Molecular junctions of metal/molecule/metal were fabricated with silver nanoparticles and functional molecules through layer-by-layer self-assembly techniques. The Raman scattering of the interconnecting molecules between the silver nanoparticles can be greatly enhanced. For the silver/4-aminothiophenol/silver (Ag/PATP/Ag) assembly, in particular, the larger enhancement of the b 2 modes, relative to that of the a 1 modes, is ascribed to the charge transfer between the silver nanoparticles tunneling through the interconnecting PATP molecules. The molecular dipolar momentum and surface property of the silver nanoparticles have large effects on the enhancement of the Raman scattering of the interconnecting molecules.

Forged signature threatens the authenticity of personal identity. Here, an effective SERS anti-counterfeiting system is designed for personal signatures. Mixed ligands improve the complexity of Raman spectra and expand the coding capacity. Fourteen distinct combinations are created from mere five ligands, and great expansion is possible with modest expansion of the ligand library. On the other hand, the (Au-aggregate)@Ag@PSPAA nanostructure significantly increases the surface-enhanced Raman scattering (SERS) intensity and stability so that excellent performance is achieved in SERS detection. By integrating these strategies, SERS inks are produced and applied in signature anti-counterfeiting. The resulting spectra are converted to barcodes that are readily detected through a smart phone APP. With these improvements, this work brings SERS one step closer toward practical applications in signature anti-counterfeiting.

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Silver nanoparticles were assembled on polyvinylpyridine (PVP) derivatized glass slides. Charge transfer between the adsorbed 4-aminothiophenol (PATP) and the immobilized silver nanoparticles was studied by surface-enhanced Raman spectroscopy with 1064 nm excitation, and compared with that of the silver nanoparticles in the colloid. It was demonstrated that the positive charges of the PVP layer could alter the charge distribution in the immobilized nanoparticles and induce the formation of the dipole in the nanoparticles, leading to less charge transfer from the metal to the adsorbed molecules. The coadsorption of chloride ions on the surface of the immobilized silver nanoparticles resulted in the redistribution of the charges in the nanoparticles and, in turn, altered the charge transfer between the adsorbed PATP molecules and the silver nanoparticles.