, pristine graphene is not appropriate for the digital circuitry that comprises the vast majority of integrated circuits.
To overcome this problem and make graphene more functional, researchers around the world are investigating methods for chemically altering the material. The most prevalent strategy is the “Hummers method,” a process developed in the 1940s that oxidizes graphene, but that method relies upon harsh acids that irreversibly damage the fabric of the graphene lattice.
Researchers at Northwestern’s McCormick School of Engineering and Applied Science have recently developed a new method to oxidize graphene without the collateral damage encountered in the Hummers method. Their oxidation process is also reversible, which enables further tunability over the resulting properties of their chemically modified graphene.
Atomic-scale imaging of chemisorbed atomic oxygen on epitaxial graphene.
With its exceptional charge mobility, graphene holds great promise for applications in next-generation electronics. In an effort to tailor its properties and interfacial characteristics, the chemical functionalization of graphene is being actively pursued. The oxidation of graphene via the Hummers method is most widely used in current studies, although the chemical inhomogeneity and irreversibility of the resulting graphene oxide compromises its use in high-performance devices. Here, we present an alternative approach for oxidizing epitaxial graphene using atomic oxygen in ultrahigh vacuum. Atomic-resolution characterization with scanning tunnelling microscopy is quantitatively compared to density functional theory, showing that ultrahigh-vacuum oxidization results in uniform epoxy functionalization. Furthermore, this oxidation is shown to be fully reversible at temperatures as low as 260 °C using scanning tunnelling microscopy and spectroscopic techniques. In this manner, ultrahigh-vacuum oxidation overcomes the limitations of Hummers-method graphene oxide, thus creating new opportunities for the study and application of chemically functionalized graphene.
To create the graphene oxide, researchers leaked oxygen gas (O2) into an ultra-high vacuum chamber. Inside, a hot tungsten filament was heated to 1500 degrees Celsius, causing the oxygen molecules to dissociate into atomic oxygen. The highly reactive oxygen atoms then uniformly inserted into the graphene lattice.
The resulting material possesses a high degree of chemical homogeneity. Spectroscopic measurements show that the electronic properties of the graphene vary as a function of oxygen coverage, suggesting that this approach can tune the properties of graphene-based devices.
“It’s unclear if this work will impact real-world applications overnight,” Hersam said. “But it appears to be a step in the right direction.”
Next, researchers will explore other means of chemically modifying graphene to develop a wider variety of materials, much like scientists did for plastics in the last century.
“Maybe oxygen isn’t enough,” Hersam said. “Through chemical modification, the scientific community has developed a wide range of polymers, from hard plastics to nylon. We hope to realize the same degree of tunability for graphene.”