Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects

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Abstract

We review recent work on Raman spectroscopy of graphite and graphene. We focus on the origin of the D and G peaks and the second order of the D peak. The G and 2D Raman peaks change in shape, position and relative intensity with number of graphene layers. This reflects the evolution of the electronic structure and electron–phonon interactions. We then consider the effects of doping on the Raman spectra of graphene. The Fermi energy is tuned by applying a gate-voltage. We show that this induces a stiffening of the Raman G peak for both holes and electrons doping. Thus Raman spectroscopy can be efficiently used to monitor number of layers, quality of layers, doping level and confinement.

Introduction

Graphene is the two-dimensional (2D) building block for carbon allotropes of every other dimensionality. It can be stacked into 3D graphite, rolled into 1D nanotubes, or wrapped into 0D fullerenes. Its recent discovery [1], [2], [3] completes the carbon-family. This finally opens the opportunity to study experimentally its electronic and phonon properties, which so far had to be inferred from theory.

In general, carbon-based materials play a major role in today’s science and technology and the discovery of graphene is the last of a long string of continuous advances in the science of carbon. These include, for example, the chemical vapour deposition of diamond [4], the discovery of fullerenes [5] and carbon nanotubes [6], [7], [8], and mastering the properties of amorphous and disordered carbons [9], [10], [11], [12], to span, on demand, almost all the range from graphite to diamond to carbon polymers [9], [10], [11], [12], [13], [14], [15], [16], [17]. Indeed, amorphous and diamond-like carbons (DLC) are currently used in many every-day life applications, such as, for example, magnetic hard disk coatings, wear protective and anti-reflective coatings for tribological tools, engine parts, razor blades and sunglasses, biomedical coatings (such as hips or stents) and microelectro-mechanical systems [9], [10]. Graphitic carbon and, to an extent, carbon nanotubes, are also utilized in batteries [18]. Applications in field emission displays, microwave amplifiers, transistors, supercapacitors, structural and conductive composites, photonic devices although all well beyond the proof-of-principle stage, have yet to make it to market. One of the main advantages of graphene is the possible advent of a planar technology, compatible with existing manufacturing processes [1].

A key requirement for carbon research and applications is the ability to identify and characterize all the members of the carbon family, both at the lab- and at mass-production scale. To be appealing, a characterization tool must be nondestructive, fast, with high resolution and give the maximum structural and electronic information. Raman spectroscopy provides all these. It is the backbone of research in such diverse fields, ranging from physics, to engineering, chemistry and biology. Indeed, most of the papers published every year on carbon materials have at least a Raman spectrum in them [19].

Raman spectroscopy can thus become the standard also in the fast growing field of graphene. One should remember that in the process of making graphene, be it from mechanical cleavage [1], [2], “expitaxial growth” [20], [21], chemical vapour deposition [21], [22], chemical exfoliation [23], all sorts of carbon species can in principle occur, similarly to what happens when making nanotubes. Unwanted by-products and structural damage can also be created while shaping graphene into devices. It would thus be advisable to have a structural reference, monitored, for example, by Raman spectroscopy, as common denominator to compare the materials used by different groups. This is standard practice in the field of nanotubes and amorphous and diamond-like carbons [19]. In the case of nanotubes, other optical structural characterization techniques, such as photoluminescence excitation spectroscopy, are now very popular [24], as ellipsometry or XPS are in amorphous and diamond like carbons [25]. It is thus foreseeable that other optical techniques (maybe even simpler than Raman spectroscopy) will become available also for graphene, once the field expands experimentally.

The toll for the simplicity of Raman measurements is paid when it comes to spectral interpretation. The Raman spectra of all carbon systems show only a few prominent features, no matter the final structure, be it a conjugated polymer or a fullerene [19]. The spectra appear deceivingly simple: just a couple of very intense bands in the 1000–2000 cm−1 region and few other second-order modulations. However, their shape, intensity and positions allow to distinguish a hard amorphous carbon, from a metallic nanotube, giving as much information as that obtained by a combination of other lengthy and destructive approaches [19]. The peculiar dispersion of the π electrons in graphene is the fundamental reason why Raman spectroscopy in carbons is always resonant and, thus, a powerful and efficient probe of their electronic properties, not only of their vibrations [19]. This explains why the interpretation of the Raman spectra of graphitic materials was investigated for almost 40 years [19], [26] and why intense effort has been put towards the Raman measurement of few-layer graphite samples [27], [28], even before the discovery of graphene.

Section snippets

D and G peaks, double resonance and Kohn anomalies

Fig. 1 compares the Raman spectra of a few representative carbon materials: graphite, metallic and semiconducting nanotubes and high and low sp3 amorphous carbons, all measured for visible excitation. Fig. 2 plots the D peak position as a function of excitation energy for defected graphite.

The main features in the Raman spectra of carbons are the so-called G and D peaks, which lie at around 1560 and 1360 cm−1 respectively for visible excitation. In amorphous carbons a peak at around 1060 cm−1 (T

Electron–phonon coupling from phonon dispersions and Raman line widths

Electron–phonon coupling (EPC) is a key physical parameter in graphene and nanotubes. Ballistic transport, superconductivity, excited state dynamics, Raman spectra and phonon dispersions all fundamentally depend on it. In nanotubes, the optical phonons EPC are also extremely relevant since electron scattering by optical phonons sets the ultimate limit to high field ballistic transport [56], [57], [58], [59], [60]. Many tight-binding calculations of optical phonons EPC in graphene and nanotubes

The Raman spectrum of graphene and graphene layers

Fig. 5 compares the Raman spectra of graphene and bulk graphite measured at 514.5 nm excitation [29]. The two most intense features are the G peak at 1580 cm−1 and a band at ∼2700 cm−1, historically named G, since it is the second most prominent band always observed in graphite samples [38]. However we now know that this band is the second order of the D peak. Thus we believe it is more convenient to refer to it as 2D peak [29]. Fig. 5 also shows another peak at ∼3250 cm−1. Its frequency is

The Raman spectrum of doped graphene: Breakdown of the adiabatic Born–Oppenheimer approximation

Doping changes the Fermi surface of graphene. This moves the Kohn anomaly away from q=0. Thus, since first order non-double resonant Raman scattering probes q=0 phonons, intuitively we expect a stiffening of the G peak. Indeed, refs. [30], [79] reported that the G peak of graphene responds to doping. The doping level was controlled by applying a gate voltage. The G peak upshifts for both holes and electron doping [30], [79].

Fig. 8(a) and (b) reports the G peak position and FWHM measured at

Disordered graphite and graphene

In order to compare different samples and devices, or different locations on the same sample, another crucial parameter, besides doping, is the amount of disorder. For multilayers assessing turbostraticity is also important.

We introduced a three-stage classification of disorder, leading from graphite to amorphous carbons [13], [14], which allows to simply assess all the Raman spectra of carbons. The Raman spectrum is considered to depend on:

  • (i)

    clustering of the sp2 phase;

  • (ii)

    bond disorder;

  • (iii)

    presence of

Edges and ribbons

The sample edges can be always seen as defects. Thus, when the laser spot includes them, even if the bulk sample is perfect, a D peak will appear. Fig. 5 shows no D peak at the centre of a typical graphene layer, proving the absence of a significant number of defects in the structure. A single D peak is only observed at the sample edge, Fig. 11, consistent with the single 2D peak discussed in Section 4. On the other hand the D peak at the edge of graphite consists of two peaks D1 and D2 [36],

Conclusions

A review of the Raman spectra of graphite and graphene was presented. The G and 2D Raman peaks change in shape, position and relative intensity with number of graphene layers. This reflects the evolution of the electronic structure and electron–phonon interactions. Doping upshifts and sharpens the G peak for both both holes and electrons. Disorder can be monitored via the D peak. Thus Raman spectroscopy can be efficiently used to monitor a number of layers, quality of layers, doping level and

Acknowledgements

The author acknowledges S. Pisana, M. Lazzeri, C. Casiraghi, V. Scardaci, S. Piscanec, K.S. Novoselov, A.K. Geim, F. Mauri, J.C. Meyer, J. Robertson and funding form the Royal Society and The Leverhulme Trust.

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