A key element to improve the analytical capabilities of surface-enhanced Raman spectroscopy (SERS) resides in the performance characteristics of the SERS-active substrate. Variables such as shape, size, and homogeneous distribution of the metal nanoparticles throughout the substrate surface are important in the design of more analytically sensitive and reliable substrates. Electron-beam lithography (EBL) has emerged as a powerful tool for the systematic fabrication of substrates with periodic nanoscale features. EBL also allows the rational design of nanoscale features that are optimized to the frequency of the Raman laser source. In this work, the efficiency of EBL fabricated substrates are studied by measuring the relative SERS signals of Rhodamine 6G and 1,10-phenanthro-line adsorbed on a series of cubic, elliptical, and hexagonal nanopatterned pillars of ma-N 2403 directly coated by physical vapor deposition with 25 nm films of Ag or Au. The raw analyte SERS signals, and signals normalized to metal nanoparticle surface area or numbers of loci, are used to study the effects of nanoparticle morphology on the performance of a rapidly created, diverse collection of substrates. For the excitation wavelength used, the nanoparticle size, geometry, and orientation of the particle primary axis relative to the excitation polarization vector, and particularly the density of nanoparticles, are shown to strongly influence substrate performance. A correlation between the inverse of the magnitude of the laser backscatter passed by the spectrometer and SERS activities of the various substrate patterns is also noted and provides a simple means to evaluate possible efficient coupling of the excitation radiation to localized surface plasmons for Raman enhancement.

Surface-enhanced Raman spectroscopy (SERS) has proven to be a very powerful tool in the analysis of a wide range of compounds. However, continuous irradiation of the laser beam over the SERS substrate can promote the gross decomposition of the sample analytes and significantly broaden and diminish the intensities of observed spectral bands. In addition, the incident radiation can promote thermal or photolytic fragmentation of analytes, thereby altering the observable bands and possibly leading to a misinterpretation of analytical data. Finally, chemical or morphological changes in the SERS substrate are possible. This work presents the use of a sample translation technique (STT) as a means to minimize these adverse effects. By spinning the sample rapidly, the effective residence time of analytes and substrate within the irradiated zone is dramatically decreased without reduction of spectral acquisition time or the density of analyte in the zone. The technique is studied by acquiring SERS spectra of Naproxen USP, riboflavin, folic acid, Rhodamine 6G, and 4-aminothiophenol using silver islands on glass and silver-poly(dimethylsiloxane) composite substrates under various spinning and stationary conditions. In all cases, spectra show improvements upon spinning at laser powers as low as 4.2 (+/- 0.1) mW. Specific differences in the appearance of the spectra and the potential use of STT for improved SERS qualitative and quantitative determinations are presented.

Polymer-nano-metallic-particle composites have demonstrated technological potential due to their unique optical and electrical properties. Herein, we report on composites prepared via physical vapor deposition of silver metal onto pliable poly(dimethylsiloxane) (PDMS) polymer. Rapid Ag diffusion and nano-metallic-particle formation in a phase-separated surface layer of the PDMS creates unique sub-surface-based composites whose properties vary based on rate of deposition and average Ag thickness. Additionally, nanometallic-particle spacing can be altered with fair reproducibility and reversibility by physically manipulating the Ag-PDMS composite. The optical properties of the materials are studied by visible wavelength optical extinction spectrometry and surface-enhanced Raman scattering (SERS), including studies performed during physical manipulation. Direct current (DC) conductivity measurements were made during Ag deposition to study percolation conditions for the materials. Depth-profiling was performed by X-ray photoelectron spectrometry. Sample Raman spectral data collected with the composite as a SERS substrate are included. A practical technological characteristic of these composite materials arises from their potential to be molded into functional devices.

The presence of naphthalene, phenol and benzoic acid derivatives in natural waters constitutes a public health issue. The toxicity and chemical activity of these chemicals and their persistence in the environment depend on the types of functional groups attached to their basic aromatic structure. Surface-enhanced Raman scattering (SERS) spectroscopy has shown promise for the analysis of aromatic compounds owing to a tremendous enhancement of the analytical response and also a large amount of available structural information. Despite these advantages, SERS has not been established as a routine analytical tool owing to limitations in the analytical figures of merit such as reproducibility and linear dynamic range. This paper reports the use of silver-polydimethylsiloxane nanocomposites in combination with a sample translation technique for the improved qualitative and quantitative analysis of model environmental pollutants in water. This novel approach considerably improves the reproducibility and the sensitivity of the technique by minimizing the thermal and photolytic effects inherent in SERS. The results show a linear dynamic range of at least two orders of magnitude with detection limits as low as 2.9 × 10 −8 M and a precision of <10% relative standard deviation. The influences of different experimental variables such as irradiation time, translation rate and pH and the potential use of the technique for the analysis of environmental pollutants are presented.