Use of Polycrystalline Ice for Assembly of Large Area Au Nanoparticle Superstructures as SERS Substrates

It is still a great challenge to develop simple and low-cost methods for preparation of surface-enhanced Raman scattering (SERS) substrates with high sensitivity and reproducibility. Taking advantage of the microstructure of polycrystalline ice, we developed a new method to assemble large area gold nanoparticle (AuNP) superstructures as SERS substrates without external templating and aggregating agent. The assembly was conducted by freezing AuNP colloid at -20 °C, which concentrated AuNPs in the ice veins and produced an AuNP superstructure upon thawing the ice. The AuNP superstructures exhibited high SERS activity with enhancement factors on the order of 7.63 × 10⁷ owing to the high-density hot spots throughout the superstructures. The SERS activity was found to increase with particle size and aggregate size of AuNP superstructures. Besides, the substrates showed good uniformity and reproducibility with relative standard deviations of 11.9% and 12.4%, respectively. The substrates showed long-term stability, maintaining SERS activity over a period of five months without noticeable change in morphology of the superstructures. The substrates was further used for label-free detection of trace Thiram on apple fruit with high sensitivity down to the concentration of 0.28 ng/cm², offering great potential to monitor Thiram levels in foodstuffs and environmental samples.