Functional hybrid systems based on large-area high-quality graphene

Acc Chem Res. 2013 Oct 15;46(10):2193-201. doi: 10.1021/ar3001519.

Abstract

The properties of sp² carbon allotropes can be tuned and enriched by their interaction with other materials. The large interface to the outside world in these forms of carbon is ideally suited for combining in an optimal manner several functionalities thanks to this interaction. A wide range of novel materials holding strong promise in energy, optoelectronics, microelectronics, mechanics, or medical applications have been designed accordingly. Graphene, the last representative of this family of sp² carbon materials, has already yielded a wealth of hybrid systems. A new class of these hybrids is emerging, which allows researchers to exploit the properties of truly single-layer graphene. These systems rely on high-quality graphene. In this Account, we describe our recent efforts to develop hybrid systems through various approaches and with various scopes. Depending on the interaction between graphene and molecules, metal clusters, layers, and substrates, either graphene may essentially preserve the electronic properties that make it a unique platform for electronic transport, or new organization and properties in the materials may arise due to the graphene contact at the expense of deep modification of graphene's properties. We prepare our graphene samples by both mechanical exfoliation of graphite and chemical vapor deposition on metals. We use this to study graphene in contact with various species, which either decorate graphene or are intercalated between it and its substrate. We first address the electronic and magnetic properties in systems where graphene is in epitaxy with a metal and discuss the potential to manipulate the properties of both materials, highlighting graphene's role as a protective capping layer in magnetic functional systems. We then present graphene/metal dot hybrids, which can utilize the two-dimensional gas properties of Dirac fermions in graphene. These hybrids allow one to tune the coupling between clusters hosting electronically ordered states such as superconductivity and explore quantum phase transitions controlled by electrostatic back gates. We finally discuss the optical properties of hybrids in which graphene is decorated with optically active molecules. Depending on how close these molecules are to the graphene's electromechanical systems, the interaction of the system with light can be changed. Fields such as spintronics and catalysis could benefit from high-quality graphene based hybrid systems, which have not been fully explored.