Binary “island” shaped arrays with high-density hot spots for surface-enhanced Raman scattering substrates

Abstract

We have demonstrated a facile and low-cost approach for the fabrication of binary “island” shaped arrays (BISA) with high-density hot spots as reproducible surface-enhanced Raman scattering (SERS) substrates by depositing a self-assembled monolayer Au nanoparticle (AuNP) film with small gaps onto a two-dimensional (2D) silica microsphere opal structure. By varying the size of silica spheres, the SERS performance of the BISA substrate with an enhancement factor (EF) of 3.74 × 10¹⁰ magnitude and the corresponding signal intensity deviation of below 8% using 770 nm silica sphere arrays were achieved. Compared with the assembled monolayer AuNP film on a planar substrate, the BISA enabled the installation of more AuNPs as a source of hot spots due to the undulation of morphology on the nanoscale within the designated laser-illumination area. In addition, a finite-difference time-domain (FDTD) simulation suggested that the BISA structure provided geometric conditions for increasing the intensity of the formed hot spots, and the strong periodic electric fields on the BISA are located not only in the gap between adjacent AuNPs, but also along the boundary of the neighboring island of silica spheres. Surface plasmon-decayed hot carriers (hot electrons and hot holes) from AuNPs can be applied in the field of energy conversion (i.e., photocatalysis), integrated with the SERS as a sensitive optical indicator to accurately monitor the catalytic reaction process. Furthermore, we examined the catalytic reaction process of the dimerization of 4-ATP into DMAB and found that photocatalytic activity could be tuned by changing the size of silica spheres. This study provides a new design route for the fabrication of the SERS platform with high sensitivity and reproducibility to detect molecules or improve catalyst efficiency.