Raman spectroscopy as a versatile tool for studying the properties of graphene
Source abstract
Abstract
Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all sp(2)-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Graphene research and applications · Diamond and Carbon-based Materials Research · Carbon Nanotubes in Composites
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (100+)
Show source-provided references
1. Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).10.1126/science.1102896 ↗
2. Geim, A. K. & Novoselov, K. S. The rise of graphene. Nature Mater. 6, 183–191 (2007).10.1038/nmat1849 ↗
3. Charlier, J. C., Eklund, P. C., Zhu, J. & Ferrari, A. C. Electron and phonon properties of graphene: Their relationship with carbon nanotubes. Topics Appl. Phys. 111, 673–709 (2008).10.1007/978-3-540-72865-8_21 ↗
4. Bonaccorso, F., Sun, Z., Hasan, T. & Ferrari, A. C. Graphene photonics and optoelectronics. Nature Photon. 4, 611–622 (2010).10.1038/nphoton.2010.186 ↗
5. Bonaccorso, F., Lombardo, A., Hasan, T., Sun, Z., Colombo, L. & Ferrari, A. C. Production and processing of graphene and 2d crystals. Materials Today 15, 564–589 (December, 2012).10.1016/S1369-7021(13)70014-2 ↗
6. Lin, Y. M. et al. 100-GHz transistors from wafer-scale epitaxial graphene. Science 327, 662 (2010).10.1126/science.1184289 ↗
7. Torrisi, F. et al. Inkjet-printed graphene electronics. ACS Nano 6, 2992–3006 (2012).10.1021/nn2044609 ↗
8. Sun, Z. et al. Graphene mode-locked ultrafast laser. ACS Nano 4, 803–810 (2009).10.1021/nn901703e ↗
9. Landsberg, G. S. & Mandelshtam, L. I. Eine neue Erscheinung bei der Lichtzerstreuung in Krystallen. Naturwissenshaften 16, 557 (1928).10.1007/BF01506807 ↗
10. Raman, C. V. & Krishnan, K. S. A new type of secondary radiation. Nature 121, 501–502 (1928).10.1038/121501c0 ↗
11. Tuinstra, F. & Koenig, J. L. Raman spectrum of graphite. J. Chem. Phys. 53, 1126–1130 (1970).10.1063/1.1674108 ↗
12. Ferrari, A. C. et al. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97, 187401 (2006).10.1103/PhysRevLett.97.187401 ↗
13. Ferrari, A. C. & Robertson, J. (eds) Raman spectroscopy in carbons: from nanotubes to diamond, Theme Issue, Phil. Trans. R. Soc. A 362, 2267–2565 (2004).
14. Ferrari, A. C. Raman spectroscopy of graphene and graphite: Disorder, electron-phonon coupling, doping and nonadiabatic effects. Solid State Comm. 143, 47–57 (2007).10.1016/j.ssc.2007.03.052 ↗
15. Ferrari, A. C. & Robertson, J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 61, 14095–14107 (2000).10.1103/PhysRevB.61.14095 ↗
16. Ferrari, A. C. & Robertson, J. Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon. Phys. Rev. B 64, 075414 (2001).10.1103/PhysRevB.64.075414 ↗
17. Casiraghi, C. et al. Rayleigh imaging of graphene and graphene layers. Nano. Lett. 7, 2711–2717 (2007).10.1021/nl071168m ↗
18. Blake, P. et al. Making graphene visible. Appl. Phys. Lett. 91, 063124 (2007).10.1063/1.2768624 ↗
19. Kalbac, M. et al. The influence of strong electron and hole doping on the Raman intensity of chemical vapor-deposition graphene. ACS Nano 10, 6055–6063 (2010).10.1021/nn1010914 ↗
20. Chen, C. F. et al. Controlling inelastic light scattering quantum pathways in graphene. Nature 471, 617–620 (2011).10.1038/nature09866 ↗
21. Casiraghi, C. et al. Raman fingerprint of charged impurities in graphene. Appl. Phys. Lett. 91, 233108 (2007).10.1063/1.2818692 ↗
22. Das, A. et al. Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. Nature Nanotech. 3, 210–215 (2008).10.1038/nnano.2008.67 ↗
23. Zhao, W. J., Tan, P. H., Liu, J. & Ferrari, A. C. Intercalation of few-layer graphite flakes with FeCl3: Raman determination of Fermi level, layer by layer decoupling, and stability. J. Am. Chem. Soc. 133, 5941–5946 (2011).10.1021/ja110939a ↗
24. Das, A. et al. Phonon renormalisation in doped bilayer graphene. Phys. Rev. B 79, 155417 (2009).10.1103/PhysRevB.79.155417 ↗
25. Pisana, S. et al. Breakdown of the adiabatic Born-Oppenheimer approximation in graphene. Nature Mater. 6, 198–201 (2007).10.1038/nmat1846 ↗
26. Yan, J. et al. Electric field effect tuning of electron-phonon coupling in graphene. Phys. Rev. Lett. 98, 166802 (2007).10.1103/PhysRevLett.98.166802 ↗
27. Yan, J. et al. Observation of anomalous phonon softening in bilayer graphene. Phys. Rev. Lett. 101, 136804 (2008).10.1103/PhysRevLett.101.136804 ↗
28. Basko, D. M. Boundary problems for Dirac electrons and edge-assisted Raman scattering in graphene. Phys. Rev. B 79, 205428 (2009).10.1103/PhysRevB.79.205428 ↗
29. You, Y., Ni, Z., Yu, T. & Shen, Z. Edge chirality determination of graphene by Raman spectroscopy. Appl. Phys. Lett. 93, 163112 (2008).10.1063/1.3005599 ↗
30. Gupta, A. K., Russin, T. J., Gutiérrez, H. R. & Eklund, P. C. Probing graphene edges via Raman scattering. ACS Nano 3, 45–52 (2009).10.1021/nn8003636 ↗
31. Casiraghi, C. et al. Raman spectroscopy of graphene edges. Nano Lett. 9, 1433–1441 (2009).10.1021/nl8032697 ↗
32. Cong, C., Yu, T. & Wang, H. Raman study on the G mode of graphene for determination of edge orientation. ACS Nano 4, 3175–3180 (2010).10.1021/nn100705n ↗
33. Ryu, S., Maultzsch, J., Han, M. Y., Kim, P. & Brus, L. E., Raman spectroscopy of lithographically patterned graphene nanoribbons. ACS Nano 5, 4123–4130 (2011).10.1021/nn200799y ↗
34. Huang, M., Hugen, Y., Heinz, T. F. & Hone, J. Probing strain induced electronic structure change in graphene by Raman spectroscopy. Nano Lett. 10, 4074–4079 (2010).10.1021/nl102123c ↗
35. Mohr, M., Maultzsch, J. & Thomsen, C. Splitting of the Raman 2D band of graphene subjected to strain. Phys. Rev. B 82, 201409(R) (2010).10.1103/PhysRevB.82.201409 ↗
36. Yoon, D., Son, Y. W. & Cheong, H. Strain-dependent splitting of double resonance Raman scattering band in graphene. Phys. Rev. Lett. 106, 155502 (2011).10.1103/PhysRevLett.106.155502 ↗
37. Mohiuddin, T. M. G. et al. Uniaxial strain in graphene by Raman spectroscopy: G peak splitting, Gruneisen parameters, and sample orientation. Phys. Rev. B 79, 205433 (2009).10.1103/PhysRevB.79.205433 ↗
38. Ni, Z. H. et al. Uniaxial strain on graphene: Raman spectroscopy study and band-gap opening. ACS Nano 2, 2301–2305 (2008).10.1021/nn800459e ↗
39. Proctor J. E. et al. Graphene under hydrostatic pressure. Phys. Rev. B 80, 073408 (2009).10.1103/PhysRevB.80.073408 ↗
40. Huang, M. et al. Phonon softening and crystallographic orientation of strained graphene studied by Raman spectroscopy. Proc. Natl Acad. Sci. USA 106, 7304–7308 (2009).10.1073/pnas.0811754106 ↗
41. Venezuela, P., Lazzeri, M. & Mauri, F. Theory of double-resonant Raman spectra in graphene: Intensity and line shape of defect-induced and two-phonon bands. Phys. Rev. B 84, 035433 (2011).10.1103/PhysRevB.84.035433 ↗
42. Lucchese, M. M. et al. Quantifying ion-induced defects and Raman relaxation length in graphene. Carbon 48, 1592–1597 (2010).10.1016/j.carbon.2009.12.057 ↗
43. Cançado, L. G. et al. Quantifying defects in graphene via Raman spectroscopy at different excitation energies. Nano Lett. 11, 3190–3196 (2011).10.1021/nl201432g ↗
44. Gokus, T. et al. Making graphene luminescent by oxygen plasma treatment. ACS Nano 3, 3963–3968 (2009).10.1021/nn9012753 ↗
45. Elias, D. C. et al. Control of graphene's properties by reversible hydrogenation: Evidence for graphane. Science 323, 610–613 (2009).10.1126/science.1167130 ↗
46. Nair, R. R. et al. Fluorographene: mechanically strong and thermally stable two-dimensional wide-gap semiconductor. Small 6, 2877–2884 (2010).10.1002/smll.201001555 ↗
47. Ni, Z. et al. On resonant scatterers as a factor limiting carrier mobility in graphene. Nano Lett. 10, 3868–3872 (2010).10.1021/nl101399r ↗
48. Chen, J. H., Cullen, W. G., Jang, C., Fuhrer, M. S. & Williams, E. D. Defect scattering in graphene. Phys. Rev. Lett. 102, 236805 (2008).10.1103/PhysRevLett.102.236805 ↗
49. Balandin, A. A. et al. Superior thermal conductivity of single-layer graphene. Nano Lett. 8, 902–907 (2008).10.1021/nl0731872 ↗
50. Bonini, N., Lazzeri, N., Marzari, N. & Mauri, F. Phonon anharmonicities in graphite and graphene. Phys. Rev. Lett. 99, 176802 (2007).10.1103/PhysRevLett.99.176802 ↗
51. Basko, D. M. & Aleiner, I. L. Interplay of Coulomb and electron–phonon interactions in graphene. Phys. Rev. B 77, 041409(R) (2008).10.1103/PhysRevB.77.041409 ↗
52. Basko, D. M. Calculation of the Raman G peak intensity in monolayer graphene: role of Ward identities. New J. Phys. 11, 095011 (2009).10.1088/1367-2630/11/9/095011 ↗
53. Basko, D. M. Theory of resonant multiphonon Raman scattering in graphene. Phys. Rev. B 78, 125418 (2008).10.1103/PhysRevB.78.125418 ↗
54. Grüneis, A. et al. Phonon surface mapping of graphite: Disentangling quasi-degenerate phonon dispersions. Phys. Rev. B 80, 085423 (2009).10.1103/PhysRevB.80.085423 ↗
55. May, P. et al. Signature of the two-dimensional phonon dispersion in graphene probed by double-resonant Raman scattering. Phys. Rev. B 87, 075402 (2013).10.1103/PhysRevB.87.075402 ↗
56. Lazzeri, M. et al. Impact of the electron-electron correlation on phonon dispersion: Failure of LDA and GGA DFT functionals in graphene and graphite. Phys. Rev. B 78, 081406(R) (2008).10.1103/PhysRevB.78.081406 ↗
57. Lazzeri, M & Mauri, F. Nonadiabatic Kohn anomaly in a doped graphene monolayer. Phys. Rev. Lett. 97, 266407 (2006).10.1103/PhysRevLett.97.266407 ↗
58. Faugeras, C. et al. Tuning the electron-phonon coupling in multilayer graphene with magnetic fields. Phys. Rev. Lett. 103, 186803 (2009).10.1103/PhysRevLett.103.186803 ↗
59. Kossacki, P. et al. Electronic excitations and electron-phonon coupling in bulk graphite through Raman scattering in high magnetic fields. Phys. Rev. B 84, 235138, (2011).10.1103/PhysRevB.84.235138 ↗
60. Faugeras, C. et al. Magneto-Raman scattering of graphene on graphite: Electronic excitations and their coupling to optical phonons. Phys. Rev. Lett. 107, 036807 (2011).10.1103/PhysRevLett.107.036807 ↗
61. Kim, Y. et al. Magnetophonon resonance in graphite: High-field Raman measurements and electron-phonon coupling contributions. Phys. Rev. B 121403(R) (2012).10.1103/PhysRevB.85.121403 ↗
62. Kim, Y. et al. Filling-factor-dependent magnetophonon resonance with circularly polarized phonons in graphene revealed by high-field magneto-Raman spectroscopy. Preprint at http://arxiv.org/abs/1211.6094 (2012).
63. Faugeras, C. et al. Effect of a magnetic field on the two-phonon Raman scattering in graphene. Phys. Rev. B 81, 155436 (2010).10.1103/PhysRevB.81.155436 ↗
64. Faugeras, C. et al. Probing the band structure of quadri-layer graphene with magneto-phonon resonance. New J. Phys. 14, 095007 (2012).10.1088/1367-2630/14/9/095007 ↗
65. Yan J. et al. Observation of magneto-phonon resonance of Dirac fermions in graphite. Phys. Rev. Lett. 105, 227401 (2010).10.1103/PhysRevLett.105.227401 ↗
66. Goerbig, M. O. et al. Filling-factor-dependent magnetophonon resonance in graphene. Phys. Rev. Lett. 99, 087402 (2007).10.1103/PhysRevLett.99.087402 ↗
67. Ando, T. Magnetic oscillation of optical phonon in graphene. J. Phys. Soc. Jpn 76, 024712 (2007).10.1143/JPSJ.76.024712 ↗
68. Tan, P. H. et al. The shear mode of multilayer graphene. Nature Mater. 11, 294–300 (2012).10.1038/nmat3245 ↗
69. Lui, C. et al. Observation of layer-breathing mode vibrations in few-layer graphene through combination Raman scattering. Nano Lett. 12, 5539–5544 (2012).10.1021/nl302450s ↗
70. Lui, C. H. & Heinz. T. F. Measurement of layer breathing mode vibrations in few-layer graphene. Phys. Rev. B 87, 121404 (2013).10.1103/PhysRevB.87.121404 ↗
71. Sato, K. et al. Raman spectra of out-of-plane phonons in bilayer graphene. Phys. Rev. B 84, 035419 (2011).10.1103/PhysRevB.84.035419 ↗
72. Herziger, F., May, F. & Maultzsch, J. Layer number determination in graphene using out-of-plane vibrations. Phys. Rev. B 85, 235447 (2012).10.1103/PhysRevB.85.235447 ↗
73. Maultzsch, J., Reich, S. & Thomsen, C. Double-resonant Raman scattering in graphite: Interference effects, selection rules, and phonon dispersion. Phys. Rev. B 70, 155403 (2004).10.1103/PhysRevB.70.155403 ↗
74. Yoon, D. et al. Interference effect on Raman spectrum of graphene on SiO2/Si. Phys. Rev. B 80, 125422 (2009).10.1103/PhysRevB.80.125422 ↗
75. Wang, Y. Y. et al. Interference enhancement of Raman signal of graphene. Appl. Phys. Lett. 92, 043121 (2008).10.1063/1.2838745 ↗
76. Schedin, F. et al. Surface enhanced Raman spectroscopy of graphene. ACS Nano 4, 5617–5626 (2010).10.1021/nn1010842 ↗
77. Malard, L. M., Pimenta, M. A., Dresselhaus, G. & Dresselhaus, M. S. Raman spectroscopy in graphene. Phys. Rep. 473, 51–87 (2009).10.1016/j.physrep.2009.02.003 ↗
78. Jorio, A., Dresselhaus, M. S., Saito, R. & Dresselhaus, G. Raman Spectroscopy in Graphene Related Systems (Wiley, 2011).10.1002/9783527632695 ↗
79. Saito, R., Hofmann, M., Dresselhaus, G., Jorio, A. & Dresselhaus, M. S. Raman spectroscopy of graphene and carbon nanotubes. Adv. Phys. 60, 413–550 (2011).10.1080/00018732.2011.582251 ↗
80. Piscanec, S., Lazzeri, M., Mauri, F., Ferrari, A. C. & Robertson, J. Kohn anomalies and electron-phonon interactions in graphite. Phys. Rev. Lett. 93, 185503 (2004).10.1103/PhysRevLett.93.185503 ↗
81. Nemanich, R. J., Lucovsky, G. & Solin, S. A. Infrared active optical vibrations of graphite. Solid State Comm. 23, 117–120 (1977).10.1016/0038-1098(77)90663-9 ↗
82. Reich, S. & Thomsen, C. Raman spectroscopy of graphite. Phil. Trans. R. Soc. A 362, 2271–2288 (2004).10.1098/rsta.2004.1454 ↗
83. Mani, K. K. & Ramani, R. Lattice dynamics of graphite. Phys. Stat. Sol. B 61, 659–668 (1974).10.1002/pssb.2220610232 ↗
84. Maultzsch, J., Reich, S., Thomsen, C., Requardt, H. & Ordejón, P. Phonon dispersion in graphite. Phys. Rev. Lett. 92, 075501 (2004).10.1103/PhysRevLett.92.075501 ↗
85. Thomsen, C. & Reich, S. Double resonant Raman scattering in graphite. Phys. Rev. Lett. 85, 5214–5217 (2000).10.1103/PhysRevLett.85.5214 ↗
86. Baranov, A. V. et al. Interpretation of certain characteristics in Raman spectra of graphite and glassy carbon. Opt. Spectroscopy 62, 612–616 (1987).
87. Pocsik, I., Hundhausen, M., Koos, M & Ley, L. Origin of the D peak in the Raman spectrum of microcrystalline graphite. J. Non-Cryst. Solids 227–230, 1083–1086 (1998).10.1016/S0022-3093(98)00349-4 ↗
88. Basko, D. M., Piscanec, S. & Ferrari, A. C. Electron-electron interactions and doping dependence of the two-phonon Raman intensity in graphene. Phys. Rev. B 80, 165413 (2009).10.1103/PhysRevB.80.165413 ↗
89. Nemanich, R. J. &. Solin, S. A. First- and second-order Raman scattering from finite-size crystals of graphite. Phys. Rev. B 20, 392–401 (1979).10.1103/PhysRevB.20.392 ↗
90. Tan, P. H., Deng, Y. M. & Zhao, Q. Temperature-dependent Raman spectra and anomalous Raman phenomenon of highly oriented pyrolytic graphite. Phys. Rev. B 58, 5435–5439 (1998).10.1103/PhysRevB.58.5435 ↗
91. Tan, P. H. et al. Probing the phonon dispersions of graphite from the double-resonance process of Stokes and anti-Stokes Raman scatterings in multiwalled carbon nanotubes. Phys. Rev. B 66, 245410 (2002).10.1103/PhysRevB.66.245410 ↗
92. Tan, P. H., Hu, C. Y., Dong, J., Shen, W. C. & Zhang, B. F. Polarization properties, high-order Raman spectra, and frequency asymmetry between Stokes and anti-Stokes scattering of Raman modes in a graphite whisker. Phys Rev B 64, 214301 (2001).10.1103/PhysRevB.64.214301 ↗
93. Kawashima, Y. & Katagiri, G. Fundamentals, overtones, and combinations in the Raman spectrum of graphite. Phys. Rev. B 52, 10053–10059 (1995).10.1103/PhysRevB.52.10053 ↗
94. Nemanich, R. J., Lucovsky, G. & Solin, S. A. in Proc. Int. Conf. on Lattice Dynamics (ed. Balkanski, M.) 619–621 (Flammarion, 1975).
95. Zhang, X. et al. Raman spectroscopy of shear and layer breathing modes in Multilayer MoS2 . Phys. Rev. B 87, 115413 (2013).10.1103/PhysRevB.87.115413 ↗
96. Latil, S., Meunier, V. & Henrard, L. Massless fermions in multilayer raphitic systems with misoriented layers: Ab initio calculations and experimental fingerprints. Phys. Rev. B 76, 201402(R) (2007).10.1103/PhysRevB.76.201402 ↗
97. Wallace, P. R. The band theory of graphite. Phys. Rev. 71, 622–634 (1948).10.1103/PhysRev.71.622 ↗
98. Kashuba, A. & Fal'ko, V. I. Signature of electronic excitations in the Raman spectrum of graphene. Phys. Rev. B 80, 241404 (2009).10.1103/PhysRevB.80.241404 ↗
99. Kashuba, O. & Fal'ko, V. I., Role of electronic excitations in magneto-Raman spectra of graphene. New J. Phys. 14, 105016 (2012).10.1088/1367-2630/14/10/105016 ↗
100. Wang, F. et al. Multiphonon Raman scattering from individual single-walled carbon nanotubes. Phys. Rev. Lett. 98, 047402 (2007).10.1103/PhysRevLett.98.047402 ↗