A method for producing planar extended electrodes with nanoscale spacings that exhibit very large SERS signals, with each nanoscale gap having one well-defined hot spot. The resulting highly sensitive substrate has extended metal electrodes separated by a nanoscale gap. The electrodes act as optical antennas to enhance dramatically the local electromagnetic field for purposes of spectroscopy or nonlinear optics. SERS response is consistent with a very small number of molecules in the hotspot, showing blinking and wandering of Raman lines. Sensitivity is sufficiently high that SERS from physisorbed atmospheric contaminants may be detected after minutes of exposure to ambient conditions.