Engineering Nanoparticle Cluster Arrays for Bacterial Biosensing: The Role of the Building Block in Multiscale SERS Substrates

Noble metal nanoparticle cluster arrays (NCAs) are a novel class of engineered substrates for surface enhanced Raman spectroscopy (SERS), in which the noble metal nanoparticles interact on multiple length scales to create a multiscale E‐field cascade enhancement. In this work the role of the building block for the NCA performance is quantified. Periodic NCAs with constant cluster diameter (D = 200 nm) but variable nanoparticle diameter (d) and intercluster separation (Λ) were assembled on glass and their optical response and SERS enhancement were systematically characterized as a function of D, Λ, and d. An increase of d from 40 to 80 nm and simultaneous decrease of Λ from 200 to 50 nm led to an improvement of the ensemble averaged SERS enhancement factor by a factor of up to ∼8. The coefficient of variation (cv) of the enhancement factors (G) is significantly lower for the d = 80 nm NCAs than for the d = 40 nm and d = 60 nm NCAs. Optimized (D = 200 nm, Λ = 50 nm, d = 80 nm) NCAs show the overall highest signal reproducibility of all investigated NCAs and random nanoparticle substrates and achieve effective single cell detection sensitivity.