Raman spectroscopy and in situ Raman spectroelectrochemistry of isotopically engineered graphene systems.

CONSPECTUS: The special properties of graphene offer immense opportunities for applications to many scientific fields, as well as societal needs, beyond our present imagination. One of the important features of graphene is the relatively simple tunability of its electronic structure, an asset that extends the usability of graphene even further beyond present experience. A direct injection of charge carriers into the conduction or valence bands, that is, doping, represents a viable way of shifting the Fermi level. In particular, electrochemical doping should be the method of choice, when higher doping levels are desired and when a firm control of experimental conditions is needed. In this Account, we focus on the electrochemistry of graphene in combination with in situ Raman spectroscopy, that is, in situ Raman spectroelectrochemistry. Such a combination of methods is indeed very powerful, since Raman spectroscopy not only can readily monitor the changes in the doping level but also can give information on eventual stress or disorder in the material. However, when Raman spectroscopy is employed, one of its main strengths lies in the utilization of isotope engineering during the chemical vapor deposition (CVD) growth of the graphene samples. The in situ Raman spectroelectrochemical study of multilayered systems with smartly designed isotope compositions in individual layers can provide a plethora of knowledge about the mutual interactions (i) between the graphene layers themselves, (ii) between graphene layers and their directly adjacent environment (e.g., substrate or electrolyte), and (iii) between graphene layers and their extended environment, which is separated from the layer by a certain number of additional graphene layers. In this Account, we show a few examples of such studies, from monolayer to two-layer and three-layer specimens and considering both turbostratic and AB interlayer ordering. Furthermore, the concept and the method can be extended further beyond the three-layer systems, for example, to heterostructures containing other 2-D materials beyond graphene. Despite a great deal of important results being unraveled so far through the in situ spectroelectrochemistry of graphene based systems, many intriguing challenges still lie immediately ahead. For example, apart from the aforementioned 2-D heterostructures, a substantial effort should be put into a more detailed exploration of misoriented (twisted) bilayer or trilayer graphenes. Marching from the oriented, AB-stacked to AA-stacked, bilayers, every single angular increment of the twist between the layers creates a new system in terms of its electronic properties. Mapping those properties and interlayer interactions dependent on the twist angle represents a sizable task, yet the reward might be the path toward the realization of various types of advanced devices. And last but not least, understanding the electrochemistry of graphene paves the way toward a controlled and targeted functionalization of graphene through redox reactions, especially when equipped with the possibility of an instantaneous monitoring of the thus introduced changes to the electronic structure of the system.