Methods of forming NERS-active structures are disclosed that include ordered arrays of nanoparticles. Nanoparticles covered with an outer shell may be arranged in an ordered array on a substrate using Langmuir-Blodgett techniques. A portion of the outer shell may be removed, and the exposed nanoparticles may be used in a system to perform nanoenhanced Raman spectroscopy. An ordered array of nanoparticles may be used as a mask for forming islands of NERS-active material on a substrate. NERS-active structures and an NERS system that includes an NERS-active structure are also disclosed. Also disclosed are methods for performing NERS with NERS-active structures.