Novel multilayered SERS substrates for trace chemical and biochemical analysis

We have developed and characterized novel multilayered metal film-based surface-enhanced Raman scattering (SERS) substrates capable of enhancing SERS signals over an order of magnitude compared to conventional single layer substrates. In addition to enhanced signal intensity, these multilayered metal film substrates also exhibit longer SERS active lifetimes, higher reproducibility and lower detection limits than single layer silver substrates. Multilayered metal film substrates were fabricated by repeated vapor deposition of metal films over nanometer sized silica spheres. Different sizes of silica spheres were evaluated in order to obtain the optimal SERS enhancements. Meanwhile, different coating methods, drop coating and spin coating, were applied to form silica sphere layers that provided the roughness for SERS enhancements. These two coating methods were also compared for various silica sphere sizes by investigating their effects on the SERS enhancements. By applying additional silver layers on top of silver film over silica sphere SERS substrates, multi-layer enhancements can be observed. Additionally, different metals, such as gold, were used to further optimize the stability and reproducibility of these novel substrates. In order to speed up the fabrication of these multiple metal layer SERS substrates, silver oxide layers produced in an oven were investigated, reducing fabrication time by a factor of 50.

[1]  Tuan Vo-Dinh,et al.  Cancer gene detection using surface-enhanced Raman scattering (SERS) , 2002 .

[2]  H. Lee,et al.  Surface-enhanced raman scattering (SERS) on chemically prepared silver film , 1985 .

[3]  Kathy L. Rowlen,et al.  Influence of vapor deposition parameters on SERS active Ag film morphology and optical properties , 1994 .

[4]  T. Vo‐Dinh,et al.  Silver-Coated Alumina as a New Medium for Surfaced-Enhanced Raman Scattering Analysis , 1989 .

[5]  Tieqiao Wu,et al.  Surface-enhanced Raman spectroscopy of insect nuclear polyhedrosis virus , 2001 .

[6]  Hua-Zhong Yu,et al.  Surface-Enhanced Raman Scattering (SERS) from Azobenzene Self-Assembled “Sandwiches” , 1999 .

[7]  J. C. Hoogvliet,et al.  Electrochemical pretreatment of polycrystalline gold electrodes to produce a reproducible surface roughness for self-assembly: a study in phosphate buffer pH 7.4 , 2000, Analytical chemistry.

[8]  T. Cotton,et al.  Silver-island films as substrates for enhanced Raman scattering: effect of deposition rate on intensity. , 1991, Analytical chemistry.

[9]  M. Natan,et al.  Colloidal Au-enhanced surface plasmon resonance immunosensing. , 1998, Analytical chemistry.

[10]  Tuan Vo-Dinh,et al.  Titanium Dioxide Based Substrate for Optical Monitors in Surface-Enhanced Raman Scattering Analysis , 1989 .

[11]  L. Dick,et al.  Metal film over nanosphere (MFON) electrodes for surface-enhanced Raman spectroscopy (SERS): Improvements in surface nanostructure stability and suppression of irreversible loss , 2002 .

[12]  C. A. Murray,et al.  Measurement of the molecule–silver separation dependence of surface enhanced Raman scattering in multilayered structures , 1982 .

[13]  R. Gu,et al.  Comparison of the Surface Properties of the Assembled Silver Nanoparticle Electrode and Roughened Silver Electrode , 2002 .

[14]  T. Cotton,et al.  Chemical procedure for preparing surface-enhanced Raman scattering active silver films. , 1986, Analytical chemistry.

[15]  M. Muniz-Miranda.  Surface enhanced Raman scattering of 2,2′-bipyridine adsorbed on smooth nickel surfaces , 2000 .

[16]  M. Odziemkowski,et al.  Study of Adsorption, Condensation, Orientation, and Reduction of Quinoline Molecules on a Pure Mercury Electrode Using Raman Microprobe Spectroscopy , 2000 .

[17]  M. Natan,et al.  Three‐layer substrates for surface‐enhanced Raman scattering: preparation and preliminary evaluation , 2003 .

[18]  A. Brolo,et al.  Investigation of the Adsorption of L-Cysteine on a Polycrystalline Silver Electrode by Surface-Enhanced Raman Scattering (SERS) and Surface-Enhanced Second Harmonic Generation (SESHG) , 2002 .

[19]  Christine D. Keating,et al.  Protein:Colloid Conjugates for Surface Enhanced Raman Scattering: Stability and Control of Protein Orientation , 1998 .

[20]  R. V. Van Duyne,et al.  Toward a glucose biosensor based on surface-enhanced Raman scattering. , 2003, Journal of the American Chemical Society.

[21]  J. Bukowska,et al.  Surface‐enhanced Raman scattering (SERS) of 4‐mercaptobenzoic acid on silver and gold substrates , 2003 .

[22]  Richard A. Dluhy,et al.  Development of a novel dual-layer thick Ag substrate for surface-enhanced Raman scattering (SERS) of self-assembled monolayers , 2002 .

[23]  R. V. Duyne,et al.  Atomic force microscopy and surface-enhanced Raman spectroscopy. I. Ag island films and Ag film over polymer nanosphere surfaces supported on glass , 1993 .

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

[25]  M. Manfait,et al.  Intracellular molecular interactions of antitumor drug amsacrine (m‐AMSA) as revealed by surface‐enhanced Raman spectroscopy , 1996, FEBS letters.

[26]  H. Chiang,et al.  Remarks on the Substrate-Temperature Dependence of Surface-Enhanced Raman Scattering , 2000 .

[27]  Arto V. Nurmikko,et al.  Strongly Interacting Plasmon Nanoparticle Pairs: From Dipole−Dipole Interaction to Conductively Coupled Regime , 2004 .

[28]  M. Porter,et al.  Immunoassay readout method using extrinsic Raman labels adsorbed on immunogold colloids. , 1999, Analytical chemistry.

[29]  Ramasamy Manoharan,et al.  Detection and identification of a single DNA base molecule using surface-enhanced Raman scattering (SERS) , 1998 .

[30]  Bernhard Lendl,et al.  A New Method for Fast Preparation of Highly Surface-Enhanced Raman Scattering (SERS) Active Silver Colloids at Room Temperature by Reduction of Silver Nitrate with Hydroxylamine Hydrochloride , 2003 .

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

[32]  C. Haynes,et al.  Surface-Enhanced Raman Scattering Detected Temperature Programmed Desorption: Optical Properties, Nanostructure, and Stability of Silver Film over SiO2 Nanosphere Surfaces , 2001 .

[33]  G. Xue,et al.  Stable silver substrate prepared by the nitric acid etching method for a surface-enhanced Raman scattering study , 1991 .

[34]  Tuan Vo-Dinh,et al.  Surface‐Enhanced Raman Detection of Nerve Agent Simulant (DMMP and DIMP) Vapor on Electrochemically Prepared Silver Oxide Substrates , 1996 .

[35]  Richard H. Clarke,et al.  Determination of cyanide in waste water by low‐resolution surface enhanced Raman spectroscopy on sol‐gel substrates , 2001 .

[36]  T. Vo‐Dinh,et al.  Silver-coated fumed silica as a substrate material for surface-enhanced Raman scattering , 1989 .

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

[38]  M. Natan,et al.  Heightened Electromagnetic Fields between Metal Nanoparticles: Surface Enhanced Raman Scattering from Metal−Cytochrome c-Metal Sandwiches , 1998 .

[39]  Zhidong Zhang,et al.  Surface‐enhanced Raman scattering of imidazole adsorbed on an iron surface , 2002 .

[40]  M. J. Weaver.  Surface-enhanced Raman spectroscopy as a versatilein situ probe of chemisorption in catalytic electrochemical and gaseous environments , 2002 .