Self-assembly of Au nanocrystals into large-area 3-D ordered flexible superlattice nanostructures arrays for ultrasensitive trace multi-hazard detection

Plasmonic nanoparticles that self-assemble into highly ordered superlattice nanostructures hold substantial promise for facilitating ultra-trace surface-enhanced Raman scattering (SERS) detection. Herein, we propose a boiling-point evaporation method to synthesize ordered monocrystal-like superlattice Au nanostructures (OML-Au NTs) with a polyhedral morphology. Combined with thermal nanoimprint technology, OML-Au NTs were directly transferred to impact-resistant polystyrene (IPS) flexible SERS substrates, the obtained flexible substrates (donated as OML-Au NTs/IPS) detection limit for R6G molecules as low as 10- 13 M. These results were confirmed by simulating the electromagnetic field distribution of ordered/unordered two-dimensional single-layer and three-dimensional aggregated gold nanostructures. The OML-Au NTs/IPS substrates were successfully used to detect and quantify three commonly-used agricultural pesticides, achieving detection limits as low as 10-11 M and 10-12 M, and in situ real-time detection limit reached 0.24 pg/cm2 for thiram on apple peels, which was 3 orders of magnitude lower than the current detection limit. In addition, the Raman intensity from multiple lo-cations showed a relative standard deviation lower than 7 %, exhibiting the reliability necessary for practical applications. As a result, this research demonstrates a highly reproducible method to enable the development of plasmonic nanomaterials with flexible superstructures.