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Raman Spectroscopic Characterization of Graphene
Bo Tang , Hu Guoxin & Hanyang Gao
a a a b

School of Mechanical and Power Engineering, ShangHai JiaoTong University, Shanghai, China

School of Environmental Science and Engineering, ShangHai JiaoTong University, Shanghai, China Version of record first published: 13 Apr 2010.

To cite this article: Bo Tang , Hu Guoxin & Hanyang Gao (2010): Raman Spectroscopic Characterization of Graphene, Applied Spectroscopy Reviews, 45:5, 369-407 To link to this article:

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Applied Spectroscopy Reviews, 45:369–407, 2010 Copyright © Taylor & Francis Group, LLC ISSN: 0570-4928 print / 1520-569X online DOI: 10.1080/05704928.2010.483886

Raman Spectroscopic Characterization of Graphene

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School of Mechanical and Power Engineering, ShangHai JiaoTong University, Shanghai, China 2 School of Environmental Science and Engineering, ShangHai JiaoTong University, Shanghai, China
Abstract: The recent progress using Raman spectroscopy and imaging of graphene is reviewed. The intensity of the G band increases with increased graphene layers, and the shape of 2D band evolves into four peaks of bilayer graphene from a single peak of monolayer graphene. The G band will blue shift and become narrow with both electron and hole doping, whereas the 2D band will blue shift with hole doping and red shift with electron doping. Frequencies of the G and 2D band will downshift with increasing temperature. Under compressed strain, the upshift of the G and 2D bands can be found. Moreover, the strong Raman signal of monolayer graphene is explained by interference enhancement effect. As for epitaxial graphene, Raman spectroscopy can be used to identify the superior and inferior carrier mobility. The edge chirality of graphene can be determined by using polarized Raman spectroscopy. All results mentioned here are closely relevant to the basic theory of graphene and application in nanodevices. Keywords: Raman spectroscopy, graphene, doping, strain, FWHM

Graphene, a strictly two-dimensional material with a honeycomb lattice of sp2-bonded carbon atoms, has attracted extensive study since being experimentally discovered by Novoselov et al. in 2004 (1). In physical structure, graphene is the basic building block of carbon nanomaterials, including one-dimensional carbon nanotubes and zero-dimensional fullerenes. For the electronic bands structure, the conduction and valence band touch each other at the K and K points in the Brillouin zone. Graphene exhibits an unusual linear energy dispersion relationship (the electron energy has a linear relationship with wave vector near K and K points), which make the electrons like the massless relativistic Dirac fermions with a vanishing density of states at the Fermi level (2, 3). In the last 5 years, some novel properties of graphene were discovered, such as the quantum spin hall effect (4, 5), electron mobility as high as 120,000 cm2/Vs (the charge carriers mobility of graphene is higher than any other semiconductor at room temperature) (1, 6, 7), ballistic transport at room temperature (8–12), enhanced coulomb interaction (13–17), high mechanical strength (18), high thermal conduction (19–22), and suppression of weak localization (23, 24). These unique properties of graphene make it a candidate for theoretical study and potential device

Address correspondence to Hu Guoxin, School of Mechanical and Power Engineering, ShangHai JiaoTong University, No. 800 Dong Chuan Road, Shanghai City, 200240, China. E-mail: hugx@



B. Tang et al.

applications (4, 25–29). Furthermore, the application of graphene in the spin device has attracted interest (the spin relaxation length reaches ∼2 µm). In order to fabricate this potentially exciting material, some methods including micromechanical cleavage of graphite (MG) (1), chemical vapor deposition (CVD) (30, 31), epitaxial growth on an SiC surface (32–34), and reduction of graphite oxides (35–39) have been developed. The charge carrier mobility of epitaxial graphene growth on SiC is lower, whereas numerous functional groups always remain on the surface of the reduced graphene. Micromechanical cleavage of graphite is the most frequently used method to produce graphene but with a small size (<1,000 µm2). Recently, larger-scale (<1 cm2) graphene has been fabricated by CVD (30). Characterizing graphene is another major area of study because the results are closely relevant to the application of graphene. Some modern measurement technologies are used to characterize graphene, including scanning electron microscopy (SEM) (30, 40), transmission electron microscopy (TEM) (30, 40, 41), atomic force microscopy (AFM) (41), and Raman spectroscopy (40–47). SEM and TEM can be used to obtain physical morphology, but the graphene may be damaged during the complicated measurement process. The precise depth of graphene can be determined by AFM but can be time consuming. Moreover, measuring the electronic properties of graphene is beyond the ability of these three techniques. Raman spectroscopy is not only a versatile tool (number of graphene layers, doping level, and edge chirality of graphene can be obtained at the same time) but is a rapid and nondestructive method to study graphene. Raman spectroscopy is widely used to characterize electronic properties and microstructure of graphite materials (48–51). As a nondestructive technique, a considerable amount of work on graphene has been performed by Raman spectroscopy (46, 47). According to the electronic characteristics of graphite materials, it is well known that the common features of graphene in Raman spectroscopy are in the wavelength region of 800–3,000 cm−1. Three major peaks are found around 1,580, 1,350, and 2,700 cm−1, so-called G, D, and 2D bands, respectively (52–54). The G band associates with E2g phonon at the Brillouin zone center (55). The disorder-induced D band is another fingerprint peak in graphite material with a concentration of defects (56). A 2D peak is the second order of the D peak and caused by the double resonant Raman scattering with two-phonon emissions (52, 57). Interestingly, the 2D band, sensitive to the number of graphene layers, is free of defect and has no D peak (52). It can be fitted with a single peak of the monolayer graphene and fitted with multiple peaks of multilayer graphene (58). Doping is a common phenomenon during fabrication of graphene. The peak positions of the G and 2D bands always shift under doping condition due to electron–phonon coupling (42, 44). Except that the peak shift of G and 2D band can be used to determine the density of a charged impurity, the ratio of integrated intensity of the 2D band to the G band I2D /IG is another method to identify the doping level of graphene (59). The temperature fluctuation in graphene can also be studied by Raman spectroscopy: a linear red shift of the G and 2D bands with increasing temperature can be found (60). Quantitative strain study of graphene results from the substrate can be calculated through Raman curves (61–63). The organization of this review article is as follows: the details of changes in the G band (position, intensity, and full width at half maximum [FWHM]) with varied number of graphene layers, strain, doping level, and fluctuation of temperature in graphene are described in the next section. In the following section the details of changes in the 2D band with number of graphene layers, strain, doping level, and fluctuation of temperature of graphene are described. The integrated intensity ratio I2D /IG is discussed in the next section. Then, attention is focused on edge chirality, so D band is the major content. Raman

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Raman Spectroscopic Characterization of Graphene


spectroscopy to study epitaxial graphene (EG) growth on SiC is reviewed in the following section. Then, an explanation about the strong Raman signal of monolayer graphene is given based on an interference enhancement model. The graphene analyzed are MG except special mention. In the final section, a summary is given.

G Band of Graphene
Intensity Change of the G Band with Varied Number of Graphene Layers An efficient and precise method to identify the number of graphene layers is needed in characterizing graphene. Graf and and Molitor (64) analyzed the change of G band with different number of graphene layers. Figure 1 shows that the intensity of the G peak increases in an almost linear relation with increased layers. This phenomenon can be easily understood as more sp2 bond carbon atoms being detected by the laser spot with increased layers of graphene. It is worthy to note that in addition to increasing intensity, the red shift of the G band takes place with increased number of graphene layers. A peak shift also takes place when graphene under doping or strain results from substrate, which will be addressed in the following section (65). It is not an accurate method to determine the number of graphene layers based on the red shift of the G band. On the other hand, the independence of G band intensity from doping and strain makes it a good criterion to identify monolayer and multilayer graphene.

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Figure 1. (a, b) SFM micrograph and cross-sectional plot of a few-layer graphene flake with central sections down to a single layer. (c) Raman maps of the integrated intensity of the G line. (e) The FWHM of the 2D band. The related cross sections (d, f) are aligned (vertical dashed lines) with the height trace (64).

The experimental data (red open circles and blue open squares. both for the suspended (red solid line) and supported regions (blue dashed line).420 cm−1) for the two regions of the sample. (a) Optical micrograph of an exfoliated graphene monolayer spanning a 300-nm-deep trench etched in the SiO2 epilayer. being induced by the substrate and ambient conditions was reported (67). 60. Normally. (2) and (3) Will be discussed in succeeding sections. for suspended and supported graphene. Unintentional doping. St´ ephane et al. 66). The 7 cm−1 blue shift in the G band frequency means that approximately 6 × 1012 cm−2 carrier Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 2. spatially resolved Raman spectroscopy is used to characterize these two portions of graphene. In Figure 2. 64). Some clear differences can be observed: (1) The G band frequency of the free-standing portion is red shift (∼7 cm−1) compared to the supported portion and accompanies a wider FWHM (14 and 6 cm−1. the MG can always be deposited on SiO2 -coated Si substrate (1. Tang et al.270–1. (65) abstracted the difference of the G band between the free-standing monolayer graphene and supported monolayer of graphene on an SiO2 substrate. (c) Raman spectra in the lower-frequency region (1. a stiffening frequency and narrow FWHM can be observed on the supported portion of graphene. as large as ∼1012/cm2. (b) Raman spectra recorded on the single-layer graphene sample of (a). On the other hand. The latter means that the suspended portion of graphene is almost charge neutral. respectively) are fit with Voigt profiles (solid lines) (65). only the G band is discussed here. . and it is important to obtain the doping level of graphene (1. (2) The 2D band of the suspended graphene is downshifted with respect to the supported portion. A micrometer-sized trench was etched in the SiO2 substrate before the prepared monolayer graphene was deposited. Peak Position and FWHM of the G Band as a Function of Doping Level The G band can not only be used to identify the number of graphene layers but can also determine doping level of graphene on various substrates according to the peak shift and FWHM. (d) Detailed comparison of normalized spectra for the G mode. (3) The ratio of integrated intensity of the 2D band to the G band is four times for the suspended portion compared to the supported portion.372 B. Doping can have a strong influence upon transport properties of graphene. respectively). The frequency of the G band of the suspended portion is similar to the single crystal of graphite (68) and the FWHM is similar to the highest value of charge neutrality graphene (69–75).

it is not a precise method to identify the number of graphene layers by using the ratio I2D /IG when graphene is deposited on a substrate. A quantitative discussion about the doping levels in free-standing monolayer graphene through Raman spectra is needed (73). Inhomogeneity of I2D /IG occurring in Figure 3c indicates that the ratio of integrated intensity of the 2D band to the G band is strongly dependent on the doping level due to substrates. (b) the G-mode line width. the frequency and FWHM of the G band is almost homogeneous around the mean values of ωG = 1. The doping level can be measured by the frequency of the G band even at low levels at low temperature (76. ID /IG .5 cm−1. In Figure 3. ωG .581 cm−1 and G = 13. (d) Correlation between ωG and G for the suspended (red open circles) and lower supported (blue open squares) regions. They pointed out that the broadening of the G mode is proportional to the statistical availability for electron-hole pair generation at the G-mode energy. In order to obtain more details. which implies a shift in the Fermi energy of ∼250 meV from the Dirac point (69). (65). which means that inhomogeneous doping occurs. some authors took the ratio of integrated intensity of the 2D to G peaks as one of the criteria to determine the number of graphene layers. for the suspended graphene. and (c) the ratio of the integrated intensity of the D mode to that of the G mode.Raman Spectroscopic Characterization of Graphene 373 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 3. (73) proposed an equation associated with FWHM of the G band with doping level. Lazzeri et al. But the frequency of the G band is expected to reach an essentially constant minimum value for all carrier densities below 6 × 1012 cm−2 at room temperature. Therefore. G . Raman spatial mapping was performed by St´ ephane et al. 77). In earlier papers. the suspended portion of graphene can easily be distinguished from the supported portion through a lower value of frequency of the G band and wider FWHM. with regions of free-standing and supported material: (a) the G-mode frequency. The frequency and FWHM of the G band of supported graphene varies point to point. Spatial maps of the Raman features of a single-layer graphene sample. density resulting from the substrate is reached in the supported portion. On the contrary. Both the frequency and FWHM of the G band are influenced by doping level through the strong electron–phonon coupling (73–75). as well as for the defective tip of the sample (gray open triangles) (65). so the line width of the .

So a blue shift and narrow FWHM of the G band can be used to identify the doping level (in order to exclude the influence of number of graphene layers. The downshift of the G band was observed with increasing temperature. The possible influence of strain on the graphene samples is neglected in the above discussion (we will discuss the change of the G band resulting from the strain in the following part). A residual strain in the free-standing graphene can be estimated to be less than 0.54 ± 0. = 0 + [fT (− ωG /2 − EF ) − fT ( ωG /2 − EF )] (1) Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Here denotes the maximum phonon broadening from electron-hole pair generation (Landau damping) as it would occur at zero temperature.5 cm−1 and no splitting of the G band occurred (65) (because anisotropic strain would lead to a splitting of the G band (61)). f T is the Fermi-Dirac distribution at temperature T . and 0 is the contribution to the line width from phonon–phonon coupling and other sources that are independent of these electronic interactions. The researchers noted that there was no obvious peak shift more than 0.582 cm−1 for the single. It is worth noting that the blue shift of the G band occurs both in electron and hole doping.374 G band can be written as: G B.62 ± 0. which we will discuss below). Temperature Dependence of the G Band Calizo et al. The extracted negative value for single-layer graphene is χ = −(1. The temperature ranged from −190 to 100◦ C.and bilayer graphene. which means that the interaction of graphene with the substrate is stronger than an intrinsic property of exfoliated graphene prepared and held under ambient conditions (65). Similar measurements were carried out for the bilayer graphene and gave the value of χ = −(1. the peak shift of the 2D band needs to considered and will be discussed below. The supported portion of graphene on SiO2 -covered Si substrate shows increased frequency and reduced FWHM of the G band. In order to distinguish the doping type.584 and 1. and the small deviation around the mean value (about 1 cm−1 (65)) of G implies that the inhomogeneity of the low doping level of free-standing monolayer graphene is less than this level. But the inhomogeneous doping occurs in the supported portion of grapheme. (1) that the average doping level of suspended graphene is less than 2 × 1011 cm−2. EF is the Fermi energy relative to the Dirac point in graphene.20) × 10−2 cm−1/K from Figure 4a. which defines the slope of the dependence. The relationship between frequency of the G mode with temperature can be represented as: ω = ω0 + χ T (2) where ω0 is the frequency of the G mode when temperature T is extrapolated to 0 K and x is the first-order temperature coefficient. (79) pointed out that the temperature dependence of Raman spectroscopy of carbon-based materials can be explained based on the elongation of the C C bond due to thermal expansion or anharmonic coupling of phonon modes. (60) studied temperature-dependent Raman spectroscopy of monolayer and multilayer graphene. Ci et al.06) × 10−2 cm−1/K from Figure 4b. The extrapolated ω0 values are 1.1% according to the experimentally determined shift ratio (78). St´ ephane et al. Polarization Raman was performed to exclude residual uniaxial stress. A conclusion can be made from Eq. correspondingly. Tang et al. The isotropic strain can be excluded in a suspended sample with sample geometry. the shape of the 2D bond needs to be considered too. suggested that the G band frequency reached its lowest value and maximum width for electrical neutral graphene (65). .

Although one cannot absolutely exclude the influence from the substrate. the effect does not strongly affect the value of thermal coefficients (82. the change of phonon frequency of graphene with temperature can be provided (80). the measured frequency change ω = ω − ω0 can be shown as (60): ω ≡ (χT +χV ) T = dω dT T+ V dω dV T = T dω dT T+ V dω dV T dω dT T P (3) Here. 84). Two kinds of strain can be introduced to graphene through substrate: uniaxial strain and biaxial strain. Temperature dependence of the G peak frequency for the single. 83). both contributions are reflected in the resulting Raman spectra of the temperature coefficient. which indicates that the effect of electron–phonon coupling is obviously not with this range of temperature. According to the anharmonic terms in the lattice potential energy. The temperature effects can be roughly divided into the “self-energy” shift due to the anharmonic coupling of the phonon modes and the shift contribution due to the thermal expansion of the crystal. Thus. Unlike frequency. Under constant pressure rather than constant volume. x = xV + xT . Raman curves of tensile strained graphene show an obvious red shift of the G and 2D bands. The possible effect of the substrate (Si coated with 300 nm of SiO2 ) should be considered. This means that the measured temperature coefficients for the G band are less influenced by the substrate property. The insets show the shape of G peak. it is possible to open a band gap on graphene because the strain can break the sublattice symmetry (61. Moreover. it is predicted that strain resulting from a substrate can strongly modify the electronic and optical properties of graphene. although the thermal expansion also results from the anharmonicity. The physical mechanism of the latter is different from the former but related to the change of the force constants of the material with volume. xT is defined as to be the self-energy shift due to the direct coupling of the phonon modes and xV as the shift due to the thermal expansion induced volume change. Relationship between the G Band and Uniaxial Strain in Graphene As monolayer graphite material. Zhen researched the evolution of the Raman pattern of graphene under . This result is in line with the report of the G band of highly oriented pyrolytic graphite (HOPG) (81).(a) and bilayer (b) graphene. The measured data were used to extract the temperature coefficient for G peak (60). the FWHM of the G band of monolayer and bilayer graphene is not sensitive to temperature.Raman Spectroscopic Characterization of Graphene 375 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 4.

The graphene was deposited on a transparent and flexible substrate. εyy ≈ −0. The black lines are the curve fit to the data.9cm−1 /% ε (5) The value is in accordance with the experimental result of single-layer graphene (−14. The dependence between uniaxial strain with electronic structure of graphene . it is enough to load the strain to graphene. which can be understood by the weakened bonds between carbon atoms and lower vibrational frequency due to raised distance between carbon atoms. The value of the strain is determined by dividing the extra length by the unstrained length of substrate. polyethylene terephthalate (PET) (62). The slope is 14. Tang et al. which is calculated by using the Poisson ratio of graphene (87).376 B.7 and −12.7 cm−1/%). Tensile strain on single-/three-layer graphene was loaded by stretching the substrate film in one direction.24 is the Gruneisen parameter of carbon nanotubes (CNTs) (85). and ω0 is the Raman frequency of the G band of unstrained graphene. So the relationship of frequency with strain can be written as (85. 86): ω = γ · (εxx + εyy ) ω0 (4) where r = 1. Therefore. uniaxial strain (62). The G band frequency of single-layer (black squares) and three-layer (red circles) graphene under uniaxial strain.2 cm−1/% for singlelayer graphene and 12.1 ± 0. Both uniaxial strain and shear strain are attributed to the change of peak position.186εxx is the relative strain in the perpendicular direction.186) = −15. respectively. εxx is the uniaxial strain.2 ± 0. The linear dependence between peak shifts with strain can be interpreted on the basis of phonon deformation potentials. Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 5.1 cm−1/% for three-layer graphene (62). The frequency of the G band is red shift with increasing uniaxial strain. Although the interaction between graphene and PET is van der Waals force. Figure 5 shows the frequency of the G band as a function of uniaxial strain for monolayer graphene and three-layer graphene.2 ± 0. the shear strain can be ignored because of its smaller contribution (85).6 cm−1/%. the G band frequency dependence on uniaxial tensile strain is approximately estimated as: ω = −ω0 · γ · (1 − 0. A linear dependence of the G band frequency with strain can be seen. and the slope for single-layer and three-layer graphene are −14.

(a) Schematic representation of the effect of uniaxial tensile stress on a graphene supercell.78%) in our experiment (62). was calculated by using a first-principle calculation. a band gap as big as 300 meV can be reached after loading 1% uniaxial strain on graphene. A band gap is clearly seen on the band structure of strained graphene (62). Quantitatively. . The insets show the calculated density of states (DOS) of unstrained and 1% tensile strained graphene.Raman Spectroscopic Characterization of Graphene 377 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 6. Band gap of strained graphene with the increase of uniaxial tensile strain on graphene. A band gap appears at the K point of the Brillouin zone of strained grapheme. The magnitude of the gap is determined by the gap opening of the density of states. The dashed line and red solid dot indicate the calculated band gap of graphene under the highest strain (0. Calculated band structure of unstrained (b) and 1% tensile strained (c) graphene. The results are shown in Figures 6 and 7. which can be attributed to the breaking of sublattice symmetry (88–90). Figure 7. The dashed (solid) lattices indicate the unstrained (strained) graphene.

Figure 6(c) indicates the graphene transfer to a semiconductor material with an obvious band gap of the π band at the K point of the boundary of the Brillouin zone after loading the uniaxial strain. whereas the intensity of D band decreases. Tang et al. The SiO2 capping layers (5 nm) were deposited on the top of the graphene by pulsed laser deposition (PLD).378 B. an almost linear relationship between uniaxial strain and band gap can be seen. Relationship between the G Band and Biaxial Strain in Graphene Zhen et al. (b) The intensity ratio of the D band and G band (I D /I G ) of graphene sheets with one to four layers (coated with SiO2 ) after annealing at different temperature. followed by annealing at different temperatures to load the biaxial strain to the graphene. Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 8.) The peak shift of the G band is attributed to the compressive stress on graphene result from SiO2 . (63) also studied graphene with biaxial strain. so exerted compressive stress loaded in the graphene through van der Waals force. (We only discuss the G band here. (a) Raman spectra of single-layer graphene coated by 5-nm SiO2 and annealed at different temperature. From the above discussion we know that the effect of doping from the substrate can modify the frequency of the G band. Therefore. The biaxial compressive stress is similar to the biaxial stress at thin film. The I D /I G (defects) decreased significantly upon annealing (63). which indicates that the effect of doping can be ignored (in the next section we will see that the information of the 2D band further proves this opinion). the 2D and Ds band will be discussed later. . The capping film becomes denser during the process of annealing. which results from the lattice mismatch with substrate. too. Figure 8 clearly shows that both the G and 2D bands blue shift with increased annealing temperature. From Figure 7. In this case only a small fluctuation (1 cm−1) appears about the FWHM. the biaxial compressive stress on graphene can be estimated as follows.

Using A = −1. The appearance of such large stress is mainly because graphene sheets are very thin (0. so graphene can be easily compressed or expanded.47 cm−1/GPa. With all shear components of strain equal to zero. The estimated stress on single-layer graphene with varies annealing temperature as shown in Figure 9d. (61) did some detailed research of the G band of graphene under uniaxial stress. There is only one solution for this equation: λ = A(εxx + εyy ) = 2Aεxx = 2A(S11 + S12 )σ Therefore. while the splitting increases. The compressive stress on graphene was as high as ∼2.335 nm in thickness for single-layer graphene) (94). Both peaks are red shift with increasing strain. the stress coefficient is estimated to be 7. ωσ − ω0 = λ λ A(S11 + S12 )σ ≈ = = ασ ωτ + ω0 2ω0 ω0 (8) (9) where a = A(S11 + S12 )/ω0 is the stress coefficient for Raman peak shift. The G band split into two components after the strain reached about 0. the secular equation of such a system can be written as: A(εxx + εyy ) − λ B (εxx − εyy ) =0 B (εxx − εyy ) A(εxx + εyy ) − λ (7) Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 2 2 where λ = ωσ − ω0 .16 × 10−12 Pa−1 (93). One of the components polarized along the strain and another polarized perpendicular the strain. and the stress on single-layer graphene can be fitted by the following formula: σ = −0. It has been reported that even very weak van der Waals interaction can produce large stress on singlewall carbon nanotubes (95). . The G band of graphene red shifted by ∼5 cm−1 after silicon deposition. and ω0 = 1.5%. εxy = εyz = εzx = 0.155 + (2. The evolution of the G and 2D bands with varied strain are shown in Figure 10.67 GPa on graphene sheet (63).44 × 107 cm−2 (91) and graphite elastic constants S11 = 0. Mohiuddin et al.580 cm−1.17 × 10−6 )T 2 (10) where σ is the compressive stress (GPa) and T is temperature (◦ C). εxx = 2S13 σ . The double degenerate E2g optical mode splits into two components (named G+ and G−) under a strong enough uniaxial strain.98 × 10−12 Pa−1. with ωσ and ω0 being the frequencies of Raman E2g phonon under stressed and unstressed conditions. which corresponds to a tensile stress of ∼0. the strain ε induced by an biaxial stress can be expressed as (91.36 × 10−3 )T + (5. S12 = −0.Raman Spectroscopic Characterization of Graphene 379 For a hexagonal system.1 GPa after depositing SiO2 following annealing at 500◦ C. Tensile stress was introduced onto graphene by depositing a thin cover layer of silicon. 92) ⎤ ⎡ ⎡ ⎤⎡ ⎤ S11 S12 S13 σ εxx ⎢ εyy ⎥ ⎢ S12 S11 S13 ⎥⎢σ ⎥ ⎥ ⎢ ⎢ ⎥⎢ ⎥ ⎢ εzz ⎥ ⎢ S13 S13 S33 ⎥⎢ 0 ⎥ ⎥=⎢ ⎢ ⎥⎢ ⎥ (6) ⎢ εyz ⎥ ⎢ ⎥⎢ 0 ⎥ S44 ⎥ ⎢ ⎢ ⎥⎢ ⎥ ⎣ εzx ⎦ ⎣ ⎦⎣ 0 ⎦ S44 0 εxy 2(S11 − S12 ) with the coordinates x and y in the graphene plane and with z perpendicular to the plane. so that εxx = εyy = (S11 − S12 )σ .

. and 2D band (c) of graphene sheets with one to four layers (coated with SiO2 ) after annealing at different temperature.380 B. Figure 10. D band (b). Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 9. The Raman peak frequency of G band (a). which were attributed to the strong compressive stress on graphene.8%. (d) Magnitude of compressive stress on single-layer graphene controlled by annealing temperature. Tang et al. whereas this does not happen for the 2D peak. (a) G and (b) 2D peaks as a function of uniaxial strain. Note that the doubly degenerate G peak splits into two subbands G+ and G−. The spectra are measured with incident light polarized along the strain direction. are indicated on the right side of the spectra (61). The red line is a curve fit to the experimental data (63). ranging from 0 to 0. Blue shifts of all the Raman bands were observed after annealing. collecting the scattered light with no analyzer. The strains.

(62). the calculation in Mohiuddin et al. (61) than Zhen et al. 97). (2) The factual strain in graphene is less than the value of calculation.7 cm−1/% and −27. and ∂ω2D /∂ε ∼ −64 cm−1/%. Figure 11 was plotted with the linear fit and yield ∂ωG+ /∂ε ∼ −10. (61).8 cm−1/%) and −64 cm−1/% are abstracted in Mohiuddin et al.8% (far higher than 0. There are at least two reasons that can lead to the small result (∂ωG /∂ε and ∂ω2D /∂ε) in Zhen et al. (62). −14. ∂ωG− /∂ε ∼ −31. The slopes of the fitting lines are also indicated (61).7 cm−1/%. These big differences cannot be attributed to inaccuracy of the apparatus. (62) is the Gruneisen parameter of CNTs (85). We are more in accord with Mohiuddin et al. although the strain reached 0. (61) and Zhen et al. (62): (1) The graphene is not single but multilayer. The next one is about the value of ∂ωG /∂ε and ∂ω2D /∂ε. This may be why the G band did not split even though the strain reached 0. because strain is more effectively applied on a thinner graphene sheet. . 61). Moreover. (62). Secondly. such as nanotubes (96.8 cm−1/%. Positions of the (a) G+ and G− and (b) 2D peaks as a function of applied uniaxial strain. the resulting ∂ωG /∂ε is smaller than the real value. (61) is performed with a more accurate value of Gruneisen parameter r (1. The value of ε is calculated directly from the change of PET (substrate) instead of directly from the change of graphene. (62).78% in Zhen et al. Firstly.8 cm−1/% are from Zhen et al. (62).24) used in Zhen et al. The first one is about splitting. G band splitting is a common phenomenon of carbon nanomaterial under strain. whereas −31.5% in Mohiuddin et al.8 ± 0.2 ± 0.Raman Spectroscopic Characterization of Graphene 381 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 11. two sets of results are in accordance with each theoretical calculation. There are two different conclusions between Mohiuddin et al. The lines are linear fit to the data.7 cm−1/% (−10. If the strain did not sufficiently load on graphene.99) on the basis of Grimvall (98). whereas the value of r (1. which does not occur in Zhen et al.

Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 2D Band of Graphene Shape Evolution of 2D Band with Varied Number of Graphene Layers The 2D peak in Raman spectra of graphene is another useful tool to identify the number of graphene layers. 2D peaks for an increasing number of graphene layers along with HOPG as a bulk reference (64).382 B. Although the integrated intensity of the 2D line stays almost constant. This model explains the origin of the 2D line in the following way (see Figure 14a): an electron is vertically excited from point A in the π band to point B in the π ∗ band by absorbing a photon.and (b) double-layer graphene (collected at spots A and B. see (b) (64). at high resolution. The excited electron is inelastically scattered to point C by emission of a phonon with wave vector q. Evolution of the 2D peak width with increased layer count of graphene or. Tang et al. its splitting into some Lorentzian components (see Figure 13) can be explained in the framework of the double-resonant Raman model (52. Raman spectra of (a) single. 64. it narrows to a single peak at a lower wave number as a single-layer graphene. . The prominent difference in the 2D peak between monolayer and bilayer graphene is shown in Figure 12 according to Graf and Molitor (64). Figure 12. Inelastic backscattering to the vicinity of point A by emission another phonon with wave Figure 13. 99).

Electronic band structure: (a) single-layer graphene. the splitting value obtained from first-principles calculation is only half as large as that of experimental result (19 cm-1). (b) double-layer graphene.8/10. However. In the case of double layer graphene.1 1.Raman Spectroscopic Characterization of Graphene 383 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 14.0 .6/1. and (c) bulk graphite (64). However.6 2(v2 − v1 ) (cm−1) 19.398.393.9/1.393. the outer two peaks (corresponding to the phonons qo and q3 ) have very low weight which is contradicted with the calculated result.4/19.400.395.395. the π and π ∗ bands split into two bands each and give rise to four differently possible excitations (1-4 in Figure 14b).6 1. The phonon frequencies v1 and v2 are corresponding to the wave vectors q1 and q2 by calculation (100). The values of v1 .0/1.6 1. The corresponding electron-phonon coupling matrix elements for the phonons qo ∼q4 are almost equal in theoretical calculation. v2 .2/1.1 v2 (cm−1) 1. and 2(v2 . This discrepancy is related to the fact that the double-resonant Raman model Table 1 Frequencies of the optical phonons involved in the double-resonant Raman model (64) v1 (cm−1) Bulk Double layer Single layer 1.402.v1 ) corresponding to bulk graphite/double layer graphene/single layer graphene are given in Table 1 (64).0 8. which is in line with experimental data (see Figure 13: 2D band decomposes into four peaks). then electron-hole recombination and emission a photon whose energy is less than the incident photon.403. The evolution of the electronic band structure of the monolayer graphene/double-layer graphene/bulk graphite is shown in Figure 13.400. vector q.

Ferrari et al.5 cm−1. the double-resonant Raman model can qualitatively explain the fourfold splitting of the 2D line in the bilayer graphene. but the amount of the splitting and the relative heights of the peaks are not properly described. Note that the dynamic effects are neglected in the model because phonons of the 2D peak are far away from the Kohn anomalies at the K point. (71). 102) or (2) the splitting of the electronic bands (103). which is in line with the experimental data (see Figure 13). . So far. respectively. After calculation (104). q1 and q2 represent the possible process of 2D mode. Calculations are in qualitative agreement with experiments. the observed four components of the 2D band could due to two reasons: (1) the splitting of the phonon branches (101. Position of the 2D peak (Pos(2D)) as a function of doping. 73). the Fermi-level shifts on the phonon frequencies within a density functional theory (DFT) framework. A theoretical model of the Fermi surface shift due to varied concentrations of electrons in a graphene system was given in Das et al. much smaller than the experimental result. (52) explained the phenomenon of splitting of the 2D band of bilayer graphene for the first time. whereas the excess defect has a contraction effect. Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 15. In the bilayer case. The reason for the peak shift of the 2D band with doping can be considered as follows: (1) the equilibrium lattice parameter is modified with a consequent stiffening/softening of the phonons (105) and (2) due to the onset of dynamic effects beyond the Born-Oppenheimer approximation that modify the phonon dispersions close to the Kohn anomalies (70. And the splitting between them is lager than double layer graphene. Positions of the 2D band of theoretical and experimental results are shown in Figure 15. The dependence of the position of the 2D peak on doping can be investigated by calculation. Tang et al.384 B. Peak Shifts of the 2D Band as a Function of Doping Level and Type Frequency shift of the 2D peak takes place when graphene was doped with electron or hole. the π and π ∗ bands split into continued bands. 70). The solid line is adiabatic DFT calculation (71). Unlike the unique blue shift of the G band with both electron and hole doping (65. For the bulk graphite. the splitting of the phonon branch is less than 1. based on ab initio calculations also predicts a value for the dispersion of the 2D line with incident laser energy that amounts only to about half of the experimentally observed value of 99 cm-1/eV (64). The excess charge leads to an expansion of the crystal lattice. So the splitting is attributed to electronic band effects. the 2D peak upshifts with hole doping and red shifts with electron doping (67. 71).

(46). Figure 16. which was been identified as a highly doped and disordered region. as well as for the defective tip of the sample (gray open triangles) (65). Spatial maps for the same sample as in Figure 2 but presenting results for the Raman spectra of the 2D mode: (a) the mode frequency. shows the highest 2D-mode frequency and is associated with increased and scattered values of the line width. although the general tendency of the 2D band under electron doping condition is the red shift. the initial slight blue shift with low-density electron doping (lower than 1.Raman Spectroscopic Characterization of Graphene 385 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 More attention should focus on the right part of Figure 15. and (c) the ratio of the integrated intensity of 2D mode to that of the G mode. an incorrect conclusion that the 2D line stiffens for both electron and hole doping was made. the resulting wider 2D band may partly be due to the phonon confinement effect.5 and 633 nm laser is shown in Figure 17 (67). Correlation between position (2D band) and position (G band) under hole doping with 514. (b) the line width (FWHM). because the concentration of doping is small (±6 × 1012 cm−2). The scale of the vertical and horizontal axes shows that the frequency of 2D peak is more sensitive to hole doping than the G peak. whereas the FWHM becomes narrow in the suspended portion. which indicates that this change may not be due to doping only (64). ω2D . Panel b shows that the 2D peak exhibits a greater width on the supported portion of the graphene (about +5 cm−1) and a significant upshift in frequency (about +10 cm−1) compared to the response of the free-standing graphene.5 × 1013 cm−2) may lead to contrary conclusion. (d) Correlation between ω2D and 2D for the suspended (red open circles) and lower supported (blue open squares) regions. which is in line with Calizo et al. . In Stampfer et al. (60) and Mohiuddin et al. 2D . From the (a) and (b) panels we can see that the frequency of the 2D band is lower in the suspended portion (the area between white lines) than in the supported portion. (61). The tip of the sample (most narrow portion). The Raman mapping of the 2D band with and without hole doping is shown in Figure 16. As far as we know. I 2D /I G . The overall stiffening of the 2D mode in the supported region indicates that the graphene is hole doped (with low concentration 8 × 1012 cm−2) after being deposited on the SiO2 -coated Si substrate (64). This is the first time that the 2D band line width showed a significant change after doping.

x2D is almost three to four times greater than xG .687 2.066 Peak at 0 K (cm−1) 2. At the same time. which has been recognized as the most striking feature to distinguish single layer from a few-layer graphene. The reason for the red shift was discussed in the previous section (60). the peak position of the G and 2Ds band can serve as a powerful tool to identify the type and quantity of doping. at least for significant (>5 × 1011 cm−2) carrier concentration (65).034 −0. Position of 2D as a function of the position of G at 514 and 633 nm (67). (2) from the previous section: ω2D = ω2D0 + χ T (2) where x represents the 2D mode temperature coefficient.687 Temperature range (K) 83–373 113–373 . In brief. Figure 18 shows the position of the 2D band of monolayer and bilayer graphene when temperature varies from 113 to 373 K. and ω2D0 is the frequency of the 2D band when the temperature T is extrapolated to 0 K. 106) also studied the temperature dependence of the 2D peak of graphene. the peak width of the 2D line.386 B. which indicates that the position of the 2D band is more sensitive than the G band under varied temperature. Temperature Dependence of the 2D Band Calizo et al. (60. Use Eq. Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 17. The calculated values of the temperature coefficients x2D and zero temperature frequencies x2D0 for the 2D peak from the curves of monolayer and bilayer graphene are summarized in Table 2 (106). Table 2 Temperature coefficients for the 2D peaks in single-layer and bilayer graphene (106) Material Single-layer graphene Bilayer graphene cm−1 (K) −0. is insensitive to doping. Tang et al. It is easy to see in these curves that the 2D band red shifts with the increased temperature.

The red shift can be understood by considering the elongation of the C C bonds. The right-side image of Figure 19a shows the positions of the 2D bands of unstrained.78% strained. and relaxed graphene.8 cm−1/% for monolayer graphene and −29 ± 1.18%.61%. The scale of these images is from 2. which weakens the bonds and lowers the vibrational frequency. The frequency . The 2D frequency is plotted as a function of strain and shown as two lines with a slope of −27.8 ± 0. (a5) 0.78%.35%.710 cm−1 and darker color represents lower frequency. Raman curves of 2D peak frequency at 113 and 373 K for (a) single layer graphene and (b) bilayer graphene (106). which we discussed above (86. and (a6) relaxed. strained. (a3) 0. respectively. Figure 19b shows the 2D frequencies of unstrained.650 to 2. The resulting curves indicate that the position of the 2D band can recover after the strain relaxation. 0. It is obvious that with the increased strain. which can be used to quantify the strain coefficient.1 cm−1/% for three-layer graphene. the color becomes increasingly darker. The high strain sensitivity of graphene makes it a potential material as an ultrasensitive strain sensor. (63). The evolution of the 2D band of graphene with different layers (one to four layers) under biaxial strain was also studied by Zhen et al. Relationship between the 2D Band with Uniaxial Strain and Biaxial Strain in Graphene Figure 19a presents the 2D frequency of Raman mapping of graphene under various conditions: (a1) unstrained. The calculation and theory of the correlation between strain with peak shift were shown in the previous section. suggesting that a red shift of the 2D band occurs over the strained sample. The linear dependence of the frequency of the 2D band with strain can be expected by phonon deformation potentials.Raman Spectroscopic Characterization of Graphene 387 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 18. 87). (a4) 0. (a2) strained 0. and relaxed graphene.

particularly on the condition of low charged impurity concentration. Compared with the G band (15 cm−1). Integrated Intensity Ratio of 2D Band to G Band I2D /IG In some earlier papers (53. the uniaxial strain is different from the biaxial strain.78% (a5) strained. 0. of the 2D band blue shift changes with increasing annealing temperature and up to 25 cm−1 after annealing at 500◦ C. However. (a) Two-dimensional frequency Raman images of unstrained (a1). and relaxed (a6) graphene. the blue shift is greater in the 2D band. the integrated intensity ratio I2D /IG was suggested to be used to estimate the number of graphene layers.8 cm−1/% for single-layer graphene and 21. 54). The Raman spectra on the right-hand side are taken from the 2D band SLG of a1.388 B. (b) The analyzed 2D band frequency of single. 0.710 cm−1. It is worth noting that although both uniaxial strain and biaxial strain lead to a peak shift of the G (2D) band. I2D /IG is more sensitive to the presence of charged impurity than the blue shift of the G band. a5. I2D /IG can be used to determine the density of charged impurity in graphene. 0. (76). similar to the peak shift of the G and 2D bands. and 0. The slope is 27. On the other hand. Tang et al. Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 19. The green square/circle is the frequencies of relaxed graphene.9 cm−1/% for three-layer graphene (62). from the highlighted area of inset figures. and a6. which suggests that the 2D band is more sensitive under biaxial stress.18% (a2).61% (a4).650 to 2. in studies reported by Poncharal and Ayari (45) and Calizo et al. . The blue lines are the curve fit to the data. The result is plotted in Figure 9c and it can be interpreted by the strong compressive stress on graphene due to the substrate (63). The scale bar of all the images is 2.35% (a3).(black squares) and three-layer (red circles) graphene under different uniaxial strain. which indicates that this parameter is not a good criterion to determine the number of graphene layers. it was concluded that the variation of I2D /IG in a single layer graphene deposited on the SiO2 coated Si substrate far exceeds that assigned to the increase of number of graphene layers. The former would affect the electronic properties of graphene much more significantly as it breaks the equivalence of sublattice of graphene.

The bright area with 2D width of 57 cm−1 is three-layer graphene. Graphene samples were prepared by micromechanical cleavage and then deposited on the fabricated substrate (59). (a) Optical image of a graphene sheet on a patterned substrate covering a hole. Single-layer graphene can be distinguished from three-layer graphene in Figure 20b from the FWHM of the 2D band as discussed previously.Raman Spectroscopic Characterization of Graphene 389 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Zhen and Ting (59) employed Raman spectroscopy to study the probing charged impurities concentration in suspended graphene. For different samples the similar I2D /IG ratio occurred in panels g–i. respectively. First of all. following the deep reactive-ion etching. The integrated intensity difference of the G band between NSG with SG is a result of the interference enhancement effect. The diameter of the holes wa from 3 to 8 µm. A strange phenomenon can be found: the intensity of the G band from supported graphene (NSG) is stronger than suspended gaphene (SG).9 for NSG. In order to obtain a suspended graphene sample. The I2D /IG ratios of SG are much higher than those of NSG.7 for SG to 3. Panels c and d show the Raman mapping of the G and 2D bands. The dark strip with a 2D bandwidth of 30 cm−1 is SLG. In order to rule out the influence from strain. (f) Raman imaging of the I2D /IG ratio. The scale bars in Raman images are 2 µm (59). 10-µm-thick photoresist was spin-coated on SiO2 /Si substrate (the thickness of the SiO2 was 285 nm). Photolithography was used to pattern holes into the photoresist. The absence of an obvious D band in both the suspended and the supported portion means that the samples were high quality and exclude disorder induce the change of I2D /IG . whereas the intensity of the 2D band from NSG is weaker than NG instead. respectively. some other potential reasons need to be excluded. which we will discuss below (107). (g–i) Raman images of I2D /IG ratio of three more samples. (e) Raman spectra of SG and NSG taken from the red and blue dots in panel d. the G band frequencies from different pieces of suspended graphene and supported graphene were recorded by Zhen and Ting (59) Figure 20. a process for fabricating the substrate is needed. . respectively. Figure 20a shows the optical image of graphene where the diameter of the hole on the substrate is 8 µm. Panels c and d are the Raman imaging of G and 2D band intensity. Panel f is constructed using the I2D /IG ratio. The next step was to removal the photoresist. First of all. and the ratio changes obviously from 8. (b) Raman imaging using the 2D bandwidth. whereas the difference between the 2D band arises from doping.

Figure 21.51.0 ± 0.6 29. whereas the ratio of the 2D band has a larger range.6 ± 1.2 ± 1.7 1.5.8 1. we know that the frequency of the G band is sensitive to strain.9 29.4 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 and are shown in Table 3. But in Table 3 the G frequency of supported single graphene has the same value (within an experimental error of ∼1 cm−1). . The 2D bandwidths of SG and NSG are also presented (59) Samples 1 2 3 4 5 SG 1.8 SG 28. According to the previous discussion.7 27.0 26.4 1.582.3 NSG 31.579. The ratio of the G band is almost a constant around 0.6 1.8 ± 1. This indicates that the difference in intensity of the G band between them is only due to different interference and multiple reflection conditions.8 35.581.9 ± 0.8 31. the intensity ratio of the G band between suspended and supported graphene is ∼0.7 31.6 ± 0.2 1. and the shift coefficient reaches 10–20 cm−1/%.580.6 ± 1. though there must be other factors that contribute to such a discrepancy of the 2D band.1 ± 1.1 ± 1.7 ± 1.6 ± 2.6 ± 1.7 to 1.580. The integrated intensity ratio (G and 2D bands) of SG and NSG are shown in Figure 21.4 ± 0.9 1.3 1.5 ± 1.3 1. Table 3 The G band frequencies of SG and NSG from five different samples.1 28.581. Tang et al. The G and 2D band integrated intensity ratio of suspended and nonsuspended graphene (59).390 B.7 ± 1.4 ± 1. from 0.2 NSG 1.8 ± 0.1 ± 0.4.579.2 ± 0. Under the interference enhancement model (59).580.578.577. 109). which suggests that the strain in suspended graphene can be ignored (108. Now consider the influence of intensity of the 2D band from charged impurities.5 ± 1.

. 110): M≈v s0. E2 are the energies of these states and 2r is the inverse lifetime of the electron or hole due to collisions or scattering. v is the Fermi velocity.s2 i |H e−em |s0 s0 |H e−ph |s1 s1 |H e−ph |s2 s2 |H e−em |f (Ei − E0 + 2iγ )(Ei − E1 + 2iγ )(Ei − E2 + 2iγ ) ∧ ∧ ∧ ∧ (12) Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 where i| and | f are the initial and final states of the process. which we have mentioned above (57). 112).. it is easy to see that the intensity of 2D band of supported graphene will decrease as a result of the charged impurities from the SiO2 substrate. Ei and E0 . and S2 are the intermediate states where an electron-hole pair is created. The solid line is a guide for the eye. M is the mass of the carbon atom. ωin and ωK are the frequencies of the incident laser and the 2D phonon at around the K point. The G and 2D band integrated intensity ratio of SLG with different CI concentration: blue and red squares for NSG and SG. . and the charged impurity concentration in SG is estimated to be 1010 to 1011 cm−2 (111. respectively. the integrated intensity of G band is insensitive to the doping condition. The higher the ratio. Compared with the blue shift (approximately 1012 cm−2 to 1 cm−1) of the G band. .Raman Spectroscopic Characterization of Graphene 391 The matrix element of the electron scattering in graphene can be represented as (57. S0 . . a is the lattice constant of graphene. The squares in Figure 22 show the I2D /IG ratios of tens of single-layer graphene (SG and NSG) at different charged impurity concentrations. On the other hand. The charged impurity concentration in NSG is estimated by the blue shift of G band (42).s1. the relation between the G band blue shift and CI concentration is also presented: black and purple triangles represent NSG and SG. For comparison. The intensity of the 2D band can be written as: I2D 2 2 (e c)2 v 2 ωin 9FK = 2 2 48π c γ MωK v 2 2 √ 27a 2 4 2 (13) Here. where 2r is the electron or whole inelastic scattering rate as mentioned above. So I2D is proportional to 1/r2. and FK is the coupling constant. According to Eq. the value of I2D /IG is more sensitive even at low doping concentration. S1 . the lower the concentration of charged impurity in graphene. respectively (59). The relation between doping level and I2D /IG is presented in Figure 22. (12). The relation between the blue shift of G the band and doping level is also Figure 22. respectively.

is related to double resonance Raman scattering process. It is well known that the D band. (a) Optical image of a typical MG sheet and the angles between edges. Two premises must be satisfied to active D band: (1) q must from K point to K point. scattering (120. Raman spectroscopy is a fast and nondestructive method to determine the edge chirality. 113–116). the second condition is satisfied automatically. 121). in other words. The D mode will not appear by a perfect zigzag edge because the D band requires scattering between two nonequivalent cones. Contrarily. (2) Both phonon and edge must back-scatter with electrons. it is crucial to distinguish two edge types (armchair and zigzag) of graphene and GNR. The resulting angles are shown in Figure 23. Two adjacent edges have different chirality when the angle between them is 30◦ . 90◦ . It is worth noting that the excitation laser must invariable when directly comparing the I2D /IG ratio. Raman spectroscopy is a good tool to identify the zigzag Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 23. Therefore.392 B. (118) found that a typical graphene sheet has an angle of n × 30◦ between two adjacent edges. because that this value is affected by the excitation laser energy.The optical and magnetic properties of GNR are strongly dependent on quantum confinement effect and definite edge chirality (29. 150◦ . TO phonons around the K-point of the Brillouin-zone. Yu et al. both edges have the same chirality when the angle is 60◦ and120◦ . A detailed description was given by Casiraghi et al. (b) The statistical results of the included angle of adjacent edges. (119). where q. (c) Illustration of the relationship between angles and the chiralities of the adjacent edges (118). . have received intense attention (1. Tang et al. As defect scattering. The blue shift of the G band is too small to distinguish the experimental error when the concentration is low (<1012 cm−2). Edge Chirality of Graphene One-dimensional graphene nanoribbon (GNR). presented in the Figure 22 for comparison. The wave vector of a phonon must twice that of an electron with opposite direction. 117). where n is an integer. stands for phonon frequency. which can be produced by traditional lithography technique from graphene sheet.

Figure 25. The value of ID /IG depends on position of the laser spot. The evolution of the D band of a fixed edge with varied polarization direction is shown in Figure 24a.Raman Spectroscopic Characterization of Graphene 393 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 24. The Imin is not zero. Note that ID /IG does not go to zero for perpendicular polarization (119). which means that the edge of graphene is not ideally smooth but both of armchair and zigzag segment (118. which indicates that the edge can be mixed and disordered at least on the laser spot scale. (B) ID /IG as a function of θ in . and armchair edges. (A) Raman spectra of one edge measured for different incident polarization at 633 nm. Figure 24b and Figure 25 show ID /IG as a function of θ in . simply. . Based on the curves. 2. but it is too early to say that a high ID represents armchair edge or a low ID stands for zigzag edge for the following reasons: 1. and up to maximum intensity when the angle is 0◦ . 119). It is wrong to say that high ID /IG represents armchair edge. ID /IG as a function of θ in measured on two edges forming an angle of 90◦ (119). The minimum intensity appears when the angle between laser polarization and graphene edge is 90◦ . polarization dependence must be considered when identifying the average edge orientation. The intensity of the D band is strongly dependent on the polarization of incidence laser because of the backscattering condition (119).

Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 26. This can make Raman spectroscopy a useful . (a) Raman image constructed by the intensity of the G band with the expected arrangement in blue. The resulting polarized Raman images are shown in Figure 26. For the 60◦ and 90◦ included angles. A weak D band observed in curve a of panel d suggests that a small portion of carbon atoms is in armchair arrangement in edge 2. respectively.6 for different edges chirality. while the value is greater than 1. which indicates that they have different chirality. For 30◦ and 90◦ included angles. Panels b and c show the intensity of the D band with horizontal laser polarization and vertical laser polarization. respectively (118). Spectra a and b are recorded at edges 1 and 2. (118). Both curves hardly show any D band because of the polarization effect. respectively. According to the previous discussion. The angle between edge 1 and 2 is 30◦ . which indicates a good quality of sample. (e) The solid and dotted lines represent the D band intensity profile (solid/dash) plotted along the solid line on (b) and the dashed line on (c). the adjacent edges have different intensities of the D band. Note that the armchair or zigzag arrangement mentioned here for edges 1 and 2 is a result of the majority of carbon atoms along the edge being arranged in one kind of chirality (either armchair or zigzag). and the angle between edge 2 and 3 is 120◦ .7 times of that of edge 2. Tang et al. whereas edge 2 and 3 have the same chirality. Curves c and d in panel e are recorded at edges 1 and 2. Further experimental results are shown in Figure 27 (118). Spectra c and d were also collected from edges 1 and 2. edge 1 and 2 have different chirality. Edge 1 can be identified as an armchair edge and edge 2 as zigzag edge. two adjacent edges show similar D band intensity. Panel a shows uniform intensity of the G band over the whole graphene. respectively. with vertical laser polarization. which is similar to that of graphite edges. with a vertical laser polarization. The D band intensity of edge 1 is 1. The ID intensity ratio of adjacent edges with same edges chirality is around 1. (b) and (c) are images constructed by the D band intensity with horizontal and vertical polarization. which means that they have the same atomic arrangements at the edge. (d) Raman spectra taken from edge 1 (spectrum a) and edge 2 (spectrum b) with horizontal laser polarization. respectively. A single-layer graphene with three edges was used by Yu et al. The results prove that these adjacent edges have different chirality as expected and the D band shows strong polarization dependence. The defect-induced D band at the edges was found to be strongly polarization dependent.394 B. respectively.

a simple and fast method to identify superior and inferior carrier mobility of EG relying on Raman spectroscopy was proposed by Joshua and Maxwell (122). Raman Spectroscopy of Epitaxial Graphene Except for micromechanical exfoliation from HOPG. Raman imaging results from edges with angles (a) 30◦ . It is well known that varied strain appearing in graphene drives from the difference of lattice parameter of the SiC substrate and graphene. Recently. The quality of epitaxial graphene (EG) is not as good as mechanical exfoliation graphene. The laser polarization is indicated by the green arrows. Furthermore. After growth. Epitaxial graphene films EGSi and EGC were grown on the SiC(0001) (Si-face) and SiC(0001) (Cface). both the substrate not atomically smooth and the process of sample cooling induces the anisotropic strain.Raman Spectroscopic Characterization of Graphene 395 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 27. Contrarily. The uniformity of the 2D band around the entire EGSi corresponds to high electronic mobility. such as Hall effect. (b) 60◦ (zigzag). The thickness. In order to promote this relatively simple synthesis method. which is important for the study of graphene and graphene-based devices. The . thus Raman curve shows a similar 2D band to bulk graphite (generally fit with two Lorentzian functions) (see Figure 28). whereas the carrier mobility depends strongly on the stacking order for the EGC . and (d) 60◦ (armchair). (c) 90◦ . doping. epitaxial growth from bulk SiC substrate is another method to fabricate graphene (122). as well as the electron mobility. and stack between graphene layers play important roles to determine the EG’s characteristics. The 2D peak of the Raman curve can be fitted with a single Lorentzian function of single-layer EGsi and evolves to four Lorentzian functions to bilayer EGsi. a transition layer can be seen between the SiC substrate with EGsi through TEM. which always requires further destructive process. Measuring the electronic feature of EG is a complicated process. The superimposed frameworks are guides for the eye indicating the edge chirality (118). some means are used to improve the quality of EG. way to determine the crystallographic orientation of the graphene. strain. EGC always several layers thick. respectively. The 2D band can be used to identify the monolayer and multilayer graphene not only for MG but for EG.

Graphene layer stacking is correlated with 2D Raman peak width for EG on SiC(0001) (d) (122).690–2. on the other hand. Figure 29d: AFM figure) can Figure 29. and Hall mobility (e) data are used to identify the influence of graphene uniformity on carrier mobility of EGSi (122). (c). Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 28. The 2D Raman peak of epitaxial graphene is used to rapidly identify (a) monolayer and bilayer graphene on SiC(0001) and layer stacking on SiC(0001) . The value of mobility reaches 1000 cm2/vs when the Raman topography map is uniform over half of the device and over 2000 cm2/vs when EGSi is uniform over the entire device. low mobility EGSi has a significant variation in the 2D band position (2.760 cm−1) (see Figure 29). atomic force microscopy (b). . which is identified in Raman topography by a uniformly distributed 2D peak position. Raman topography (a). EGSi with high carrier mobility exhibits a uniform 2D signature. Film thickness confirmed via TEM (b). High mobility EGSi exhibits uniform strain with minimal thickness variation. (c). Tang et al. (d).396 B. Low mobility graphene (Figure 29c: Raman topography.

represented by a narrow 2D band fitted by a single Lorentzian component in Raman spectroscopy. however. Note that the correlation between FWHM and mobility only exists for the device with a uniform EGC film (122). The Raman signal of graphene (single or few layers) should be very weak or even . the layer stacking of EGC . Arrows in Figures 29a and 29b indicate the location of the SiC terrace step edge. the 2D peak splits to two Lorenzian components and follows a low mobility. whereas wider 2D peaks indicate the AB stacking (Figure 28d. EGC exhibits better carrier mobility compared with EGSi . On the other hand. the mobility decreases strongly from a high value of 18. a narrow 2D peak fitted with a single Lorentzian function (Figure 28d. The model of layer stacking of EGC is complex in two ways: (1) AB stacked (Bernal stacked) (2) grows with a high density of rotational faults where adjacent sheets are rotated relative to each other (123). As rotationally faulted EGC .100 to 50 cm2/vs (122). the rotationally faulted EGC means a high mobility graphene. Luckily. top). the length scale of the Raman topography uniformity is significantly smaller than the device length scale. be mono. The Raman topography domain size and Hall mobility from EGSi Hall crosses indicates that the uniformity of strain of the graphene film significantly influences carrier mobility (Figure 29e). The single peak of the 2D band indicates that the AB stacked does not appear in the EGC and shows high carrier mobility.Raman Spectroscopic Characterization of Graphene 397 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 30. middle and bottom). Interference Enhancement Model of Raman Signal of Graphene Laser penetration depth of Raman spectroscopy is around 50–100 nm (514–488 nm laser). As the Lorentzian components of the 2D band increase. The Raman 2D peak width is strongly from a high value of 18. In order to fabricate high-quality EGSi . which can be extracted from the 2D band. the uniform stress and thickness are needed. When the rotationally faulted EGc and AB stacked appear in the EGc at the same time.or bilayer.100 to 50 cm2/Vs (122). But it is difficult to determine the thickness of EGc through the 2D band of Raman spectroscopy as mentioned. So the 2D band can be used as a quick way to identify the superior and inferior carrier mobility of EGSi and EGC . strongly affects the carrier mobility.

When the thickness of SiO2 is satisfied. Schematic of Si/Ag/Al2 O3 with graphene on it (127). Calculation result of enhancement factor E as a function of thickness of SiO2 (124). at and substrate to enhancement the intensity of Raman signal is choosing n1 Figure 32. The thickness of the SiO2 capping layer is a key factor to determine the intensity of the Raman signal of graphene. According to Fresnel’s equations (125. in other words. multi-reflection of Raman light must be taken into account to explain the signal of single-layer graphene which is comparable to bulk graphite (124). Except the interference of laser. The enhancement factor E is a function of the thickness of SiO2 . invisible. 3 4 on. the resulting interference between all transmitted optical paths in graphene films (124). Tang et al. and so calculation (124). so the interference of the laser enhances the Raman signal of graphene. the intensity of the signal depends on the electronic field distribution. where E represents the ratio of Raman signal intensity of single-layer graphene with SiO2 a capping layer to without this capping layer. but the experimental result always contradicts this view.398 B. . Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 31. Micromechanical cleavage graphene is always deposited on the Si wafer with 300 nm SiO2 capping layer. 126). nSiO2 × dSiO2 /λ ≈ 1/4. The general selection of the capping layer n2 n3 . Figure 31 shows the result of the . the maximum enhancement can be reached.

substrate and thickness of capping layer. the maximum intensity is reached (Figure 33). In order to find the optimized substrate structure. Duhee. was adopted (shown in Figure 32). combining surface enhanced and interference enhanced Raman signals. and so on.000 by optimizing the substrate structure. the thickness of Ag and Al2 O3 are various to get the strongest Raman signal. A question may be raised: Does the interference effect influence the relative intensity ratio of the 2D band to the G band of graphene? It is important to answer this question because the intensity ratio of the 2D band to the G band is always used as a criterion to determine the doping level. The interference enhanced Raman scattering (IERS) is mentioned above. . (127) proposed a co-enhanced Raman scattering technique to characterize graphene. answered this question. all graphene samples must be deposited on Si substrate with the same thickness of the SiO2 capping layer. and d2 represent refractive indices of graphene. Y. Figure 34 shows Raman spectroscopy of graphene on kinds of substrates. 3/4. capping layer. or choosing n1 n2 n3 with n2 × d2 /λ = 1/4. Enhancement effect comparison of graphene on different substrates. n3 . as mentioned above (59). When I2D /IG is used to determine doping level. n2 . (b) Raman spectra of graphene on an Si substrate with 72-nm-thick Al2 O3 layer and different thicknesses of Ag film (127). respectively. Surface enhanced Raman scattering (SERS) is another technique that combines modern laser spectroscopy with the exciting optical properties of metallic nanostructures and dramatically enhances Raman signals (128–131). the intrinsic intensity ratio of I2D /IG can be got after factor out the interference effect (66). The resulting Raman signal intensity of monolayer graphene is great enhanced on the optimized substrate (Si/50 nm Ag/72 nm Al2 O3 and Si/50 nm Au/72 nm Al2 O3 ) compared with the corresponding IERS substrate Figure 33. An enhancement ratio reaches ∼1. and so on (n1 .Raman Spectroscopic Characterization of Graphene 399 Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 the same time n2 × d2 /λ = 1/4. When thickness of Ag and Al2 O3 are 50 nm and 72 nm. respectively). et al. Si/Ag/Al2 O3 . Recently. If the intensity ratio data from samples on different thickness of SiO2 . A typical active metal/oxide layer substrate. Li et al. 3/4. (a) Raman spectra of graphene on an Si substrate with 50-nm-thick Ag film and different thickness of Al2 O3 layers.

400 B. and intensity of the G and 2D bands. a review of Raman spectroscopy and imaging of graphene has been presented. The intensity of the D band of polarized Raman spectroscopy is a useful criterion to determine the edge chirality of graphene. All of the experimental results are provided in Table 4. whereas the shape of 2D band evolves into four components of bilayer graphene from a single peak of monolayer graphene. The G band will blue shift and become narrow with both electron and hole doping. The intensity of the G peak increases in an almost linear relation with increased layers. (Si/72 nm Al2 O3 ). whereas the 2D band will blue shift with hole doping and red shift with electron doping. which can be interpreted according to the elongation of the C C bond due to thermal expansion or anharmonic coupling of phonon modes. both edges have the same chirality when the included angle is 60◦ and 120◦ . The number of graphene layers can be determined quickly by using Raman spectroscopy. The doping level. Under compressed strain (both uniaxial and biaxial strain) the blue shift of the G and 2D bands can be found. This technique makes Raman spectroscopy a strong tool to probe tiny structural changes and surface structure changes of graphene. which are closely related to frequency. The value of I2D /IG decreases with increased doping level and is sensitive to doping even under low doping level. 150◦ . The value of ID /IG depends on the position of . Two adjacent edges have different chirality when the angle between them is 30◦ . Raman spectra of graphene deposited on kinds of substrates (127). Frequencies of bot the G band and 2D band will red shift with increasing temperature. fine structural information of graphene can be probed. Conclusion In summary. fluctuation of temperature in graphene. Raman spectroscopy is a versatile tool to study graphene. SERS substrate (Si/50 nm Ag). Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Figure 34. strain. Contrarily. FWHM. Because of the great enhancement ratio. as well as edge chirality of graphene also can be determined through Raman curve. Tang et al. 90◦ . and an original Si substrate (without oxide layer).

64) Intensity Frequency Number of layers Narrow (65. 70) Blue shift with compressed strain (62) Blue shift with compressed strain (61.Downloaded by [Centro de Investigaciones en Optica] at 17:05 19 March 2013 Table 4 Classified experiment results G band FWHM Constant (60. 72). 76) — — — Biaxial strain 401 Splitting to some components with increased layers (52. 70. 76) Biaxial strain Blue shift with both electron and hole doping (65–67) Red shift with increasing temperature (60. becomes narrow (64) Not sensitive(60) Not sensitive Not sensitive Intensity Not sensitive (64. 69. 70) Blue shift with compressed strain (62) Blue shift with compressed strain (61. 99) Blue shift with hole doping and red shift with electron doping (71) Red shift with increasing temperature (60. 76) Not sensitive (60) Not sensitive (62) Not sensitive (61) 2D band FWHM Bigger for bilayer than single-layer (52. 71. 63) Frequency Number of layers Doping concentration Temperature dependence Uniaxial strain Decreasing with increased layers (64) Decreasing with increased electron concentration (45. 125) Decreasing with increased electron concentration (59) Constant Constant Constant I2D /IG Constant Constant Constant Red shift with increased layers (64) Doping concentration Temperature dependence Uniaxial strain Linear increasing with increased layers (64. 64) Not sensitive (46. 63) . 65) Constant (65. 64.

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