We report on the self-assembling of clusters of gold-nanoparticles (Au-NPs) directed by the phase separation of poly(styrene)-b-poly(methylmethacrylate) (PS-b-PMMA) block-copolymer (BCP) on indium tin oxide coated glass, which induces the onset of vertical lamellar domains. After thermal evaporation of gold on BCP, Au-NPs of 4 nm are selectively included into PS-nanodomains by thermal annealing, and then clustered with large density of hot spots (> 10⁴ μm²) in a random two-dimensional pattern. The resulting nanostructure exhibits near-hyperuniform long-range correlations. The consequent large degree of homogeneity of this isotropic plasmonic pattern gives rise to a highly reproducible Surface-Enhanced Raman Scattering (SERS) enhancement factor over the centimeter scale (std. dev. ∼ 10% over 0.25 cm²). We also discuss the application of a static electric field for modulating the BCP host morphology. The electric field induces an alignment of Au-NP clusters into ordered linear chains, exhibiting a stronger SERS activity, but reduced SERS spatial reproducibility.

Disordered hyperuniform (DH) media have been recognized as a new state of disordered matter that broadens our vision of material engineering. Here, long-range correlated disordered two-dimensional patterns are fabricated by self-assembling of spherical diblock-copolymer (BCP) micelles. Control of the self-assembling parameters leads to the formation of DH patterns of micelles that can host nanoscale material inclusions, therefore providing an effective strategy for fabricating multimaterial DH structures at molecular scale. Centroidal patterns are accurately determined by virtue of BCP micelles loaded with metal nanoparticles. Our analysis reveals the signature of nearly ideal DH BCP assemblies in the local density fluctuation and a dominant linear scaling in the local number fluctuation.