Raman Radiation Patterns of Graphene

We report the angular distribution of the G and 2D Raman scattering from graphene on glass by detecting back focal plane patterns. The G Raman emission can be described by a superposition of two incoherent orthogonal point dipoles oriented in the graphene plane. Due to double resonant Raman scattering, the 2D emission can be represented by the sum of either three incoherent dipoles oriented 120° with respect to each other, or two orthogonal incoherent ones with a 3:1 weight ratio. Parameter-free calculations of the G and 2D intensities are in excellent agreement with the experimental radiation patterns. We show that the 2D polarization ratio and the 2D/G intensity ratio depend on the numerical aperture of the microscope objective. This is due to the depolarization of the emission and excitation light when graphene is on a dielectric substrate, as well as to tight focusing. The polarization contrast decreases substantially for increasing collection angle, due to polarization mixing caused by the air-dielectric interface. This also influences the intensity ratio I(2D)/I(G), a crucial quantity for estimating the doping in graphene. Our results are thus important for the quantitative analysis of the Raman intensities in confocal microscopy. In addition, they are relevant for understanding the influence of signal enhancing plasmonic antenna structures, which typically modify the sample’s radiation pattern.

[1]  Wei Ji,et al.  Interface Coupling in Twisted Multilayer Graphene by Resonant Raman Spectroscopy of Layer Breathing Modes. , 2015, ACS nano.

[2]  L. Novotný,et al.  Raman characterization of defects and dopants in graphene , 2015, Journal of physics. Condensed matter : an Institute of Physics journal.

[3]  M. Prato,et al.  Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. , 2015, Nanoscale.

[4]  Andrea C. Ferrari,et al.  Resonant Raman spectroscopy of twisted multilayer graphene , 2014, Nature Communications.

[5]  A. Ferrari,et al.  Doping dependence of the Raman spectrum of defected graphene. , 2014, ACS nano.

[6]  A. Jorio,et al.  Theory of spatial coherence in near-field Raman scattering , 2014, 1403.7351.

[7]  Weitao Su,et al.  Visualizing graphene edges using tip-enhanced Raman spectroscopy , 2013 .

[8]  Giorgio Volpe,et al.  Multipolar radiation of quantum emitters with nanowire optical antennas , 2013, Nature Communications.

[9]  D. Basko,et al.  Raman spectroscopy as a versatile tool for studying the properties of graphene. , 2013, Nature nanotechnology.

[10]  A. Ferrari,et al.  Production and processing of graphene and 2d crystals , 2012 .

[11]  K. Sasaki,et al.  The Origin of Raman D Band: Bonding and Antibonding Orbitals in Graphene , 2012, 1211.4915.

[12]  R. Saito,et al.  Observation of layer-breathing mode vibrations in few-layer graphene through combination Raman scattering. , 2012, Nano letters.

[13]  A. Jorio,et al.  Mechanism of near-field Raman enhancement in two-dimensional systems , 2012 .

[14]  P. Lambin,et al.  Theoretical polarization dependence of the two-phonon double-resonant Raman spectra of graphene , 2012, 1206.3827.

[15]  Alexandre Bouhelier,et al.  Launching propagating surface plasmon polaritons by a single carbon nanotube dipolar emitter. , 2012, Nano letters.

[16]  S. Sahoo,et al.  Polarized Raman scattering in monolayer, bilayer, and suspended bilayer graphene , 2011 .

[17]  Jin Sung Park,et al.  Raman spectra of out-of-plane phonons in bilayer graphene , 2011 .

[18]  Y. Wang,et al.  The shear mode of multilayer graphene. , 2011, Nature materials.

[19]  R. Saito,et al.  Observation of out-of-plane vibrations in few-layer graphene using combination and overtone Raman modes , 2011, 1204.1702.

[20]  M. Lazzeri,et al.  Theory of double-resonant Raman spectra in graphene: Intensity and line shape of defect-induced and two-phonon bands , 2011, 1103.4582.

[21]  D. Yoon,et al.  Strain-dependent splitting of the double-resonance Raman scattering band in graphene. , 2011, Physical review letters.

[22]  F. Hennrich,et al.  Enhancing and redirecting carbon nanotube photoluminescence by an optical antenna. , 2010, Optics express.

[23]  A. Ferrari,et al.  Graphene Photonics and Optoelectroncs , 2010, CLEO 2012.

[24]  D. Basko,et al.  Electron-electron interactions and doping dependence of the two-phonon Raman intensity in graphene , 2009, 0906.0975.

[25]  K. Novoselov,et al.  Raman spectroscopy of graphene edges. , 2008, Nano letters.

[26]  B. Park,et al.  Strong polarization dependence of double-resonant Raman intensities in graphene. , 2008, Nano letters.

[27]  H. R. Krishnamurthy,et al.  Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. , 2008, Nature nanotechnology.

[28]  Tim H. Taminiau,et al.  Optical antennas direct single-molecule emission , 2008 .

[29]  V. Sandoghdar,et al.  Modification of single molecule fluorescence close to a nanostructure: radiation pattern, spontaneous emission and quenching , 2007, 0710.4092.

[30]  S. Latil,et al.  Massless fermions in multilayer graphitic systems with misoriented layers: Ab initio calculations an , 2007, 0709.2315.

[31]  A. Ferrari,et al.  Raman spectroscopy of graphene and graphite: Disorder, electron phonon coupling, doping and nonadiabatic effects , 2007 .

[32]  K. Novoselov,et al.  Rayleigh imaging of graphene and graphene layers. , 2007, Nano letters.

[33]  Colin J R Sheppard,et al.  Investigation of the point spread function of surface plasmon-coupled emission microscopy. , 2007, Optics express.

[34]  K. Novoselov,et al.  Breakdown of the adiabatic Born-Oppenheimer approximation in graphene. , 2007, Nature materials.

[35]  K. Novoselov,et al.  Born-Oppenheimer Breakdown in Graphene , 2006, cond-mat/0611714.

[36]  Andre K. Geim,et al.  Raman spectrum of graphene and graphene layers. , 2006, Physical review letters.

[37]  B. Hecht,et al.  Principles of nano-optics , 2006 .

[38]  A. Jorio,et al.  Influence of the atomic structure on the Raman spectra of graphite edges. , 2004, Physical review letters.

[39]  J. Robertson,et al.  Raman spectroscopy of amorphous, nanostructured, diamond–like carbon, and nanodiamond , 2004, Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences.

[40]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[41]  J. Robertson,et al.  Kohn anomalies and electron-phonon interactions in graphite. , 2004, Physical review letters.

[42]  Lukas Novotny,et al.  Single-molecule orientations determined by direct emission pattern imaging , 2004 .

[43]  John Robertson,et al.  Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon , 2001 .

[44]  Andreas Volkmer,et al.  Vibrational Imaging with High Sensitivity via Epidetected Coherent Anti-Stokes Raman Scattering Microscopy , 2001 .

[45]  T G Brown,et al.  Longitudinal field modes probed by single molecules. , 2001, Physical review letters.

[46]  Thomsen,et al.  Double resonant raman scattering in graphite , 2000, Physical review letters.

[47]  J. Robertson,et al.  Interpretation of Raman spectra of disordered and amorphous carbon , 2000 .

[48]  Novotny,et al.  Local Excitation, Scattering, and Interference of Surface Plasmons. , 1996, Physical review letters.

[49]  T. Wilson,et al.  The axial response of confocal microscopes with high numerical aperture objective lenses , 1995 .

[50]  F. Tuinstra,et al.  Raman Spectrum of Graphite , 1970 .

[51]  Y. Wang,et al.  The shear mode of multi-layer graphene , 2011 .

[52]  A. Jorio,et al.  Mechanism of near-field Raman enhancement in one-dimensional systems. , 2009, Physical review letters.