Laser microzone damage in surface‐enhanced Raman scattering by pyridine on cooper electrodes

Abstract

Surface‐enhanced Raman scattering (SERS) by pyridine on anodized copper electrode surfaces has been shown to arise from laser damage zones. On the basis of pH dependence studies, the intensely scattering species appears to be a copper complex. Evidence for semi‐macroscopie laser damage zones (ca 0.1 mm in diameter, ca 500 nm or ca 1400 atom layers in depth) emerges from laser perforation of thin film electrodes, visual examination, scanning electron micrescopy (SEM), Raman line intensification for laser illumination during the oxidation‐reduction cycle (ORC), uniform laser‐flux perturbations of the cyclic voltammograms and laser interruption intensity studies. These results argue for a much reduced metal surface enhancement factor for this system and against the use of copper SERS effects in studies of electrosorption on undamaged surfaces. SERS from this system at excitation wavelengths greater than 620 nm is expected to involve conventional (non‐surface)resonance enhancement arising from copper(II)‐pyridine complexes (λmax ⩾ 590 nm) formed by copper corrosion within the laser damage zone. On the basis of these findings the Cu/pyridine system has been classified as SERS Type III. Show more