Nanoporous Copper Films as Platform for UV-SERS: Sensitivity and Ability to Perform Chiral Discrimination

Abstract

Surface enhanced Raman spectroscopy (SERS) in the ultraviolet (UV) region offers important advantages for biomolecular detection, including resonance enhancement and reduced fluorescence interference. However, the development of UV SERS substrates that combine low cost, reproducibility, and chemical stability remains challenging. Here, we employ a dry synthesis approach to fabricate nanoporous Cu and copper oxide (CuO) films on silicon substrates and systematically evaluate their UV SERS performance using adenine as a Raman reporter under 325 nm excitation. Among the substrates investigated, nanoporous Cu exhibits the strongest enhancement, enabling adenine detection down to 10 microM. In contrast, no detectable adenine Raman signal is observed under 532 nm excitation, indicating that the enhancement is dominated by a UV induced chemical, charge transfer mechanism rather than conventional electromagnetic enhancement. The Cu substrates further enable the UV Raman spectroscopy of streptavidin, as a test protein, and, more interestingly, the discrimination between L and D tryptophane based solely on differences in UV SERS intensity, without chiral selectors or additional surface functionalization. By varying the substrate rotation speed during metal evaporation, the enantioselective response can be tuned, yielding L over D intensity ratios from 1.10 to 2.35 and demonstrating the critical role of substrate morphology in chiral discrimination. The dry synthesized nanoporous films provide a simpler, scalable, and ligand free fabrication strategy while offering additional capability for enantioselective detection. These findings establish dry processed nanoporous Cu films as promising platforms for UV-SERS biosensing and label free chiral analysis.