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Controlling inelastic light scattering quantum pathways in graphene

Nature volume 471, pages 617–620 (2011)Cite this article

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Abstract

Inelastic light scattering spectroscopy has, since its first discovery1,2, been an indispensable tool in physical science for probing elementary excitations, such as phonons3, magnons4 and plasmons5 in both bulk and nanoscale materials. In the quantum mechanical picture of inelastic light scattering, incident photons first excite a set of intermediate electronic states, which then generate crystal elementary excitations and radiate energy-shifted photons6. The intermediate electronic excitations therefore have a crucial role as quantum pathways in inelastic light scattering, and this is exemplified by resonant Raman scattering6 and Raman interference7,8. The ability to control these excitation pathways can open up new opportunities to probe, manipulate and utilize inelastic light scattering. Here we achieve excitation pathway control in graphene with electrostatic doping. Our study reveals quantum interference between different Raman pathways in graphene: when some of the pathways are blocked, the one-phonon Raman intensity does not diminish, as commonly expected, but increases dramatically. This discovery sheds new light on the understanding of resonance Raman scattering in graphene. In addition, we demonstrate hot-electron luminescence9 in graphene as the Fermi energy approaches half the laser excitation energy. This hot luminescence, which is another form of inelastic light scattering, results from excited-state relaxation channels that become available only in heavily doped graphene.

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Figure 1: Controlling the optical transitions in graphene with ion-gel gating.
Figure 2: Controlling inelastic light scattering with electrostatic doping.
Figure 3: Quantum interference between graphene Raman pathways.
Figure 4: Hot luminescence in graphene.

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References

  1. Raman, C. V. A change of wave-length in light scattering. Nature 121, 619 (1928)

    Article  CAS  ADS  Google Scholar 

  2. Landsberg, G. & Mandelstam, L. Eine neue Erscheinung bei der Lichtzerstreuung in Krystallen. Naturwissenschaften 16, 557 (1928)

    Article  CAS  Google Scholar 

  3. Rao, A. M. et al. Diameter-selective Raman scattering from vibrational modes in carbon nanotubes. Science 275, 187–191 (1997)

    Article  CAS  Google Scholar 

  4. Devereaux, T. P. & Hackl, R. Inelastic light scattering from correlated electrons. Rev. Mod. Phys. 79, 175–233 (2007)

    Article  CAS  ADS  Google Scholar 

  5. Goñi, A. R. et al. One-dimensional plasmon dispersion and dispersionless intersubband excitations in GaAs quantum wires. Phys. Rev. Lett. 67, 3298–3301 (1991)

    Article  ADS  Google Scholar 

  6. Cardona, M. Light Scattering in Solids I 2nd edn (Springer, 1982)

    Google Scholar 

  7. Ralston, J. M., Wadsack, R. L. & Chang, R. K. Resonant cancelation of Raman scattering from CdS and Si. Phys. Rev. Lett. 25, 814–818. (1970)

  8. Basko, D. M. Calculation of the Raman G peak intensity in monolayer graphene: role of Ward identities. N. J. Phys. 11, 095011 (2009)

    Article  Google Scholar 

  9. Elsaesser, T., Shah, J., Rota, L. & Lugli, P. Initial thermalization of photoexcited carriers in GaAs studied by femtosecond luminescence spectroscopy. Phys. Rev. Lett. 66, 1757–1760 (1991)

    Article  CAS  ADS  Google Scholar 

  10. Novoselov, K. S. et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature 438, 197–200 (2005)

    Article  CAS  ADS  Google Scholar 

  11. Zhang, Y. B., Tan, Y. W., Stormer, H. L. & Kim, P. Experimental observation of the quantum Hall effect and Berry's phase in graphene. Nature 438, 201–204 (2005)

    Article  CAS  ADS  Google Scholar 

  12. Ferrari, A. C. et al. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97, 187401 (2006)

    Article  CAS  ADS  Google Scholar 

  13. Pimenta, M. A. et al. Studying disorder in graphite-based systems by Raman spectroscopy. Phys. Chem. Chem. Phys. 9, 1276–1291 (2007)

    Article  CAS  Google Scholar 

  14. Das, A. et al. Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. Nature Nanotechnol. 3, 210–215 (2008)

    Article  CAS  Google Scholar 

  15. Dresselhaus, M. S., Jorio, A., Hofmann, M., Dresselhaus, G. & Saito, R. Perspectives on carbon nanotubes and graphene Raman spectroscopy. Nano Lett. 10, 751–758 (2010)

    Article  CAS  ADS  Google Scholar 

  16. Pisana, S. et al. Breakdown of the adiabatic Born-Oppenheimer approximation in graphene. Nature Mater. 6, 198–201 (2007)

    Article  CAS  ADS  Google Scholar 

  17. Yan, J., Zhang, Y. B., Kim, P. & Pinczuk, A. Electric field effect tuning of electron-phonon coupling in graphene. Phys. Rev. Lett. 98, 166802 (2007)

    Article  ADS  Google Scholar 

  18. Li, Z. Q. et al. Dirac charge dynamics in graphene by infrared spectroscopy. Nature Phys. 4, 532–535 (2008)

    Article  CAS  ADS  Google Scholar 

  19. Wang, F. et al. Gate-variable optical transitions in graphene. Science 320, 206–209 (2008)

    Article  CAS  ADS  Google Scholar 

  20. Zhang, Y. et al. Direct observation of a widely tunable bandgap in bilayer graphene. Nature 459, 820–823 (2009)

    Article  CAS  ADS  Google Scholar 

  21. Cho, J. H. et al. Printable ion-gel gate dielectrics for low-voltage polymer thin-film transistors on plastic. Nature Mater. 7, 900–906 (2008)

    Article  CAS  ADS  Google Scholar 

  22. Kim, B. J. et al. High-performance flexible graphene field effect transistors with ion gel gate dielectrics. Nano Lett. 10, 3464–3466 (2010)

    Article  CAS  ADS  Google Scholar 

  23. Lui, C. H., Mak, K. F., Shan, J. & Heinz, T. F. Ultrafast photoluminescence from graphene. Preprint at 〈http://arXiv.org/abs/1006.5769〉 (2010)

  24. Stoehr, R. J., Kolesov, R., Pflaum, J. & Wrachtrup, J. Fluorescence of laser created electron-hole plasma in graphene. Preprint at 〈http://arXiv.org/abs/1006.5434〉 (2010)

  25. Dresselhaus, M. S., Dresselhaus, G., Saito, R. & Jorio, A. Raman spectroscopy of carbon nanotubes. Phys. Rep. 409, 47–99 (2005)

    Article  ADS  Google Scholar 

  26. 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)

    Article  ADS  Google Scholar 

  27. Kashuba, O. & Fal'ko, V. I. Signature of electronic excitations in the Raman spectrum of graphene. Phys. Rev. B 80, 241404(R) (2009)

    Article  ADS  Google Scholar 

  28. Ilani, S., Donev, L. A. K., Kindermann, M. & McEuen, P. L. Measurement of the quantum capacitance of interacting electrons in carbon nanotubes. Nature Phys. 2, 687–691 (2006)

    Article  CAS  ADS  Google Scholar 

  29. Wang, C. J., Shim, M. & Guyot-Sionnest, P. Electrochromic nanocrystal quantum dots. Science 291, 2390–2392 (2001)

    Article  CAS  ADS  Google Scholar 

  30. Li, X. S. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009)

    Article  CAS  ADS  Google Scholar 

Download references

Acknowledgements

This work was supported by the US Department of Energy, Laboratory Directed Research and Development Program of Lawrence Berkeley National Laboratory under contract no. DE-AC02-05CH11231 (C.-F.C. and F.W.), by the Office of Basic Energy Sciences under contract nos DE-AC02-05CH11231 (B.W.B. and R.A.S.), DE-AC03-76SF0098 (Materials Science Division) (C.G., A.Z.) and DE-AC02-05CH11231 (Advanced Light Source), and by ONR MURI award N00014-09-1-1066 (J.H., C.-H.P., S.G.L., M.F.C.). C.-F.C. also acknowledges fellowship support from the National Science Council and National Tsing Hua University, Taiwan, under awards NSC98-2811-M-007-008 and NSC98-2120-M-007-004.

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Authors and Affiliations

  1. Department of Physics, University of California at Berkeley, Berkeley, 94720, California, USA

    Chi-Fan Chen, Cheol-Hwan Park, Jason Horng, Baisong Geng, Caglar Girit, Alex Zettl, Michael F. Crommie, Steven G. Louie & Feng Wang

  2. Department of Chemical and Biomolecular Engineering, University of California at Berkeley, Berkeley, 94720, California, USA

    Bryan W. Boudouris & Rachel A. Segalman

  3. Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, 94720, California, USA

    Bryan W. Boudouris, Alex Zettl, Michael F. Crommie, Rachel A. Segalman, Steven G. Louie & Feng Wang

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  1. Chi-Fan Chen
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Contributions

F.W. designed the experiment; C.-F.C. and J.H. carried out optical measurements; B.G., C.G. and B.W.B. contributed to sample growth and fabrication; and C.-H.P., S.G.L. and F.W. performed theoretical analysis. All authors discussed the results and wrote the paper together.

Corresponding author

Correspondence to Feng Wang.

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The authors declare no competing financial interests.

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The file contains Supplementary Data and Supplementary Figures 1-3 with legends. (PDF 361 kb)

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Chen, CF., Park, CH., Boudouris, B. et al. Controlling inelastic light scattering quantum pathways in graphene. Nature 471, 617–620 (2011). https://doi.org/10.1038/nature09866

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