Engineering Efficient Self-Assembled Plasmonic Nanostructures by Configuring Metallic Nanoparticle’s Morphology

We reveal the significance of plasmonic nanoparticle’s (NP) shape and its surface morphology en route to an efficient self-assembled plasmonic nanoparticle cluster. A simplified model is simulated in the form of free-space dimer and trimer nanostructures (NPs in the shape of a sphere, cube, and disk). A ~200% to ~125% rise in near-field strength (gap mode enhancement) is observed for spherical NPs in comparison with cubical NPs (from 2 nm to 8 nm gap sizes). Full-width three-quarter maximum reveals better broad-spectral optical performance in a range of ~100 nm (dimer) and ~170 nm (trimer) from spherical NPs as compared to a cube (~60 nm for dimer and trimer). These excellent properties for sphere-based nanostructures are merited from its dipole mode characteristics.

Designing an Efficient Self-Assembled Plasmonic Nanostructures from Spherical Shaped Nanoparticles

We reveal the significance of plasmonic nanoparticle’s (NP) shape and its surface morphology en route to an efficient self-assembled plasmonic nanoparticle cluster. A simplified model is simulated in the form of free-space dimer and trimer nanostructures (NPs in shape of sphere, cube, and disk). A ~ 200 % to ~ 125% raise in near field strength (gap mode enhancement) is observed for spherical NPs in comparison with cubical NPs (from 2 nm to 8 nm gap sizes). Full-width three-quarter maximum reveals better broad-spectral optical performance in a range of ~ 100 nm (dimer) and ~ 170 nm (trimer) from spherical NPs as compared to a cube (~ 60 nm for dimer and trimer). These excellent properties for sphere-based nanostructures are merited from its dipole mode characteristics.

Understanding the Role of Different Substrate Geometries for Achieving Optimum Tip-Enhanced Raman Scattering Sensitivity

Tip-enhanced Raman spectroscopy (TERS) has experienced tremendous progress over the last two decades. Despite detecting single molecules and achieving sub-nanometer spatial resolution, attaining high TERS sensitivity is still a challenging task due to low reproducibility of tip fabrication, especially regarding very sharp tip apices. Here, we present an approach for achieving strong TERS sensitivity via a systematic study of the near-field enhancement properties in the so-called gap-mode TERS configurations using the combination of finite element method (FEM) simulations and TERS experiments. In the simulation study, a gold tip apex is fixed at 80 nm of diameter, and the substrate consists of 20 nm high gold nanodiscs with diameter varying from 5 nm to 120 nm placed on a flat extended gold substrate. The local electric field distributions are computed in the spectral range from 500 nm to 800 nm with the tip placed both at the center and the edge of the gold nanostructure. The model is then compared with the typical gap-mode TERS configuration, in which a tip of varying diameter from 2 nm to 160 nm is placed in the proximity of a gold thin film. Our simulations show that the tip-nanodisc combined system provides much improved TERS sensitivity compared to the conventional gap-mode TERS configuration. We find that for the same tip diameter, the spatial resolution achieved in the tip-nanodisc model is much better than that observed in the conventional gap-mode TERS, which requires a very sharp metal tip to achieve the same spatial resolution on an extended metal substrate. Finally, TERS experiments are conducted on gold nanodisc arrays using home-built gold tips to validate our simulation results. Our simulations provide a guide for designing and realization of both high-spatial resolution and strong TERS intensity in future TERS experiments.

Graphene-coupled nanowire hybrid plasmonic gap mode–driven catalytic reaction revealed by surface-enhanced Raman scattering

The single-layer graphene (SLG)-coupled nanowire (NW) hybrid plasmonic gap mode (PGM)-driven molecular catalytic reaction was investigated experimentally and theoretically. First, an SLG-coupled NW was constructed, then the surface-enhanced Raman scattering (SERS) effect of graphene in the hybrid plasmonic gap was studied via the normal and oblique incidence of excitation light. The SERS peaks of the D and G of graphene are more intensely enhanced by oblique incidence than by normal incidence. Furthermore, the catalytic reaction of the dimerization of the 4-nitrobenzenethiol molecule to p,p′-dimercaptoazobenzene molecule driven by PGM was carried out by SERS. It was demonstrated that the efficiency of the PGM-driven catalytic reaction is much higher for oblique incidence than that for normal incidence. The mechanism of the PGM-driven catalytic reaction was studied by a finite-difference time-domain numerical simulation. When the PGM is excited by oblique incidence with θ = 30°, the coupling between the NW and SLG/SiO2 substrate increases to the maximum value. This is clearly evidenced by the excitation of a vertical bonding dipolar plasmon mode under the dipole approximation. The theoretical and experimental results were consistent with each other. This research may open up a pathway toward controlling PGM-driven catalytic reactions through polarization changes in excitation laser incidence on single anisotropic nanostructures.