Self-assembly of colloidal nanoparticles into 2D arrays at water–oil interfaces: rational construction of stable SERS substrates withaccessible enhancing surfaces and tailored plasmonic response

Self-assembly at water–oil interfaces has been shown to be a cheap, convenient and efficient route to obtain densely packed layers of plasmonic nanoparticles which have small interparticle distances. This creates highly plasmonically active materials that can be used to give strong SERS enhancement and whose structure means that they are well suited to creating the highly stable, reproducible and uniform substrates that are needed to allow routine and accurate quantitative SERS measurements. A variety of methods have been developed to induce nanoparticle self-assembly at water–oil interfaces, fine tune the surface chemistry and adjust the position of the nanoparticles at the interface but only some of these are compatible with eventual use in SERS, where it is important that target molecules can access the active surface unimpeded. Similarly, it is useful to transform liquid plasmonic arrays into easy-to-handle freestanding solid films but these can only be used as solid SERS substrates if the process leaves the surface nanoparticles exposed. Here, we review the progress made in these research areas and discuss how these developments may lead towards achieving rational construction of tailored SERS substrates for sensitive and quantitative SERS analysis.