Study of the Fabrication of Gold Nanoparticle–Graphene-Arrayed Micro/Nanocavities as SERS Substrates Compared to Two Different Angles of Triangular Pyramid Tips

Abstract

Surface-enhanced Raman scattering (SERS) has attracted attention because of its enormous potential to detect molecules with low concentrations. The method of fabricating SERS substrates is of great importance for improving the detection resolution. However, SERS substrates with different triangular pyramid tips fabricated by using the tip-based nanoindentation method has not been reported. Here, we prepared arrayed micro/nanocavities on copper-based graphene using the continuous indentation method with a Berkovich tip and a cube-corner tip, which have different face angles. Gold nanoparticles were then sputtered onto the graphene-copper micro/nanocavities to form the Au@GR@Cu micro/nanocavities SERS substrates. The substrates formed using the Berkovich tip and cube-corner tip were labeled B2-B9 and C2-C9, respectively, in which the numbers indicate the machining feed. Rhodamine 6G (R6G) was employed, and the Raman intensities of R6G on the differently arrayed Au@GR@Cu micro/nanocavities were measured. The Raman intensities of R6G were stronger on the pile-ups than on the inverted triangular pyramid cavities. The Raman intensities of R6G were highest on the C2 and B2 structures and lowest on the C9 and B9 structures. The Raman intensities of R6G on the arrayed Au@GR@Cu micro/nanocavities fabricated by the cube-corner tip were stronger than those on the arrayed Au@GR@Cu micro/nanocavities fabricated using the Berkovich tip with the same machining feed. In addition, the electric field intensity and distribution of the B9 and C9 arrayed Au@GR@Cu were simulated using Comsol software. Au@GR@Cu structures fabricated by the cube-corner tip were generated with higher electric field intensities. Furthermore, the relative standard deviations at 1362 cm-1 of R6G were 6.19 and 6.62% on the C2 and C4 surfaces, respectively, showing good homogeneity. The SERS spectra of 10-9 mol/L malachite green solution and 10-6 mol/L carbaryl solution were recognized on the C1, C2, and C4 surfaces on day 1 and after 3 months, respectively. After storage at room temperature for 3 months, the reductions in the Raman intensities were less than 10%, indicating excellent stability. The results showed that the arrayed Au@GR@Cu micro/nanocavities fabricated using the cube-corner tip performed better than those fabricated using the Berkovich tip and exhibited excellent uniformity, availability, and stability, providing great potential for detecting pesticides at low concentrations.