Normal and surface-enhanced Raman spectroscopy of nitroazobenzene submonolayers and multilayers on carbon and silver...

Raman and ultraviolet-visible (UV-Vis) absorption spectra were obtained for nitroazobenzene (NAB) chemisorbed on smooth and rough silver, and they were compared to published spectra for NAB on sp(2) hybridized pyrolyzed photoresist film (PPF) surfaces. High signal-to-noise ratio Raman spectra were obtained for 4.5 nm thick NAB films on PPF and smooth Ag due to significant enhancement of the NAB scattering relative to that observed in solution. The UV-Vis spectra of chemisorbed NAB exhibited a significant shift toward longer wavelength, thus bringing the NAB absorption closer to the 514.5 nm laser wavelength. The red shift was larger for PPF than for smooth Ag, consistent with the approximately 5x stronger Raman signal obtained on PPF. Deposition of Ag onto quartz without a chromium adhesion layer produced a rough Ag surface that enhanced the Raman spectrum of chemisorbed NAB by a factor of approximately 1000, as expected for roughened Ag due to electromagnetic field enhancement. The strong Raman signal permitted observation of NAB at low coverage and revealed changes in the NAB spectrum as the film progressed from submonolayer to multilayer thicknesses. Finally, deposition of Ag onto PPF/NAB samples through a metal grid produced Ag squares on top of the NAB, which enhanced the Raman scattering of the NAB layer by a factor of approximately 100. Deposition of a final conducting film on the Ag squares should permit in situ observation of a wide range of molecules in operating molecular electronic junctions.