Assemblies of silver nanocubes for highly sensitive SERS chemical vapor detection

We suggest that silver nanocube (AgNC) aggregates within cylindrical pores (PAM-AgNC) can be employed as efficient nanostructures for highly efficient, robust, tunable, and reusable surface-enhanced Raman scattering (SERS) substrates for trace level organic vapor detection which is a challenging task in chemical detection. We demonstrate the ability to tune both the detection limit and the onset of signal saturation of the substrate by switching the adsorption behavior of AgNCs between highly aggregated and more disperse by varying the number of adsorption-mediating polyelectrolyte bilayers on the pore walls of the membrane. The different AgNC distributions show large differences in the trace vapor detection limit of the common Raman marker benzenethiol (BT) and a widely used explosive binder N-methyl-4-nitroaniline (MNA), demonstrating the importance of the large electromagnetic field enhancement associated with AgNC coupling. The SERS substrate with highly aggregated AgNCs within the cylindrical pores allows for consistent trace detection of mid ppb (similar to 500) for BT analyte, and a record limit of detection of low ppb (similar to 3) for MNA vapors with an estimated achievable limit of detection of approximately 600 ppt. The dispersed AgNC aggregates do not saturate at higher ppb concentrations, providing an avenue to distinguish between higher ppb concentrations and increase the effective range of the SERS substrate design. A comparison between the AgNC substrate and an electroless deposition substrate with silver quasi-nanospheres (PAM-AgNS) also demonstrates a higher SERS activity, and better detection limit, by the nanocube aggregates. This is supported by FDTD electromagnetic simulations that suggest that the higher integrated electromagnetic field intensity of the hot spots and the large specific interfacial areas impart greatly improved SERS for the AgNCs. Moreover, we demonstrated that the AgNC substrate can be reused multiple times without significant loss of SERS activity which opens up new avenues for in-field monitoring.