Abstract. The Raman scattering is inelastic process when photon
scatters on the molecule or a group of the molecules and changes its frequency.
The frequency shift of the photon carries the information about the oscillation
degreases of freedom of the molecule. In particular, the photon can gain or
lose energy that equal to the energy of the one phonon of the molecule. If the
molecule is placed near to the metal surface then the Raman scattering dramatically
increases. This effect is called SERS. The spectroscopy based on this effect is
applied in material sciences, nanotechnology, chemistry and even biology. In this
paper enhancement of SERS effect by the phonons of the metal substrate is
studied. Since the size and shape of the plasmonic particle is very small
(about 30 nm) at room temperature the particle is in the near liquid state and
can easily change its shape under the influence of the phonons. The periodic
shape changing causes the modulation of the interaction constant between the
molecule and the plasmon. Numerical calculations show that when the modulation
frequency is close to the oscillation frequency of the molecule, the modulation
depth of few percent leads to possibility of an enhancement of SERS signal by
the order of magnitude.
Keywords: Raman scattering, SERS, phonon, plasmon.
References
1. V. M. Shalaev, A. K. Sarychev. Nonlinear optics of
random metal-dielectric films. Physical Review B. 1998.
Vol. 57. No. 20. pp. 13265.
2. B. Pettinger et al. Tip-enhanced Raman
spectroscopy: near-fields acting on a few molecules. Annual review of
physical chemistry. 2012. Vol. 63. pp. 379-399.
3. B. Sharma et al. High-performance SERS substrates:
Advances and challenges. MRS bulletin. 2013. Vol. 38.
No. 8. pp. 615-624.
4. S. Jiang et al. Distinguishing adjacent molecules
on a surface using plasmon-enhanced Raman scattering. Nature nanotechnology. 2015.
Vol. 10. No. 10. pp. 865-869.
5. X. M. Qian, S. M. Nie. Single-molecule and
single-nanoparticle SERS: from fundamental mechanisms to biomedical
application. Chemical Society Reviews. 2008. Vol. 37.
No. 5. pp.
912-920.
6. M. Fleischmann, P. J. Hendra, A. J. McQuillan.
Raman spectra of pyridine adsorbed at a silver electrod. Chemical Physics
Letters. 1974. Vol. 26. No. 2. pp. 163-166.
7. D. L. Jeanmaire, R. P. Van Duyne. Surface Raman
spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines
adsorbed on the anodized silver electrode. Journal of Electroanalytical
Chemistry and Interfacial Electrochemistry. 1977. Vol. 84. No. 1. pp. 1-20.
8. J. M. Atkin, M. B. Raschke. Techniques: Optical
spectroscopy goes intramolecula. Nature. 2013. Vol. 498. No. 7452.
pp.
44-45.
9. K. Kneipp et al. Single molecule detection using
surface-enhanced Raman scattering (SERS. Physical review letters. 1997.
Vol. 78. No. 9. pp. 1667.
10. Y. Luo, A. Aubry, J. B. Pendry. Electromagnetic
contribution to surface-enhanced Raman scattering from rough metal surfaces: a
transformation optics approach. Physical Review B. 2011. Vol. 83.
No. 15.
pp. 155422.
11. H. Xu et al. Electromagnetic contributions to single-molecule
sensitivity in surface-enhanced Raman scattering. Physical Review E. 2000.
Vol. 62. No. 3. pp. 4318.
12. M. Moskovits. Surface‐enhanced Raman spectroscopy: a brief
retrospective. Journal of Raman Spectroscopy. 2005. Vol. 36.
No. 6‐7. pp.
485-496.
13. C. Ciracì et al. Probing the ultimate limits of plasmonic
enhancement. Science. 2012. Vol. 337. No. 6098. pp. 1072-1074.
14. L. Tong, H. Xu, M. Käll. Nanogaps for SERS
application. Mrs
Bulletin. 2014. Vol. 39. No. 2. pp. 163-168.
15. R. C. Maher et al. Stokes/anti-Stokes anomalies under surface
enhanced Raman scattering condition. The Journal of chemical physics.
2004. Vol. 120. No. 24. pp. 11746-11753.
16. D. N. Klyshko. Correlation between the Stokes and anti-Stokes components
in inelastic scattering of light. Soviet Journal of Quantum Electronics.
1977. Vol. 7. No. 6. pp. 755.
17. C. A. Parra-Murillo et al. Stokes–anti-Stokes correlation in the
inelastic scattering of light by matter and generalization of the Bose-Einstein
population function. Physical Review B. 2016. Vol. 93.
No. 12. pp.
125141.
18. A. Jorio et al. Optical-phonon resonances with saddle-point
excitons in twisted-bilayer graphene. Nano letters. 2014.
Vol. 14. No. 10. pp. 5687-5692.
19. E. C. Le Ru, P. G. Etchegoin. Vibrational pumping and heating under
SERS conditions: fact or myth? Faraday discussions. 2006.
Vol. 132. pp.
63-75.
20. P. Roelli et al. Molecular cavity optomechanics as a theory of
plasmon-enhanced Raman scattering. Nature nanotechnology. 2016.
Vol. 11. No. 2. pp. 164-169.
21. M. K. Schmidt et al. Quantum mechanical description of Raman
scattering from molecules in plasmonic cavities. ACS nano. 2016.
Vol. 10. No. 6. pp. 6291-6298.
22. T. J. Kippenberg, K. J. Vahala. Cavity optomechanics: back-action
at the mesoscale. Science. 2008. Vol. 321. No. 5893. pp. 1172-1176.
23. M. Aspelmeyer, T. J. Kippenberg, F. Marquardt. Cavity optomechanics.
Reviews of Modern Physics. 2014. Vol. 86. No. 4. pp. 1391.
24. R. Esteban, J. Aizpurua, G. W. Bryant. Strong coupling of single
emitters interacting with phononic infrared antennae. New Journal of Physics. 2014.
Vol. 16. No. 1. pp. 013052.
25. E. Waks, D. Sridharan. Cavity QED treatment of interactions between
a metal nanoparticle and a dipole emitter. Physical Review A. 2010.
Vol.
82. No. 4. pp. 043845.
26. E. J. Blackie, E. C. L. Ru, P. G. Etchegoin. Single-molecule
surface-enhanced Raman spectroscopy of nonresonant molecules. Journal of the
American Chemical Society. 2009. Vol. 131. No. 40. pp. 14466-14472.
27. D. Bougeard, K. S. Smirnov. Calculation of off‐resonance Raman
scattering intensities with parametric models. Journal of Raman spectroscopy. 2009.
Vol. 40. No. 12. pp. 1704-1719.
28. M. Aspelmeyer, T. J. Kippenberg, F. Marquardt. Cavity
Optomechanics: Nano-and Micromechanical Resonators Interacting with Light,
Quantum Science and Technology. Springer, 2014.
29. M. K. Schmidt et al. Quantum mechanical description of Raman
scattering from molecules in plasmonic cavities. ACS nano. 2016.
Vol. 10. No. 6. pp. 6291-6298.
30. F. Benz et al. Single-molecule optomechanics in “picocavities”.
Science. 2016. Vol. 354. No. 6313. pp. 726-729.
31. W. Zhu, K. B. Crozier. Quantum mechanical limit to plasmonic
enhancement as observed by surface-enhanced Raman scattering. Nature
communications. 2014. Vol. 5. pp. 5228.
32. M. K. Schmidt et al. Linking classical and molecular optomechanics
descriptions of SERS. Faraday Discussions. 2017.
33. E. A. Pozzi et al. Operational Regimes in Picosecond and
Femtosecond Pulse-Excited Ultrahigh Vacuum SERS. The journal of physical
chemistry letters. 2016. Vol. 7. No. 15. pp. 2971-2976.