• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.2941-2948
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• 2011

A nanogap formed by a metal nanoparticle and a flat metal substrate is one kind of "hot site" for surface-enhanced Raman scattering (SERS). The characteristics of a typical nanogap formed by a planar Au and either an Au and Ag nanoparticle have been well studied using 4-aminobenzenethiol (4-ABT) as a probe. 4-ABT is, however, an unusual molecule in the sense that its SERS spectral feature is dependent not only on the kinds of SERS substrates but also on the measurement conditions; thus further characterization is required using other adsorbate molecules such as 1,4-phenylenediisocyanide (1,4-PDI). In fact, no Raman signal was observable when 1,4-PDI was selfassembled on a flat Au substrate, but a distinct spectrum was obtained when 60 nm-sized Au or Ag nanoparticles were adsorbed on the pendent -NC groups of 1,4-PDI. This is definitely due to the electromagnetic coupling between the localized surface plasmon of Au or Ag nanoparticle with the surface plasmon polariton of the planar Au substrate, allowing an intense electric field to be induced in the gap between them. A higher Raman signal was observed when Ag nanoparticles were attached to 1,4-PDI, irrespective of the excitation wavelength, and especially the highest Raman signal was measured at the 632.8 nm excitation (with the enhancement factor on the order of ${\sim}10^3$), followed by the excitation at 568 and 514.5 nm, in agreement with the finite-difference timedomain calculation. From a separate potential-dependent SERS study, the voltage applied to the planar Au appeared to be transmitted without loss to the Au or Ag nanoparticles, and from the study of the effect of volatile organics, the voltage transmission from Au or Ag nanoparticles to the planar Au also appeared as equally probable to that from the planar Au to the Au or Ag nanoparticles in a nanogap electrode. The response of the Au-Ag nanogap to the external stimuli was, however, not the same as that of the Au-Au nanogap.

• Bulletin of the Korean Chemical Society
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• v.34 no.3
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• pp.793-800
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• 2013

A few years ago, the plasmon-induced electronic coupling (PIEC) model was proposed in the literature to explain small changes in the surface-enhanced Raman scattering (SERS) in nanogap systems. If this model is correct, it will be very helpful in both basic and application fields. In light of this, we carefully reexamined its appropriateness. Poly(4-vinylpyridine) (P4VP) used in the earlier work was, however, never a proper layer, since most adsorbates not only adsorbed onto Ag nanoparticles sitting on P4VP but also penetrated into the P4VP layer deposited initially onto a flat Ag substrate, ultimately ending up in the SERS hot sites. Using 1,4-phenylenediisocyanide and 4-nitrophenol as the affixing layer and the foreign adsorbate, respectively, we could clearly reveal that the PIEC model is not suited for explaining the Raman signal in a nanogap system. Most of the Raman signal must have arisen from molecules situated at the gap center.