Abstract: Plasmonics-active nanostructure substrates—developed on a wafer scale in a reliable and reproducible manner such that these plasmonics-active nanostructures have nano-scale gaps (that include but are not limited to sub-10 nm gaps or sub-5 nm gaps) that provide the highest EM field enhancement between neighboring plasmonics-active metallic or metal-coated nanostructures. The plasmonics-active nanostructure substrates relate to environmental sensing based on SERS, SPR, LSPR, and plasmon enhanced fluorescence based sensing as well as for developing plasmonics enhanced devices such as solar cells, photodetectors, and light sources. Controllable development of sub-2 nm gaps between plasmonics-active nanostructures can also be achieved. Also, the size of the nano-scale gap regions can be tuned actively (e.g., by the application of voltage or current) to develop tunable sub-5 nm gaps between plasmonic nanostructures in a controllable manner.