We report the observation of an intense anomalous peak at 1608 cm$^{-1}$ in the Raman spectrum of graphene associated to the presence of chromium nanoparticles in contact with graphene. Bombardment with an electron beam demonstrates that this peak is distinct from the well studied D$'$ peak appearing as defects are created in graphene; the new peak is found non dispersive. We argue that the bonding of chromium atoms with carbon atoms softens the out-of-plane optical (ZO) phonon mode, in such a way that the frequency of its overtone decreases to $2ω_{\rm ZO}\simω_{\rm G}$, where $ω_{\rm G}$=1585~cm$^{-1}$ is the frequency of the Raman-active E$_{\rm 2g}$ mode. Thus, the observed new peak is attributed to the 2ZO mode which becomes Raman-active following a mechanism known as Fermi resonance. First-principles calculations on vibrational and anharmonic properties of the graphene/Cr interface support this scenario.
We describe Raman spectroscopy based method of measuring thermal conductivity of thin films, and review significant results achieved with this technique pertinent to graphene and other two-dimensional materials. The optothermal Raman method was instrumental for the discovery of unique heat conduction properties of graphene. In this method, Raman spectroscopy is used to determine the local temperature of the sample while the excitation laser is utilized as a heat source. The success of Raman spectroscopy in investigating thermal conductivity of suspended graphene and graphene-based thin films m…
Raman spectra were measured for mono-, bi- and trilayer graphene grown on SiC by solid state graphitization, whereby the number of layers was pre-assigned by angle-resolved ultraviolet photoemission spectroscopy. It was found that the only unambiguous fingerprint in Raman spectroscopy to identify the number of layers for graphene on SiC(0001) is the linewidth of the 2D (or D*) peak. The Raman spectra of epitaxial graphene show significant differences as compared to micromechanically cleaved graphene obtained from highly oriented pyrolytic graphite crystals. The G peak is found to be blue-shift…
We review the different results obtained in the last decade in the field of Raman scattering of graphene based systems, with an applied magnetic field. Electronic properties of graphene based systems with an applied magnetic field will first be described. The phonon response in magnetic field, the magneto-phono resonance, will then be introduced and described in different systems, including graphene, multilayer graphene and bulk graphite. Electronic Raman scattering is then be discussed in the context of Landau level spectroscopy, of electron phonon interaction and of electron-electron interac…
We synthesized three-dimensional nanoporous graphene films by a chemical vapor deposition method with nanoporous copper as a catalytic substrate. The resulting nanoporous graphene has the same average pore size as the underlying copper substrate. Our surface-enhanced Raman scattering (SERS) investigation indicates that the nanoporosity of graphene significantly improves the SERS efficiency of graphene as a substrate as compared to planar graphene substrates.
We calculate the probabilities of two- and four-phonon Raman scattering in graphene and show how the relative intensities of the overtone peaks encode information about relative rates of different inelastic processes electrons are subject to. If the most important processes are electron-phonon and electron-electron scattering, the rate of the latter can be deduced from the Raman spectra.
The results of micro-Raman scattering measurements performed on three different ``graphitic'' materials: micro-structured disks of highly oriented pyrolytic graphite, graphene multi-layers thermally decomposed from carbon terminated surface of 4H-SiC and an exfoliated graphene monolayer are presented. Despite its multi-layer character, most parts of the surface of the graphitized SiC substrates shows a single-component, Lorentzian shape, double resonance Raman feature in striking similarity to the case of a single graphene monolayer. Our observation suggests a very weak electronic coupling bet…
The paper reports a theoretical study of scattering of electrons by edges in graphene and its effect on Raman scattering. First, effective models are discussed for translationally invariant and rough edges. Second, they are used in a calculation of the edge-activated Raman D peak intensity and its dependence on the polarization of the incident/scattered light, as well as on the position of the excitation spot. Manifestations of the quasiclassical character of electron motion in Raman scattering are discussed.
A simple, non-invasive method using Raman spectroscopy for the estimation of the thickness of graphene layers grown epitaxially on silicon carbide (SiC) is presented, enabling simultaneous determination of thickness, grain size and disorder using the spectra. The attenuation of the substrate Raman signal due to the graphene overlayer is found to be dependent on the graphene film thickness deduced from X-ray photoelectron spectroscopy and transmission electron microscopy of the surfaces. We explain this dependence using an absorbing overlayer model. This method can be used for mapping graphene …
Surface enhanced Raman scattering (SERS) exploits surface plasmons induced by the incident field in metallic nanostructures to significantly increase the Raman intensity. Graphene provides the ideal prototype two dimensional (2d) test material to investigate SERS. Its Raman spectrum is well known, graphene samples are entirely reproducible, height controllable down to the atomic scale, and can be made virtually defect-free. We report SERS from graphene, by depositing arrays of Au particles of well defined dimensions on graphene/SiO$_2$(300nm)/Si. We detect significant enhancements at 633nm. To…
Graphene is an ideal platform to study the coherence of quantum interference pathways by tuning doping or laser excitation energy. The latter produces a Raman excitation profile that provides direct insight into the lifetimes of intermediate electronic excitations and, therefore, on quantum interference, which has so far remained elusive. Here, we control the Raman scattering pathways by tuning the laser excitation energy in graphene doped up to 1.05eV, above what achievable with electrostatic doping. The Raman excitation profile of the G mode indicates its position and full width at half maxi…
In Raman spectroscopy of graphite and graphene, the $D$ band at $\sim 1355$cm$^{-1}$ is used as the indication of the dirtiness of a sample. However, our analysis suggests that the physics behind the $D$ band is closely related to a very clear idea for describing a molecule, namely bonding and antibonding orbitals in graphene. In this paper, we review our recent work on the mechanism for activating the $D$ band at a graphene edge.
Edges naturally exist in a single-layer graphene sample. Similarly, individual graphene layers in a multilayer graphene sample contribute their own edges. We study the Raman spectrum at the edge of a graphene layer laid on n layer graphene (nLG). We found that the D band observed from the edge of the top graphene layer exhibits an identical line shape to that of disordered (n+1)LG induced by ion-implantation. Based on the spectral features of the D and 2D bands, we identified two types of alignment configurations at the edges of mechanically-exfoliated bilayer and trilayer graphenes, whose edg…
Massless Dirac fermions in graphene can acquire a mass through different kinds of sublattice-symmetry-breaking perturbations, and there is a growing need to determine this mass using a conventional method. We describe how the mass caused by a staggered sublattice potential is determined using Raman spectroscopy and explain the mechanism in terms of the pseudospin polarization of massive Dirac fermions.
We report the Raman spectroscopy of 12C/13C graphene isotope superlattices synthesized by chemical vapour deposition. At large periods the Raman spectra corresponds to the sum of the bulk 12C and 13C contributions. However, at small periods we observe the formation of mixed 12C/13C modes for Raman processes that involve two phonons, which results in the tripling of the 2D and 2D' Raman peaks. This tripling can be well understood in the framework of real space Raman spectroscopy, where the two emitted phonons stem from different regions of the superlattice. The intensity of the mixed peak incre…
The pressure evolution of the Raman spectrum of graphene grown by chemical vapour deposition on polycrystalline copper is investigated with the use of a polar and a non-polar pressure transmitting medium (PTM). The G and 2D Raman bands exhibit similar pressure slopes for both PTM irrespectively of any unintentional initial doping and/or strain of the samples. Our analysis suggests that any pressure-induced charge transfer effects are negligibly small to influence the pressure response of graphene. This is determined by the mechanical stress due to the pressure-induced substrate contraction and…
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 in free state has finally provided the possibility to study experimentally its electronic and phonon properties. Here we show that graphene's electronic structure is uniquely captured in its Raman spectrum that clearly evolves with increasing number of layers. Raman fingerprints for single-, bi- and few-layer graphene reflect changes in the electronic structure and electron-phon…
We present Raman spectroscopy measurements on single- and few-layer graphene flakes. Using a scanning confocal approach we collect spectral data with spatial resolution, which allows us to directly compare Raman images with scanning force micrographs. Single-layer graphene can be distinguished from double- and few-layer by the width of the D' line: the single peak for single-layer graphene splits into different peaks for the double-layer. These findings are explained using the double-resonant Raman model based on ab-initio calculations of the electronic structure and of the phonon dispersion. …
The electron-phonon matrix elements relevant to the Raman intensity and Kohn anomaly of the G band are calculated by taking into account the effect of the edge of graphene. The analysis of the pseudospin reveals that the longitudinal optical phonon mode undergoes a strong Kohn anomaly for both the armchair and zigzag edges, and that only the longitudinal (transverse) optical phonon mode is a Raman active mode near the armchair (zigzag) edge. The Raman intensity is enhanced when the polarization of the incident laser light is parallel (perpendicular) to the armchair (zigzag) edge. This asymmetr…
We synthesize large-area graphene via atmospheric-pressure (AP) chemical vapor deposition (CVD) on copper, and transfer to SiO2 wafers. In contrast to low-pressure (LP) CVD on copper, optical contrast and atomic force microscopy measurements show AP-CVD graphene contains significant multi-layer areas. Raman spectroscopy always shows a single Lorentzian 2D peak, however systematic differences are observed in the 2D peak energy, width, and intensity for single- and multi-layer regions. We conclude that graphene multi-layers grown by AP-CVD on Cu are rotationally disordered.
We carried out micro-Raman spectroscopy of graphene layers over the temperature range from approximately 80 K to 370 K. The number of layers was independently confirmed by the quantum Hall measurements and atomic force microscopy. The measured values of the temperature coefficients for the G and 2D-band frequencies of the single-layer graphene are -0.016 1/(cm K) and -0.034 1/(cm K), respectively. The G peak temperature coefficient of the bi-layer graphene and bulk graphite are -0.015 1/(cm K) and -0.011 1/(cm K), respectively.
The electromagnetic enhancement for surface enhanced Raman spectroscopy (SERS) of graphene is studied by inserting a layer of Al2O3 between epitaxial graphene and Au nanoparticles. Different excitation lasers are utilized to study the relationship between laser wavelength and SERS. The theoretical calculation shows that the extinction spectrum of Au nanoparticles is modulated by the presence of graphene. The experimental results of the relationship between the excitation laser wavelength and the enhancement factor fit well with the calculated results. An exponential relationship is observed be…
The electronic structure of bilayer graphene is investigated from a resonant Raman study using different laser excitation energies. The values of the parameters of the Slonczewski-Weiss-McClure model for graphite are measured experimentally and some of them differ significantly from those reported previously for graphite, specially that associated with the difference of the effective mass of electrons and holes. The splitting of the two TO phonon branches in bilayer graphene is also obtained from the experimental data. Our results have implications for bilayer graphene electronic devices.
The dominant phonon wavevectors $q^{*}$ probed by the 2D Raman mode of graphene are highly anisotropic and rotate with the orientation of the polarizer:analyzer direction relative to the lattice. The corresponding electronic transitions connect the electronic equibandgap contours where the product of the ingoing and outgoing optical matrix elements is strongest, showing a finite component along $\bm{K}-\bmΓ$ that sensitively determines $q^{*}$. We revoke the notion of 'inner' and 'outer' processes. Our findings explain the splitting of the 2D mode of graphene under uniaxial tensile strain. The…
A method is proposed to extract pure Raman spectrum of epitaxial graphene on SiC by using a Non-negative Matrix Factorization. It overcomes problems of negative spectral intensity and poorly resolved spectra resulting from a simple subtraction of a SiC background from the experimental data. We also show that the method is similar to deconvolution, for spectra composed of multiple sub- micrometer areas, with the advantage that no prior information on the impulse response functions is needed. We have used this property to characterize the Raman laser beam. The method capability in efficient data…
Electrostatic gating offers elegant ways to simultaneously strain and dope atomically thin membranes. Here, we report on a detailed \textit{in situ} Raman scattering study on graphene, suspended over a Si/SiO$_2$ substrate. In such a layered structure, the intensity of the Raman G- and 2D-mode features of graphene are strongly modulated by optical interference effects and allow an accurate determination of the electrostatically-induced membrane deflection, up to irreversible collapse. The membrane deflection is successfully described by an electromechanical model, which we also use to provide …
The paper presents a joint consideration of Raman spectra of sp2 amorphous carbons alongside with the nature and type of their amorphicity. The latter was attributed to the enforced fragmentation. The fragments, presented with size-restricted graphene domains with heteroatom necklaces in the circumference, are the basic structural units (BSUs) of the solids, determining them as amorphics with molecular structure. The standard G-D-2D pattern of Raman spectra of polycyclic aromatic hydrocarbons, sp2 amorphous carbons, graphene and/or graphite crystal is attributed to BSUs graphene domains. The m…
We have investigated antidot lattices, which were prepared on exfoliated graphene single layers via electron-beam lithography and ion etching, by means of scanning Raman spectroscopy. The peak positions, peak widths and intensities of the characteristic phonon modes of the carbon lattice have been studied systematically in a series of samples. In the patterned samples, we found a systematic stiffening of the G band mode, accompanied by a line narrowing, while the 2D mode energies are found to be linearly correlated with the G mode energies. We interpret this as evidence for p-type doping of th…
Raman spectroscopy, a fast and nondestructive imaging method, can be used to monitor the doping level in graphene devices. We fabricated chemical vapor deposition (CVD) grown graphene on atomically flat hexagonal boron nitride (hBN) flakes and SiO$_2$ substrates. We compared their Raman response as a function of charge carrier density using an ion gel as a top gate. The G peak position, 2D peak position, 2D peak width and the ratio of the 2D peak area to the G peak area show a dependence on carrier density that differs for hBN compared to SiO$_2$. Histograms of two-dimensional mapping are used…
Landau level broadening mechanisms in electrically neutral and quasineutral graphene were investigated through micro-magneto-Raman experiments in three different samples, namely, a natural single-layer graphene flake and a back-gated single-layer device, both deposited over Si/SiO2 substrates, and a multilayer epitaxial graphene employed as a reference sample. Interband Landau level transition widths were estimated through a quantitative analysis of the magnetophonon resonances associated with optically active Landau level transitions crossing the energy of the E_2g Raman-active phonon. Contra…
Raman measurements on monolayer graphene folded back upon itself as an ordered but skew-stacked bilayer (i.e. with interlayer rotation) presents new mechanism for Raman scattering in sp2 carbons that arises in systems that lack coherent AB interlayer stacking. Although the parent monolayer does not exhibit a D-band, the interior of the skewed bilayer produces a strong two-peak Raman feature near 1350 cm-1; one of these peaks is non-dispersive, unlike all previously observed D-band features in sp2 carbons. Within a double-resonant model of Raman scattering, these unusual features are consistent…
An experimental study of Raman scattering in N-layer graphene as a function of the top layer doping is reported. At high doping level, achieved by a CHF_3 plasma treatment, we observe a splitting of the $G$ band in the spectra of bilayer and 4-layer graphene (N even), whereas the splitting is not visible in case of monolayer and trilayer graphene (N odd). The different behaviors are related to distinct electron-phonon interactions, which are affected by symmetry breaking and Fermi level position in different ways in the various N-layer graphenes. In trilayer graphene, a weakening of the electr…
Measurements and calculations have shown significant disagreement regarding the sign and variations of the thermal expansion coefficient (TEC) of graphene $α(T)$. Here we report dedicated Raman scattering experiments conducted for graphene monolayers deposited on silicon nitride substrates and over the broad temperature range 150--900~K. The relation between those measurements for the G band and the graphene TEC, which involves correcting the measured signal for the mismatch contribution of the substrate, is analyzed based on various theoretical candidates for $α(T)$. Contrary to calculations …
The magneto-phonon resonance or MPR occurs in semiconductor materials when the energy spacing between Landau levels is continuously tuned to cross the energy of an optical phonon mode. MPRs have been largely explored in bulk semiconductors, in two-dimensional systems and in quantum dots. Recently there has been significant interest in the MPR interactions of the Dirac fermion magnetoexcitons in graphene, and a rich splitting and anti-crossing phenomena of the even parity E2g long wavelength optical phonon mode have been theoretically proposed and experimentally observed. The MPR has been found…
We study theoretically the Raman spectrum of the rotated double-layer graphene, consisting of two graphene layers rotated with respect to each other by an arbitrary angle θ. We find a relatively simple dependence of the Raman G peak intensity on the angle θ. On the other hand, the Raman 2D peak position, intensity, and width show a much more complicated dependence on the angle θ. We account for all of these effects, including dependence on the incoming photon energy, in good agreement with the experimental data. We find that it is sufficient to include the interaction between the graphene laye…
One of the greatest issues of nanoelectronics today is how to control the heating of the components. Graphene is a promising material in this area and it is essential to study its thermal properties. Here, the effect of heating a bilayer structure was investigated using in situ Raman spectroscopy. In order to observe the effects on each individual layer, an isotopically labelled bilayer graphene was synthesized where the two layers are composed of different carbon isotopes. Therefore, the frequency of the phonons in the Raman spectra is shifted in relation to each other. This technique was use…
By analytically constructing the matrix elements of an electron-phonon interaction for the $D$ band in the Raman spectra of armchair graphene nanoribbons, we show that pseudospin and momentum conservation result in (i) a $D$ band consisting of two components, (ii) a $D$ band Raman intensity that is enhanced only when the polarizations of the incident and scattered light are parallel to the armchair edge, and (iii) the $D$ band softening/hardening behavior caused by the Kohn anomaly effect is correlated with that of the $G$ band. Several experiments are mentioned that are relevant to these resu…
We investigate the evolution of the Raman spectrum of defected graphene as a function of doping. Polymer electrolyte gating allows us to move the Fermi level up to 0.7eV, as monitored by \textit{in-situ} Hall-effect measurements. For a given number of defects, we find that the intensities of the D and D' peaks decrease with increasing doping. We assign this to an increased total scattering rate of the photoexcited electrons and holes, due to the doping-dependent strength of electron-electron scattering. We present a general relation between D peak intensity and defects valid for any doping lev…
Polarization resolved micro-Raman spectroscopy was carried out at the edges of bilayer graphene. We find strong dependence of the intensity of the G band on the incident laser polarization, with its intensity dependence being 90 degrees out of phase for the armchair and zigzag case, in accordance with theoretical predictions. For the case of mixed-state edges we demonstrate that the polarization contrast reflects the fractional composition of armchair and zigzag edges, providing a monitor of edge purity, which is an important parameter for the development of efficient nanoelectronic devices.
Raman intensity of Rhodamine B (RhB) is enhanced by inserting a thin high \k{appa} dielectric layer which reduces the surface plasmon damping at the gold-graphene interface. The results indicate that the Raman intensity increases sharply by plasmonic resonance enhancement while maintaining efficient fluorescence quenching with optimized dielectric layer thickness.
The micro-Raman scattering response of a graphene-like location on the surface of bulk natural graphite is investigated both at $T=\unit{4.2}{K}$ and at room temperature in magnetic fields up to 29 T. Two different polarization configurations, co-circular and crossed-circular, are employed in order to determine the Raman scattering selection rules. Several distinct series of electronic excitations are observed and we discuss their characteristic shapes and amplitudes. In particular, we report a clear splitting of the signals associated with the inter-Landau level excitations $-n\rightarrow+n$.…
The graphene-enhanced Raman scattering of Rhodamine 6G molecules on pristine, fluorinated and 4-nitrophenyl functionalized graphene substrates was studied. The uniformity of the Raman signal enhancement was studied by making large Raman maps. The relative enhancement of the Raman signal is demonstrated to be dependent on the functional groups, which was rationalized by the different doping levels of pristine, fluorinated and 4-nitrophenyl functionalized graphene substrates. The impact of the Fermi energy of graphene and the phonon energy of the molecules was considered together for the first t…
The Raman peak position and linewidth provide insight into phonon anharmonicity and electron-phonon interactions (EPI) in materials. For monolayer graphene, prior first-principles calculations have yielded decreasing linewidth with increasing temperature, which is opposite to measurement results. Here, we explicitly consider four-phonon anharmonicity, phonon renormalization, and electron-phonon coupling, and find all to be important to successfully explain both the $G$ peak frequency shift and linewidths in our suspended graphene sample at a wide temperature range. Four-phonon scattering contr…
The polarization dependences of the G, D, and 2D (G$'$) bands in Raman spectra at graphene bulk and edge are examined theoretically. The 2D and D bands have different selection rules at bulk and edge. At bulk, the 2D band intensity is maximum when the polarization of the scattered light is parallel to that of incident light, whereas the D band intensity does not have a polarization dependence. At edge, the 2D and D bands exhibit a selection rule similar to that of the G band proposed in a previous paper. We suggest that a constraint equation on the axial velocity caused by the graphene edge is…
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 inter-defect distance ~3nm. Thus, a given ratio…
The Young's modulus of graphene is estimated by measuring the strain applied by a pressure difference across graphene membranes using Raman spectroscopy. The strain induced on pressurized graphene balloons can be estimated directly from the peak shift of the Raman G band. By comparing the measured strain with numerical simulation, we obtained the Young's modulus of graphene. The estimated Young's modulus values of single- and bi-layer graphene are 2.4\pm0.4 TPa and 2.0\pm0.5 TPa, respectively.
We present low-temperature Raman measurements on gate tunable graphene encapsulated in hexagonal boron nitride, which allows to study in detail the Raman G and 2D mode frequencies and line widths as function of the charge carrier density. We observe a clear softening of the Raman G mode (of up to 2.5 cm$^{-1}$) at low carrier density due to the phonon anomaly and a residual G~mode line width of $\approx$ 3.5 cm$^{-1}$ at high doping. From analyzing the G mode dependence on doping and laser power we extract an electron-phonon-coupling constant of $\approx$ 4.4 $\times$ 10$^{-3}$ (for the G mode…
Multi-layer graphene with rhombohedral stacking is a promising carbon phase possibly displaying correlated states like magnetism or superconductivity due to the occurrence of a flat surface band at the Fermi level. Recently, flakes of thickness up to 17 layers were tentatively attributed ABC sequences although the Raman fingerprint of rhombohedral multilayer graphene is currently unknown and the 2D resonant Raman spectrum of Bernal graphite not understood. We provide a first principles description of the 2D Raman peak in three and four layers graphene (all stackings) as well as in Bernal, rhom…
We report the direct observation of polarization resolved electronic Raman scattering in a gated monolayer graphene device. The evolution of the electronic Raman scattering spectra with gate voltage and its polarization dependence are in full agreement with theoretical expectations for non-resonant Raman processes involving interband electron-hole excitations across the Dirac cone. We further show that the spectral dependence of the electronic Raman scattering signal can be simply described by the dynamical polarizability of graphene in the long wavelength limit. The possibility to directly ob…
The most important bands for the evaluation of strain in graphene (the 2D and 2D prime modes) are investigated. It is shown that for Bernal-stacked bilayers, the two-phonon Raman features have three different components that can be assigned to processes originating solely from the top graphene layer, bottom graphene layer, and from a combination of processes originating both from the top and bottom layers. The individual components of the 2D and 2D prime modes are disentangled. The reported results enable addressing the properties of individual graphene layers in isotopically labelled turbostr…
The surface-enhanced Raman scattering in graphene deposited on AlxGa1-xN/GaN axial heterostructure nanowires was investigated. The intensity of graphene Raman spectra was found not to be correlated with aluminium content. Analysis of graphene Raman bands parameters, KPFM and electroreflectance showed a screening of polarization charges. Theoretical calculations showed that plasmon resonance in graphene is far beyond the Raman spectral range. This excludes the presence of an electromagnetic mechanism of SERS and therefore suggests the chemical mechanism of enhancement.
Raman spectroscopy is a fast, non-destructive means to characterize graphene samples. In particular, the Raman spectra show a significant dependence on doping. While the change in position and width of the G peak can be explained by the non-adiabatic Kohn anomaly at $Γ$, the significant doping dependence of the 2D peak intensity has not been explained yet. Here we show that this is due to a combination of electron-phonon and electron-electron scattering. Under full resonance, the photogenerated electron-hole pairs can scatter not just with phonons, but also with doping-induced electrons or hol…
Van der Waals layered materials with well-defined twist angles between the crystal lattices of individual layers have attracted increasing attention due to the emergence of unexpected material properties. As many properties critically depend on the exact twist angle and its spatial homogeneity, there is a need for a fast and non-invasive characterization technique of the local twist angle, to be applied preferably right after stacking. We demonstrate that confocal Raman spectroscopy can be utilized to spatially map the twist angle in stacked bilayer graphene for angles between 6.5° and 8° when…
Raman spectroscopy of graphene is reviewed from a theoretical perspective. After an introduction of the building blocks (electronic band structure, phonon dispersion, electron-phonon interaction, electron-light coupling), Raman intensities are calculated using time-dependent perturbation theory. The analysis of the contributing terms allows for an intuitive understanding of the Raman peak positions and intensities. The Raman spectrum of pure graphene only displays two principle peaks. Yet, their variation as a function of internal and external parameters and the occurrence of secondary, defect…
We report on a magneto-Raman scattering study of graphene flakes located on the surface of a bulk graphite substrate. By spatially mapping the Raman scattering response of the surface of bulk graphite with an applied magnetic field, we pinpoint specific locations which show the electronic excitation spectrum of graphene. We present the characteristic Raman scattering signatures of these specific locations. We show that such flakes can be superimposed with another flake and still exhibit a graphene-like excitation spectrum. Two different excitation laser energies (514.5 and 720 nm) are used to …
The line shape of the double-resonant $2D$ Raman mode in bilayer graphene is often considered to be characteristic for a certain laser excitation energy. Here, in a joint experimental and theoretical study, we analyze the dependence of the double-resonant Raman scattering processes in bilayer graphene on the electronic broadening parameter $γ$. We demonstrate that the ratio between symmetric and anti-symmetric scattering processes sensitively depends on the lifetime of the electronic states, explaining the experimentally observed variation of the complex $2D$-mode line shape.
Raman Spectroscopy is able to probe disorder in graphene through defect-activated peaks. It is of great interest to link these features to the nature of disorder. Here we present a detailed analysis of the Raman spectra of graphene containing different type of defects. We found that the intensity ratio of the D and D' peak is maximum (~ 13) for sp3-defects, it decreases for vacancy-like defects (~ 7) and reaches a minimum for boundaries in graphite (~3.5).
Confocal Raman spectroscopy is a versatile, non-invasive investigation tool and a major workhorse for graphene characterization. Here we show that the experimentally observed Raman 2D line width is a measure of nanometer-scale strain variations in graphene. By investigating the relation between the G and 2D line at high magnetic fields we find that the 2D line width contains valuable information on nanometer-scale flatness and lattice deformations of graphene, making it a good quantity for classifying the structural quality of graphene even at zero magnetic field.
We present complete calculations of the two-phonon Raman bands of bilayer graphene, including all overtone and combination modes, within a density-functional tight-binding model. Based on our results, we assign unambiguously the observed two-phonon Raman bands to two-phonon modes, thus resolving the existing controversies. In particular, we show that both overtone and combination modes have essential contribution to the 2D band, bringing about specific modifications of the band shape. We argue that a mid-range two-phonon Raman band, previously assigned to the 2ZO mode, should be assigned to th…
There are several growing methods for graphene. In this study, the growth of graphene-like clusters on the SiC wafers is done by annealing the wafers in a vacuum evaporation system equipped with a heating source accessory. For evaluating the quality of the growth method, the Raman spectra and infrared intensities of graphene-like clusters are studied theoretically and experimentally. For doing the theoretical study, three types of graphene clusters are considered and their Raman spectrum and infrared intensities are found using the Hartree-Fock method. The results show that the geometry of the…
