Raman spectroscopy has historically played an important role in the structural characterization of graphitic materials, in particular providing valuable information about defects, stacking of the graphene layers and the finite sizes of the crystallites parallel and perpendicular to the hexagonal axis. Here we review the defect-induced Raman spectra of graphitic materials from both experimental and theoretical standpoints and we present recent Raman results on nanographites and graphenes. The disorder-induced D and D' Raman features, as well as the G'-band (the overtone of the D-band which is always observed in defect-free samples), are discussed in terms of the double-resonance (DR) Raman process, involving phonons within the interior of the 1st Brillouin zone of graphite and defects. In this review, experimental results for the D, D' and G' bands obtained with different laser lines, and in samples with different crystallite sizes and different types of defects are presented and discussed. We also present recent advances that made possible the development of Raman scattering as a tool for very accurate structural analysis of nano-graphite, with the establishment of an empirical formula for the in- and out-of-plane crystalline size and even fancier Raman-based information, such as for the atomic structure at graphite edges, and the identification of single versus multi-graphene layers. Once established, this knowledge provides a powerful machinery to understand newer forms of sp(2) carbon materials, such as the recently developed pitch-based graphitic foams. Results for the calculated Raman intensity of the disorder-induced D-band in graphitic materials as a function of both the excitation laser energy (E(laser)) and the in-plane size (L(a)) of nano-graphites are presented and compared with experimental results. The status of this research area is assessed, and opportunities for future work are identified.

We present a Raman study of Ar(+)-bombarded graphene samples with increasing ion doses. This allows us to have a controlled, increasing, amount of defects. We find that the ratio between the D and G peak intensities, for a given defect density, strongly depends on the laser excitation energy. We quantify this effect and present a simple equation for the determination of the point defect density in graphene via Raman spectroscopy for any visible excitation energy. We note that, for all excitations, the D to G intensity ratio reaches a maximum for an interdefect distance ∼3 nm. Thus, a given ratio could correspond to two different defect densities, above or below the maximum. The analysis of the G peak width and its dispersion with excitation energy solves this ambiguity.

This work presents a systematic study of the ratio between the integrated intensities of the disorder-induced D and G Raman bands (ID∕IG) in nanographite samples with different crystallite sizes (La) and using different excitation laser energies. The crystallite size La of the nanographite samples was obtained both by x-ray diffraction using synchrotron radiation and directly from scanning tunneling microscopy images. A general equation for the determination of La using any laser energy in the visible range is obtained. Moreover, it is shown that ID∕IG is inversely proportional to the fourth power of the laser energy used in the experiment.

A study of step edges in graphite with different atomic structures combining Raman spectroscopy and scanning probe microscopy is presented. The orientation of the carbon hexagons with respect to the edge axis, in the so-called armchair or zigzag arrangements, is distinguished spectroscopically by the intensity of a disorder-induced Raman peak. This effect is explained by applying the double resonance theory to a semi-infinite graphite crystal and by considering the one-dimensional character of the defect.

In this article we review Raman studies of defects and dopants in graphene as well as the importance of both for device applications. First a brief overview of Raman spectroscopy of graphene is presented. In the following section we discuss the Raman characterization of three defect types: point defects, edges, and grain boundaries. The next section reviews the dependence of the Raman spectrum on dopants and highlights several common doping techniques. In the final section, several device applications are discussed which exploit doping and defects in graphene. Generally defects degrade the figures of merit for devices, such as carrier mobility and conductivity, whereas doping provides a means to tune the carrier concentration in graphene thereby enabling the engineering of novel material systems. Accurately measuring both the defect density and doping is critical and Raman spectroscopy provides a powerful tool to accomplish this task.

When two identical two-dimensional periodic structures are superposed, a mismatch rotation angle between the structures generates a superlattice. This effect is commonly observed in graphite, where the rotation between graphene layers generates Moiré patterns in scanning tunneling microscopy images. Here, a study of intravalley and intervalley double-resonance Raman processes mediated by static potentials in rotationally stacked bilayer graphene is presented. The peak properties depend on the mismatch rotation angle and can be used as an optical signature for superlattices in bilayer graphene. An atomic force microscopy system is used to produce and identify specific rotationally stacked bilayer graphenes that demonstrate the validity of our model.

This work reports the analysis of the G band profile in the Raman spectra of nanographites with different degrees of stacking order. Since the G band scattering coming from the 2D and 3D phases coexisting in the same sample can be nicely distinguished, the relative volumes of 3D and 2D graphite phases present in the samples can be estimated from their Raman spectra. The comparison between Raman scattering and X-Ray diffraction data shows that Raman spectroscopy can be used as an alternative tool for measuring the degree of stacking order of graphitic systems.

No abstract