Resolving the electromagnetic mechanism of surface-enhanced light scattering at single hot spots

Light scattering at nanoparticles and molecules can be dramatically enhanced in the 'hot spots' of optical antennas, where the incident light is highly concentrated. Although this effect is widely applied in surface-enhanced optical sensing, spectroscopy and microscopy, the underlying electromagnetic mechanism of the signal enhancement is challenging to trace experimentally. Here we study elastically scattered light from an individual object located in the well-defined hot spot of single antennas, as a new approach to resolve the role of the antenna in the scattering process. We provide experimental evidence that the intensity elastically scattered off the object scales with the fourth power of the local field enhancement provided by the antenna, and that the underlying electromagnetic mechanism is identical to the one commonly accepted in surface-enhanced Raman scattering. We also measure the phase shift of the scattered light, which provides a novel and unambiguous fingerprint of surface-enhanced light scattering.

[1]  D. L. Jeanmaire,et al.  Surface raman spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode , 1977 .

[2]  B. Grinstein,et al.  Polarization effects in B→D∗eve , 1987 .

[3]  R. V. Van Duyne,et al.  Probing the structure of single-molecule surface-enhanced Raman scattering hot spots. , 2008, Journal of the American Chemical Society.

[4]  Hongxing Xu,et al.  Multiple-particle nanoantennas for enormous enhancement and polarization control of light emission. , 2009, ACS nano.

[5]  Annemarie Pucci,et al.  Resonant plasmonic and vibrational coupling in a tailored nanoantenna for infrared detection. , 2008, Physical review letters.

[6]  R. Dasari,et al.  Single Molecule Detection Using Surface-Enhanced Raman Scattering (SERS) , 1997 .

[7]  Peter R. Griffiths,et al.  Handbook of Vibrational Spectroscopy: Chalmers Vibrat 5V Set , 2001 .

[8]  D. Lynch,et al.  Handbook of Optical Constants of Solids , 1985 .

[9]  R. V. Van Duyne,et al.  Wavelength-scanned surface-enhanced Raman excitation spectroscopy. , 2005, The journal of physical chemistry. B.

[10]  M. Moskovits Surface-Enhanced Raman Spectroscopy: a Brief Perspective , 2006 .

[11]  J. Aizpurua,et al.  Phase-resolved mapping of the near-field vector and polarization state in nanoscale antenna gaps. , 2010, Nano letters.

[12]  J. Chalmers,et al.  Handbook of vibrational spectroscopy , 2002 .

[13]  Louise Poissant Part I , 1996, Leonardo.

[14]  Hongxing Xu,et al.  Spectroscopy of Single Hemoglobin Molecules by Surface Enhanced Raman Scattering , 1999 .

[15]  Lukas Novotny,et al.  Principles of Nano-Optics by Lukas Novotny , 2006 .

[16]  Anika Kinkhabwala,et al.  Exploring the chemical enhancement for surface-enhanced Raman scattering with Au bowtie nanoantennas. , 2006, The Journal of chemical physics.

[17]  L. Novotný,et al.  Visualizing the optical interaction tensor of a gold nanoparticle pair. , 2010, Nano letters.

[18]  Javier Aizpurua,et al.  Mapping the plasmon resonances of metallic nanoantennas. , 2008, Nano letters.

[19]  Lukas Novotny,et al.  Effective wavelength scaling for optical antennas. , 2007, Physical review letters.

[20]  H. Metiu Surface enhanced spectroscopy , 1984 .

[21]  Jean Aubard,et al.  Experimental Verification of the SERS Electromagnetic Model beyond the |E|4 Approximation: Polarization Effects , 2008 .

[22]  Vahid Sandoghdar,et al.  Enhancement of single-molecule fluorescence using a gold nanoparticle as an optical nanoantenna. , 2006, Physical review letters.

[23]  M. Allegrini,et al.  Re-radiation enhancement in polarized surface-enhanced resonant Raman scattering of randomly oriented molecules on self-organized gold nanowires. , 2011, ACS nano.

[24]  Masatoshi Osawa,et al.  Dynamic Processes in Electrochemical Reactions Studied by Surface-Enhanced Infrared Absorption Spectroscopy (SEIRAS) , 1997 .

[25]  P G Etchegoin,et al.  Enhancement factor distribution around a single surface-enhanced Raman scattering hot spot and its relation to single molecule detection. , 2006, The Journal of chemical physics.

[26]  Pablo G. Etchegoin,et al.  Rigorous justification of the |E|4 enhancement factor in Surface Enhanced Raman Spectroscopy☆ , 2006 .

[27]  Carsten Rockstuhl,et al.  Fabry-Pérot resonances in one-dimensional plasmonic nanostructures. , 2009, Nano letters.

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

[29]  Steven R. Emory,et al.  Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering , 1997, Science.

[30]  Rainer Hillenbrand,et al.  Pseudoheterodyne detection for background-free near-field spectroscopy , 2006 .

[31]  Javier Aizpurua,et al.  Controlling the near-field oscillations of loaded plasmonic nanoantennas , 2009 .

[32]  Ken-ichi Yoshida,et al.  Quantitative evaluation of electromagnetic enhancement in surface-enhanced resonance Raman scattering from plasmonic properties and morphologies of individual Ag nanostructures , 2010 .

[33]  Martin Moskovits,et al.  Surface-Enhanced Raman Spectroscopy and Nanogeometry: The Plasmonic Origin of SERS , 2007 .

[34]  P. Biagioni,et al.  Near-field polarization shaping by a near-resonant plasmonic cross antenna , 2009 .

[35]  R. Pollard,et al.  Wavelength Dependence of Raman Enhancement from Gold Nanorod Arrays: Quantitative Experiment and Modeling of a Hot Spot Dominated System , 2010 .

[36]  L. Novotný,et al.  Enhancement and quenching of single-molecule fluorescence. , 2006, Physical review letters.

[37]  Unified treatment of fluorescence and raman scattering processes near metal surfaces. , 2004, Physical review letters.

[38]  Glenn P. Goodrich,et al.  Profiling the near field of a plasmonic nanoparticle with Raman-based molecular rulers. , 2006, Nano letters.

[39]  M. Fleischmann,et al.  Raman spectra of pyridine adsorbed at a silver electrode , 1974 .

[40]  Semion K. Saikin,et al.  Separation of Electromagnetic and Chemical Contributions to Surface-Enhanced Raman Spectra on Nanoengineered Plasmonic Substrates , 2010, The Journal of Physical Chemistry Letters.

[41]  Xu,et al.  Electromagnetic contributions to single-molecule sensitivity in surface-enhanced raman scattering , 2000, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.