Atomic force microscopy and surface-enhanced Raman spectroscopy. I. Ag island films and Ag film over polymer nanosphere surfaces supported on glass

The surface roughness and nanometer scale structure of Ag films used for surface-enhanced Raman scattering (SERS) are characterized using atomic force microscopy (AFM). Two important types of thin film based SERS-active surface have been examined in this study: (1) Ag island films (AgIF’s) on smooth, insulating substrates and (2) thick Ag films evaporated over both preroughened and smooth substrates. AFM is demonstrated to be capable of quantitatively defining the three-dimensional (3D) structure of these roughened surfaces. The effects of mass thickness, dm, and thermal annealing on the nanostructure of AgIF’s are studied in detail. Particle size histograms are calculated from the AFM images for both ‘‘as-deposited’’ and annealed IF’s with dm=1.8 and 3.5 nm. Quantitative measurements of the SERS enhancement factor (EF) are coupled with the AFM data and interpreted within the framework of the electromagnetic theory of SERS. AFM images for thick evaporated Ag films over a monolayer of polymer nanospheres (AgFON) shows the clear presence of ‘‘random substructure roughness’’ reducing their utility as controlled roughness surfaces. Similar roughness structures are observed for thick evaporated Ag films on smooth, insulating substrates. Nevertheless, AgFON surfaces are demonstrated to be among the most strongly enhancing thin film based surfaces ever studied with EF’s comparable to those found for electrochemically roughened surfaces. Applications of FON surfaces to ultrahigh sensitivity SERS, anti-Stokes detected SERS, and surface-enhanced hyper-Raman spectroscopy (SEHRS) are reported.