Design of broadband SERS substrates by the laser-induced aggregation of gold nanoparticles

Surface-enhanced Raman scattering (SERS) has already demonstrated its significant potential in analytical science. Thus, current efforts are focused on the development of affordable and reproducible SERS substrates, which exhibit high enhancement factors and uniform responses. A large number of strategies were adopted to produce effective SERS substrates; however, most of them are tuned for the use of single excitation wavelength and consequently can only be applied for a limited number of analytes. Hence, SERS substrates that demonstrate broadband plasmonic properties represent a more flexible analytical tool for multi-wavelength or tunable light sources, especially for biological applications. In the current study, we demonstrate that direct laser writing (DLW), which activates a photoreactive moiety and immobilizes functionalized gold nanoparticles on chemically modified glass substrates, can be used to produce SERS substrates of various sizes and geometries. We show that by tuning the DLW parameters a broad plasmonic response is obtained, enabling the use of these substrates for multi-wavelength SERS analysis. Two Raman reporters, a small synthetic benzotriazole azo organic dye and a larger biological molecule, hemin, are tested at three fixed excitation wavelengths in the visible range (473 nm, 532 nm and 660 nm). SERS enhancement factors show a weak dependence on the wavelength used and the molecules investigated; moreover, the possibility of creating arbitrary shaped and uniform structures is demonstrated. The reported results show that DLW is an excellent technique to engineer microstructured and broadband SERS substrates.