Abstract
Nano-Raman spectra differ from far-field Raman spectra. The differences result from a strong electric field gradient near the metal tip, propagation, and polarization, but the dependence upon probe-sample distance can only be explained by the inclusion of surface plasmons and the near-field, non-propagating terms of the dipole emission. A simple model based upon these components accurately describes distance-dependent data measured with a near-field scanning optical microscope. Our essentially near-field model will apply generally to Raman spectroscopy near a nanoscale conductor.
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References
Mansuripur M, Li L. What in the world are surface plasmons. Optics Photonics News. 1997;8:50–5. May.
Milner RG, Richards D. The role of tip plasmons in near-field Raman microscopy. J Microscopy. 2001;202(Pt 1):66–71.
Moody RL, Vo-Dinh T, Fletcher WH. Investigation of experimental parameters for surface-enhanced Raman scattering (SERS) using silver-coated microsphere substrates. Appl Spectrosc. 1987;41(6):966–70.
Baker GA, Moore DS. Source, “Progress in plasmonic engineering of surface-enhanced Raman-scattering substrates toward ultra-trace analysis”. Anal Bioanal. Chem 2005;382(8):1751–70.
Xu H, Wang X-H, Persson MP, Xu HQ, Kall M, Johansson P. Unified treatment of fluorescence and Raman scattering processes near metal surfaces. Phys Rev Lett. 2004;93(24):243002–1–4.
Ayars E, Hallen HD, Jahncke CL. Electric field gradient effects in Raman spectroscopy. Phys Rev Lett. 2000;85(19):4180–3.
Hallen HD, Jahncke CL. The electric field at the apex of a near-field probe: implications for nanoRaman spectroscopy. J Raman Spectroscopy. 2003;34(9):655–62.
Jahncke CL, Ayars EJ, Hallen HD. The effects of probe boundary conditions and propagation on nano-Raman spectroscopy. J Microsc. 2003;210(Pt 3):252–4.
Jackson JB, Westcott SL, Hirsch LR, West JL, Halas NJ. Controlling the surface enhanced Raman effect via the nanoshell geometry. Appl Phys Lett. 2003;82(2):257–9.
Poitras CA, Lipson M, Du H, Hahn MA, Krauss TD. Photoluminesce enhancement of colloidal quantum dots embedded in a monolithic cavity. Appl Phys Lett. 2003;82(23):4032–4.
Bethe HA. Theory of diffraction by small holes. Phys Rev. 1944;66:163–82.
Bouwkamp CJ. On Bethe’s theory of diffraction by small holes. Philips Res Rep. 1950;5:321.
Betzig E, Chichester RJ. Single molecules observed by near-field scanning optical microscopy. Science 1993;262:1422–5.
McDaniel EB, McClain SC, Hsu JWP. Nanometer scale polarimetry studies using a near-field scanning optical microscope. Appl Opt. 1998;37:84–92.
Ambrose WP, Goodwin PM, Martin JC, Keller RA. Alterations of single molecule fluorescence lifetimes in near-field optical microscopy. Science 1994;265:364–7.
Bian RX, Dunn RC, Xie XS, Leung PT. Single molecule emission characteristics in near-field microscopy. Phys Rev Lett. 1995;75(26):4772–5.
Ford GW, Weber WH. Electromagnetic interactions of molecules with metal surfaces. Phys Reports. 1984;113(4):195–287.
Hellen EH, Axelrod D. Fluorescence emission at dielectric and metal-film interfaces. J Opt Soc Am B. 1987;4(3):337–50.
Lukosz W, Kunz RE. Light emission by magnetic and electric dipoles close to plane interface I Total radiated power. J Opt Soc Am. 1977;67(12):1607.
Weber WH, Eagan CF. Energy transfer from en excited dye molecule to the surface plasmon in an adjacent metal. Opt Lett. 1979;4(8):236–8.
Homola J, Yee SS, Gauglitz G. Surface plasmon resonance sensors: review. Sens Actuators, B. 1999;54:3–15.
Otto A. Z Phys. 1968;216:398.
Ayars E, Hallen HD. Surface enhancement in near-field Raman spectroscopy. Appl Phys Lett. 2000;76(26):3911–3.
Hoffmann P, Dutoit B, Salathé R-P. Comparison of mechanically drawn and protection layer chemically etched optical fiber tips. Ultramicroscopy 1995;61:165–70.
Betzig E, Finn PL, Weiner JS. Combined shear force and near-field scanning optical microscopy. Appl Phys Lett. 1992;60:2484–6.
Toledo-Crow R, Yang PC, Chen Y, Vaez-Iravani M. Near-field differential scanning optical microscope with atomic force regulation. Appl Phys Lett. 1992;60:2957.
Karrai K, Grober RD. Piezoelectric tip-sample distance control for near-field optical microscopes. Appl Phys Lett. 1995;66:1842.
Jahncke CL, Hallen HD. A versatile, stable scanning proximal probe microscope. Rev Scient Instr. 1997;68:1759.
Heald M, Marion J. Classical electromagnetic radiation. 3rd ed. Pacific Grove: Brooks/Cole; 1995.
Guenther RD. Modern optics. New York: Wiley; 1990.
Yakobson BI, Paesler MA. Tip optics for illumination NSOM: extended zone approach. Ultramicroscopy 1995;57:204.
Acknowledgement
This material is based upon work supported by the National Science Foundation under Grant Nos. DMR-9975543 and DMII-0210058. We acknowledge technical discussions with Catherine Jahncke and Eric Ayars.
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Hallen, H.D. Nano-Raman Spectroscopy: Surface Plasmon Emission, Field Gradients, and Fundamentally Near Field Propagation Effects. Nanobiotechnol 3, 197–202 (2007). https://doi.org/10.1007/s12030-008-9013-1
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DOI: https://doi.org/10.1007/s12030-008-9013-1