Noble metal nanoparticles on quartz supports as SERS substrates excited by a diode laser system for SERDS

In this contribution we present surface enhanced Raman scattering (SERS) measurements of pyrene as a function of the surface plasmon resonance position of noble metal nanoparticle ensembles, which served as SERS substrates. The noble metal nanoparticle ensembles were prepared under ultrahigh vacuum (UHV) conditions by Volmer-Weber growth on quartz substrates. For the SERS measurements, the substrates were mounted in a flow-through cell as part of the optical Raman set-up. A diode laser microsystem with an emission wavelength of 488 nm was used. The system generates two slightly different emission wavelengths (Δλ ≈ 0.3 nm) with a spectral width of ≈ 10 pm and an optical power of ≈ 10 mW. With this set-up SERS as well as shifted excitation Raman difference spectroscopy (SERDS) can be carried out. For trace analysis of pyrene in water SERS/SERDS experiments were accomplished as a function of molecule concentration and spectral position of the plasmon resonance. The best results with a limit of detection of 2 nmol of pyrene were obtained with a nanoparticle ensemble with a plasmon resonance in the vicinity of the excitation wavelength of λ = 488 nm. If the plasmon resonance frequency is slightly off-resonance the detection limit is significantly lower. The latter results are discussed in more detail and we will demonstrate that the morphology and the optical properties of the SERS substrates crucially influence the LOD.