Spatially resolved surface enhanced Raman spectroscopy: feasibility, intensity dependence on sampling area and attomole mass sensitivity

Abstract Spatially resolved surface enhanced Raman scattering (SR SERS) from μm sized sampling areas has been observed in the electrochemical environment for the first time. Analysis of the equation for SR SERS intensity reveals that the detected signal should be area independent. This is demonstrated experimentally for the aqueous pyridine/Ag model system using 200 kW cm −2 peak laser irradiance. The mass detection limits for SR SERS are found to be on the order of 10 5 molecules or 0.17 attomoles!

[1]  G. Richmond Optical second harmonic generation as a surface probe of silver electrodes , 1984 .

[2]  and H. Metiu,et al.  THE ELECTROMAGNETIC THEORY OF SURFACE ENHANCED SPECTROSCOPY , 1984 .

[3]  R. Chang,et al.  Laser illumination effects on the surface morphology, cyclic voltammetry, and surface-enhanced raman scattering of Ag electrodes , 1982 .

[4]  R. Chang,et al.  Surface enhanced Raman scattering and second-harmonic generation from CN- complexes and SO2-4 on Ag electrodes during oxidation-reduction cycles , 1984 .

[5]  A. Nitzan,et al.  Theoretical model for enhanced photochemistry on rough surfaces , 1981 .

[6]  E. Brandt Spectroelectrochemical cell optimized for Raman spectrometry and its application to the study of pyridine adsorbed onto silver electrodes , 1985 .

[7]  Tony F. Heinz,et al.  Spectroscopy of Molecular Monolayers by Resonant Second-Harmonic Generation , 1982 .

[8]  Thomas E. Furtak,et al.  Surface-Enhanced Raman Scattering , 1982 .

[9]  Colin J. R. Sheppard,et al.  Imaging and Super-resolution in the Harmonic Microscope , 1979 .

[10]  Alexander Wokaun,et al.  Surface-Enhanced Electromagnetic Processes , 1984 .

[11]  C. Harris,et al.  Photochemistry on rough metal surfaces , 1984 .

[12]  M. Albrecht,et al.  Anomalously intense Raman spectra of pyridine at a silver electrode , 1977 .

[13]  R. V. Duyne,et al.  Surface enhanced Raman spectroscopy: A re-examination of the role of surface roughness and electrochemical anodization , 1981 .

[14]  G. Schatz Theoretical Studies of Surface Enhanced Raman Scattering , 1984 .

[15]  R. V. Duyne,et al.  Surface-enhanced resonance Raman spectroscopy of adsorbates on semiconductor electrode surfaces. 2. In situ studies of transition metal (iron and ruthenium) complexes on silver/gallium arsenide and silver/silicon , 1985 .

[16]  P. A. Lay,et al.  Surface-Enhanced Raman Scattering for Redox-Active Adsorbates: Pentaammineosmium(III)/(II) and Pentaammineruthenium(II) Containing Nitrogen Heterocycle Ligands. , 1984 .

[17]  T. Furtak,et al.  Surface-enhanced raman scattering magnified by photochemical activation of the silver electrode in aqueous halide electrolytes , 1982 .

[18]  R. V. Van Duyne,et al.  Surface Raman spectroscopy as an in-situ probe of laser micro chemical processes , 1986, IEEE Circuits and Devices Magazine.

[19]  A. Lytel Introduction to lasers and masers , 1966 .

[20]  P. B. Dorain,et al.  Surface-enhanced hyper-raman scattering from SO32− adsorbed on Ag powder , 1982 .

[21]  Y. Suzaki,et al.  Measurement of the microm sized radius of Gaussian laser beam using the scanning knife-edge. , 1975, Applied optics.

[22]  T. Furtak,et al.  Influence of laser illumination during an oxidation-reduction cycle on the surface structure of silver , 1984 .

[23]  M. J. Weaver,et al.  Effect of laser illumination oxidation-reduction cycles upon surface-enhanced Raman scaterring from silver electrodes , 1982 .

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

[25]  Richard M. Osgood,et al.  Direct Observation of the Local-Field-Enhanced Surface Photochemical Reactions , 1983 .

[26]  Melvin Lax,et al.  Temperature rise induced by a laser beam , 1977 .

[27]  Jeanne P. Haushalter,et al.  Surface-enhanced Raman spectroscopy of adsorbates on semiconductor electrode surfaces: tris(bipyridine)ruthenium(II) adsorbed on silver-modified n-gallium arsenide(100) , 1983 .

[28]  R. P. Duyne,et al.  Surface enhanced raman and resonance raman spectroscopy in a non-aqueous electrochemical environment: Tris(2,2′-bipyridine)ruthenium(II) adsorbed on silver from acetonitrile , 1983 .