Procedures are outlined for the electrodeposition of ultrathin films of Pt-group transition metals onto gold that provide intense surface-enhanced Raman scattering (SERS) for adsorbates bound to the overlayers yet (unlike earlier reports) are sufficiently "pinhole-free" to avoid significant spectral and chemical interferences from the underlying substrate. Constant-current electrodeposition of Pd, Rh, Pt, and Ir from perchloric acid and/or phosphate electrolytes yields essentially layer-by-layer growth, so that near-ideal pinhole-free electrochemical and spectral characteristics are achieved for film thickness of ∼2 monolayers or more. The desired film uniformity is diagnosed from the voltammetric oxide formation-removal behavior and, especially, from the absence of the characteristic C-O stretching (ν(CO)) SERS band at 2110-2120 cm(-)(1) due to CO binding to Au surface sites. Carbon monoxide is also employed as a surface environment-sensitive adsorbate to probe the electrochemical SERS characteristics as a function of the transition-metal film thickness. The Raman enhancement was observed to decrease by 2-fold every 10-20 Å or so, exhibiting a "spacer distance" dependence that is weaker than (but functionally similar to) recently reported organic insulator films. The practical value of the present films for obtaining rich vibrational spectra for diverse adsorbates on transition metals is pointed out and briefly illustrated for benzonitrile on a Pt film electrode. The more general promise of this overlayer film SERS strategy as a versatile vibrational technique for characterizing other types of chemically important surface materials is also noted.
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