Polarization-dependent SERS effects of laser-generated sub-100 nm antenna structures.

Sub-100 nm antenna arrays consisting of a star-like ridge or dome-like structures with needles in their centers are prepared in thin gold films on glass substrates using femtosecond laser pulses. The needles can be bent mechanically to be horizontally aligned to the substrate surface. Controlled variation of the pulse energy allows one to obtain nanostructures of different defined morphologies. These arrays of nanostructures are covered with a thin homogeneous layer of rhodamine molecules. Raman spectra using linearly polarized laser light of 632.8 nm are taken with the laser spot centered on individual nanostructures and at positions on the unstructured film. The average Raman enhancement within the laser spot focused onto a nanostructure is two orders of magnitude higher than on the unstructured film. The nanostructures with bent needles exhibit a polarization dependence of the SERS effect, i.e., typically the enhancement is larger by about a factor of two for excitation light polarized parallel to the needle direction than for the perpendicular case. The enhancement factor of the star-like ridge structures with needles is analyzed by the finite-element method, which agrees with the experiment. We show that the variation of the SERS activity of almost similar structures arises from the inherent randomness of the hot spots created in the fabrication process. Nevertheless, these antenna structures may be useful as elements in novel SERS devices as they can be accurately positioned on a device using a cheap fabrication process compatible with microfabrication technology.