Simultaneous LSPR and electronic sensing of potential induced ion adsorption onto gold nanowire arrays is presented. The formation of a Stern layer upon applying an electrochemical potential generated a complex optical response. Simulation of a lossy atomic layer on the nanowire array using the Multiple Multipole Program (MMP) corresponded very well to the experimentally observed peak position, intensity, and radius of curvature changes. Additionally, a significant voltage-dependent change in the resistance of the gold nanowire array was observed during the controlled formation of the electrical double layer. The results demonstrated that an applied electrochemical potential induces measurable changes in the optical and electrical properties of the gold nanowire surface. This is the first demonstration of combined plasmonic and nanowire resistance-based sensing of a surface process in the literature.
This work explores the alternative use of noble metal nanowire systems in large-scale array configurations to exploit both the nanowires’ conductive nature and localized surface plasmon resonance (LSPR). The first known nanowire-based system has been constructed, with which optical signals are influenced by the simultaneous application of electrochemical potentials. Optical characterization of nanowire arrays was performed by measuring the bulk refractive index sensitivity and the limit of detection. The formation of an electrical double layer was controlled in NaCl solutions to study the effect of local refractive index changes on the spectral response. Resonance peak shifts of over 4 nm, a bulk refractive index sensitivity up to 115 nm/RIU and a limit of detection as low as 4.5 × 10−4 RIU were obtained for gold nanowire arrays. Simulations with the Multiple Multipole Program (MMP) confirm such bulk refractive index sensitivities. Initial experiments demonstrated successful optical biosensing using a novel form of particle-based nanowire arrays. In addition, the formation of an ionic layer (Stern-layer) upon applying an electrochemical potential was also monitored by the shift of the plasmon resonance.
The controlled in situ growth of ordered gold nanoparticles and nanowire arrays has been studied by optically tracking changes in the local surface plasmon resonance (LSPR) spectrum. A spectrometer and custom-programmed analysis software track changes in the LSPR spectrum. The peak position, peak height (i.e. extinction intensity) and peak width (e.g. radius of curvature) were tracked over time to quantify the dynamic growth of gold as soon as the system was exposed to a commercial gold enhancement solution. This enables the controlled dynamic growth of nano-objects without the necessity of characterizing the growth and aggregation kinetics of the gold enhancement solution. The result was the successful enhancement of their electrically conductive and plasmonic properties, as well as the controlled growth and transformation of line-patterned nanoparticles into conductive particle-based nanowires.
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