Uniform Periodic Bowtie SERS Substrate with Narrow Nanogaps Obtained by Monitored Pulsed Electrodeposition

Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive technique with molecular specificity, making it an ideal analytical tool in various fields. However, the breadth of practical applications of SERS has been severely limited because it is still a great challenge to achieve simultaneously a high sensitivity and a high reproducibility. Herein, we report a highly controllable method to fabricate periodic bowtie SERS substrates with a narrow nanogap, high SERS enhancement, and good uniformity over a large area. The periodic bowtie template is first fabricated over a gold film by holographic lithography (HL), followed by Au deposition to obtain a conductive plasmonic bowtie array. The gap size is then narrowed down by pulsed electrodeposition of Ag simultaneously monitored in situ by electrochemical dark field spectroscopy. Thus, we are able to observe the most sensitive change in the scattering spectra when the gap is just about to merge and obtain uniform SERS substrates with a gap size down to around 5 nm. The average enhancement factor of 5 × 10⁷ to 1 × 10⁸ is obtained, which is 50 times larger than that from Au nanoparticle-assembled substrates and 140 times larger than that from commercial Klarite chips. This substrate offers a promising opportunity for SERS practical applications.