Engineering Chemical Functionality in Graphene

Graphene has attracted enormous attention due to its unique properties.  Equally important is the ability to further tailor these properties through modification of select attributes such as surface chemistry, number of layers, sheet width, and edge structures.  Manipulating the surface chemistry of graphene is important since the chemical composition strongly impacts the electronic properties as well as chemical reactivity both globally and locally. Precise control of the surface chemistry of graphene can also allow for subsequent surface procedures focused on band gap engineering, device fabrication and sensor applications. Given the strong impact of adsorbates, global chemical modification provides opportunities towards greater control over the properties of graphene films.  Control over the spatial distribution of these groups provides an even greater functionality in that the local graphene reactivity can be manipulated, opening up a wealth of opportunities in biosensing, plasmonics, catalysis, smart surfaces, and heterojunction devices. 

This work demonstrates the ability to manipulate the chemistry of graphene while regulating the spatial distribution of various functional groups on the surface. Spatial control over structural and chemical changes is characterized through micro (m-Raman and high-resolution x-ray photoelectron spectroscopy (XPS) mapping and electrical measurements are used to determine how local changes in chemistry influence the electronic properties.  Lastly, we show that the resulting chemical moieties can be used to manipulate the local surface reactivity of graphene, enabling programmable, site-specific electrochemical deposition. These findings demonstrate the ability to tailor the locality of the surface chemistry on graphene surfaces opening up a wide range of reactivity studies and synthesis capabilities, such as programmable material deposition.