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 observe Dirac fermion excitations in graphene opens the way to promising Raman investigations of electronic properties of graphene and other 2D crystals.
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 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.
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…
We present a computational study of the two-phonon Raman spectra of silicene and graphene within a density-functional non-orthogonal tight-binding model. Due to the presence of linear bands close to the Fermi energy in the electronic structure of both structures, the Raman scattering by phonons is resonant. We find that the Raman spectra exhibit a crossover behavior for laser excitation close to the π-plasmon energy. This phenomenon is explained by the disappearance of certain paths for resonant Raman scattering and the appearance of other paths beyond this energy. Besides that, the electronic…
In this letter we use graphene bubbles to study the Raman spectrum of graphene under biaxial (e.g. isotropic) strain. Our Gruneisen parameters are in excellent agreement with the theoretical values. Discrepancy in the previously reported values is attributed to the interaction of graphene with the substrate. Bilayer balloons (intentionally pressurized membranes) have been used to avoid the effect of the substrate and to study the dependence of strain on the inter-layer interactions.
We demonstrate enhancements of Raman scattering from graphene on two-dimensional photonic crystals using double resonances, which originate from simultaneous enhancements by a localized guided mode and a cavity mode. By adjusting the photonic crystal cavity parameters, the double resonance can be tuned to the G' Raman scattering. Excitation wavelength dependence measurements show a large Raman peak enhancement when the excitation and emission wavelengths meet the double resonance condition. Furthermore, spatial imaging measurements are performed to confirm that the enhancement is localized at …
A constant height of gallium nitride (GaN) nanowires with graphene deposited on them is shown to have a strong enhancement of Raman scattering, whilst variable height nanowires fail to give such an enhancement. Scanning electron microscopy reveals a smooth graphene surface which is present when the GaN nanowires are uniform, whereas graphene on nanowires with substantial height differences is observed to be pierced and stretched by the uppermost nanowires. The energy shifts of the characteristic Raman bands confirms that these differences in the nanowire height has a significant impact on the …
We present Raman spectroscopy measurements of non-etched graphene nanoribbons, with widths ranging from 15 to 160 nm, where the D-line intensity is strongly dependent on the polarization direction of the incident light. The extracted edge disorder correlation length is approximately one order of magnitude larger than on previously reported graphene ribbons fabricated by reactive ion etching techniques. This suggests a more regular crystallographic orientation of the non-etched graphene ribbons here presented. We further report on the ribbons width dependence of the line-width and frequency of …
We present a novel measurement approach which combines the electrical characterization of solution-gated field effect transistors based on epitaxial bilayer graphene on 4H-SiC (0001) with simultaneous Raman spectroscopy. By changing the gate voltage, we observed Raman signatures related to the resonant electron-phonon coupling. An analysis of these Raman bands enabled the extraction of the geometrical capacitance of the system and an accurate calculation of the Fermi levels for bilayer graphene. An intentional application of higher gate voltages allowed us to trigger electrochemical reactions,…
Using the continuum model, we investigate theoretically contribution of the low-energy electronic excitations to the Raman spectrum of superconducting monolayer graphene. We consider superconducting phases characterised by an isotropic order parameter in a single valley and find a Raman peak at a shift set by the size of the superconducting gap. The height of this peak is proportional to the square root of the gap and the third power of the Fermi level, and we estimate its quantum efficiency as $I\sim10^{-14}$.
We report a symmetry resolved electronic Raman scattering (ERS) study of a bilayer graphene device under gate voltage. We show that the ERS continuum is dominated by interband chiral excitations of $A_{2}$ symmetry and displays a characteristic Pauli-blocking behavior similar to the monolayer case. Crucially, we show that non-chiral excitations make a vanishing contribution to the Raman cross-section due to destructive interference effects in the Raman amplitude matrix elements. This is in a marked contrast to optical absorption measurements and opens interesting venues for the use of Raman sc…
We theoretically investigate multiphonons resonance Raman scattering between the Landau levels in graphene on the polar substrate using the Huang-Rhys's model. We not only present the single and multiple surface optical (SO) phonons scattering, but also propose the combined multiphonons scattering (CMS), which is composed of the SO phonon and longitudinal acoustic phonon. We find that the CMS has a blue-shift behavior with increasing the magnetic field, differing from these SO phonon resonance scattering at a special magnetic field. This behavior may be used to explain the changing shoulder of…
Understanding the energy transport by charge carriers and phonons in two-dimensional (2D) van der Waals heterostructures is essential for the development of future energy-efficient 2D nanoelectronics. Here, we performed in situ spatially resolved Raman thermometry on an electrically biased graphene channel and its hBN substrate to study the energy dissipation mechanism in graphene/hBN heterostructures. By comparing the temperature profile along the biased graphene channel with that along the hBN substrate, we found that the thermal boundary resistance between the graphene and hBN was in the ra…
We study the relaxation dynamics of the electron system in graphene flakes under Landau quantization regime using a novel approach of time-resolved Raman scattering. The non-resonant character of the experiment allows us to analyze the field dependence of the relaxation rate. Our results clearly evidence sharp increase in the relaxation rate upon the resonance between the energy of the Landau transition and the G-band and shed new light on relaxation mechanism of the Landau-quantized electrons in graphene beyond the previously studied Auger scattering.
We study electronic contribution to the Raman scattering signals of two-, three- and four-layer graphene with layers at one of the interfaces twisted by a small angle with respect to each other. We find that the Raman spectra of these systems feature two peaks produced by van Hove singularities in moiré minibands of twistronic graphene, one related to direct hybridization of Dirac states, and the other resulting from band folding caused by moiré superlattice. The positions of both peaks strongly depend on the twist angle, so that their detection can be used for non-invasive characterization of…
We present a magneto-Raman study on high-quality single-layer graphene grown by chemical vapor deposition (CVD) that is fully encapsulated in hexagonal boron nitride by a dry transfer technique. By analyzing the Raman D, G, and 2D peaks, we find that the structural quality of the samples is comparable to state-of-the-art exfoliated graphene flakes. From B field dependent Raman measurements, we extract the broadening and associated lifetime of the G peak due to anharmonic effects. Furthermore, we determine the decay width and lifetime of Landau level (LL) transitions from magneto-phonon resonan…
An analytical study is presented of the double resonant Raman scattering process in graphene, responsible for the D and D$^{\prime}$ features in the Raman spectra. This work yields analytical expressions for the D and D$^{\prime}$ integrated Raman intensities that explicitly show the dependencies on laser energy, defect concentration, and electronic lifetime. Good agreement is obtained between the analytical results and experimental measurements on samples with increasing defect concentrations and at various laser excitation energies. The use of Raman spectroscopy to identify the nature of def…
Intensity of the first- and the second-order Raman spectra are calculated as a function of the Fermi energy. We show that the Kohn anomaly effect, i.e., phonon frequency renormalization, in the first-order Raman spectra originates from the phonon renormalization by the interband electron-hole excitation, whereas in the second-order Raman spectra, a competition between the interband and intraband electron-hole excitations takes place. By this calculation, we confirm the presence of different dispersive behaviors of the Raman peak frequency as a function of the Fermi energy for the first- and th…
We report a comprehensive micro-Raman study of a pressurized suspended graphene membrane that hermetically seals a circular pit, etched in a Si/SiO$_2$ substrate. Placing the sample under a uniform pressure load results in bulging of the graphene membrane and subsequent softening of the main Raman features, due to tensile strain. In such a microcavity, the intensity of the Raman features depends very sensitively on the distance between the graphene membrane and the Si substrate, which acts as the bottom mirror of the cavity. Thus, a spatially resolved analysis of the intensity of the G- and 2D…
In this work, we study the Raman spectra of twisted bilayer graphene samples as a function of their twist-angles ($θ$), ranging from 0.03$^\circ$ to 3.40$^\circ$, where local $θ$ are determined by analysis of their associated moire superlattices, as imaged by scanning microwave impedance microscopy. Three standard excitation laser lines are used (457, 532, and 633 nm wavelengths), and the main Raman active graphene bands (G and 2D) are considered. Our results reveal that electron-phonon interaction influences the G band's linewidth close to the magic angle regardless of laser excitation wavele…
Since lattice strain and charge density affect various material properties of graphene, a reliable and efficient method is required for quantification of the two variables. While Raman spectroscopy is sensitive and non-destructive, its validity towards precise quantification of chemical charge doping has not been tested. In this work, we quantified in-situ the fractional frequency change of 2D and G peaks in response of charge density induced by sulfuric acid solution as well as native lattice strain. Based on the experimental data and theoretical corroboration, we presented an optical method …
The band structure of bilayer graphene is tunable by introducing a relative twist angle between the two layers, unlocking exotic phases, such as superconductor and Mott insulator, and providing a fertile ground for new physics. At intermediate twist angles around 10°, highly degenerate electronic transitions hybridize to form excitonic states, a quite unusual phenomenon in a metallic system. We probe the bright exciton mode using resonant Raman scattering measurements to track the evolution of the intensity of the graphene Raman G peak, corresponding to the E2g phonon. By cryogenically cooling…
Raman scattering (RS) spectra and current-voltage characteristics at room temperature were measured in six series of small samples fabricated by means of electron-beam lithography on the surface of a large size (5x5 mm) industrial monolayer graphene film. Samples were irradiated by different doses of C${}^+$ ion beam up to $10^{15}$ cm${}^{-2}$. It was observed that at the utmost degree of disorder, the Raman spectra lines disappear which is accompanied by the exponential increase of resistance and change in the current-voltage characteristics.These effects are explained by suggestion that hig…
