Near‐field plasmonic coupling and local field enhancement in metal nanoarchitectures, such as arrangements of nanoparticle clusters, have application in many technologies from medical diagnostics, solar cells, to sensors. Although nanoparticle‐based cluster assemblies have exhibited signal enhancements in surface‐enhanced Raman scattering (SERS) sensors, it is challenging to achieve high reproducibility in SERS response using low‐cost fabrication methods. Here an innovative method is developed for fabricating self‐organized clusters of metal nanoparticles on diblock copolymer thin films as SERS‐active structures. Monodisperse, colloidal gold nanoparticles are attached via a crosslinking reaction on self‐organized chemically functionalized poly(methyl methacrylate) domains on polystyrene‐block‐poly(methyl methacrylate) templates. Thereby nanoparticle clusters with sub‐10‐nanometer interparticle spacing are achieved. Varying the molar concentration of functional chemical groups and crosslinking agent during the assembly process is found to affect the agglomeration of Au nanoparticles into clusters. Samples with a high surface coverage of nanoparticle cluster assemblies yield relative enhancement factors on the order of 109 while simultaneously producing uniform signal enhancements in point‐to‐point measurements across each sample. High enhancement factors are associated with the narrow gap between nanoparticles assembled in clusters in full‐wave electromagnetic simulations. Reusability for small‐molecule detection is also demonstrated. Thus it is shown that the combination of high signal enhancement and reproducibility is achievable using a completely non‐lithographic fabrication process, thereby producing SERS substrates having high performance at low cost.
Poly(methyl methacrylate) (PMMA) domains in phase-separated polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer thin films were chemically modified for controlled placement of solution synthesized Au nanoparticles having a mean diameter of 24 nm. Colloidal Au nanoparticles functionalized with thioctic acid were immobilized on amine functionalized PMMA domains on the PS-b-PMMA template using 1-ethyl-3-[3-dimethylaminopropyl] carbodiimide hydrochloride linking chemistry and N-hydroxy sulfosuccinimide stabilizer. Atomic force microscopy and scanning electron microscopy images demonstrated immobilization of Au nanoparticles commensurate with PMMA domains. Nanoparticles form into clusters of single particles, dimers, and linear chains as directed by the PMMA domain size and shape. Capillary forces influence the spacing between Au nanoparticles on PMMA domains. Inter-particle spacings below 3 nm were achieved and these assemblies of closely spaced nanoparticle clusters are expected to exhibit strong localized electromagnetic fields. Thus, these processes and material systems provide an experimental platform for studying resonantly enhanced excitations of surface plasmons as a function of material and geometric structure as well as utilization in catalytic applications.
Discrete clusters of closely spaced Au nanoparticles can be utilized in devices from photovoltaics to molecular sensors because of the formation of strong local electromagnetic field enhancements when illuminated near their plasmon resonance. In this study, scalable, chemical self-organization methods are shown to produce Au nanoparticle clusters with uniform nanometer interparticle spacing. The performance of two different methods, namely electrophoresis and diffusion, for driving the attachment of Au nanoparticles using a chemical cross-linker on chemically patterned domains of polystyreneblock-poly(methyl methacrylate) (PS-b-PMMA) thin films are evaluated. Significantly, electrophoresis is found to produce similar surface coverage as diffusion in 1/6th of the processing time with an ∼2-fold increase in the number of Au nanoparticles forming clusters. Furthermore, average interparticle spacing within Au nanoparticle clusters was found to decrease from 2−7 nm for diffusion deposition to approximately 1−2 nm for electrophoresis deposition, and the latter method exhibited better uniformity with most clusters appearing to have about 1 nm spacing between nanoparticles. The advantage of such fabrication capability is supported by calculations of local electric field enhancements using electromagnetic full-wave simulations from which we can estimate surface-enhanced Raman scattering (SERS) enhancements. In particular, full-wave results show that the maximum SERS enhancement, as estimated here as the fourth power of the local electric field, increases by a factor of 100 when the gap goes from 2 to 1 nm, reaching values as large as 10 10 , strengthening the usage of electrophoresis versus diffusion for the development of molecular sensors.
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