Jianghao Li

Hybridized plasmon modes and near-field enhancement of metallic nanoparticle-dimer on a mirror

For the attractive plasmonic structure consisting of metal nanoparticles (NPs) on a mirror, the coexistence of near-field NP-NP and NP-mirror couplings is numerically studied at normal incidence. By mapping their 3D surface charge distributions directly, we have demonstrated two different kinds of mirror-induced bonding dipole plasmon modes and confirmed the bonding hybridizations of the mirror and the NP-dimer which may offer a much stronger near-field enhancement than that of the isolated NP dimers over a broad wavelength range. Further, it is revealed that the huge near-field enhancement of these two modes exhibit different dependence on the NP-NP and NP-mirror hot spots, while both of their near-field resonance wavelengths can be tuned to the blue exponentially by increasing the NP-NP gaps or the NP-mirror separation. Our results here benifit significantly the fundamental understanding and practical applications of metallic NPs on a mirror in plasmonics.

Analytical plasmon dispersion in subwavelength closely spaced Au nanorod arrays from planar metal–insulator–metal waveguides

Subwavelength closely spaced metallic nanorod arrays form attractive plasmonic structures. Describing their optical dispersion with an analytical model has been challenging to date, yet the collective resonances in the lattice can be finely tuned by changes in geometrical parameters and dielectric media, as reported by various publications. In this paper, we determine the plasmon dispersion relation in subwavelength closely spaced Au nanorod arrays for both hexagonal and square lattices. By 3D plasmon mapping using the finite element method (FEM), the orders of cavity modes in the lattice can be confirmed directly. Both the numerical and experimental results agree well with an analytical model for plasmon dispersion in planar metal–insulator–metal (MIM) waveguides of equivalent widths. This analytical model enables us to successfully predict the resonance wavelengths as well as the orders of cavity modes in the lattice. We attribute the physical origin of the equivalent width to a geometric effect, which can be qualitatively understood considering the Coulomb interactions between neighbouring nanorods. The work here is of significant benefit to both the optimized design of active plasmonic devices and the fundamental understanding of nano-optics.

Nanoparticle-on-mirror cavity modes for huge and/or tunable plasmonic field enhancement

We present a careful numerical study of nanoparticle (NP) faceting, highlighting the great influence of small morphological changes of NP-mirror cavities on near-field enhancement in the nanoparticle-on-mirror (NPOM) system. Using a 3D finite element method (FEM) plasmon mapping method, the active transverse cavity modes can be confirmed. For the dominant mode, we have found that, by increasing the facet width, the resonance can be tuned linearly to the red with little decrease of the peak near-field intensity. It is further demonstrated that by increasing the NP size, the near-field intensity can be strongly enhanced. Understanding of such extreme optics benefits significantly both the optimized design of potential plasmonic devices and the fundamental understanding of nano-optics. Collaborative experimental considerations are expected with the rapid development of nanotechnology.

Pinhole Effect on the Melting Behavior of Ag@Al2O3 SERS Substrates.

High-temperature surface-enhanced Raman scattering (SERS) sensing is significant for practical detections, and pinhole-containing (PC) metal@oxide structures possessing both enhanced thermal stability and superior SERS sensitivity are served as promising SERS sensors at extreme sensing conditions. Through tuning the Al2O3 precursors’ exposure time during atomic layer deposition (ALD), Al2O3 shells with different amount of pinholes were covered over Ag nanorods (Ag NRs). By virtue of these unique PC Ag@Al2O3 nanostructures, herein we provide an excellent platform to investigate the relationship between the pinhole rate of Al2O3 shells and the melting behavior, high-temperature SERS performances of these core-shell nanostructures. Pinhole effect on the melting procedures of PC Ag@Al2O3 substrates was characterized in situ via their reflectivity variations during heating, and the specific melting point was quantitatively estimated. It is found that the melting point of PC Ag@Al2O3 raised along with the decrement of pinhole rate, and substrates with less pinholes exhibited better thermal stability but sacrificed SERS efficiency. This work achieved highly reliable and precise control of the pinholes over Al2O3 shells, offering sensitive SERS substrates with intensified thermal stability and superior SERS performances at extreme sensing conditions.

Ag Nanorods-Oxide Hybrid Array Substrates: Synthesis, Characterization, and Applications in Surface-Enhanced Raman Scattering

Over the last few decades, benefitting from the sufficient sensitivity, high specificity, nondestructive, and rapid detection capability of the surface-enhanced Raman scattering (SERS) technique, numerous nanostructures have been elaborately designed and successfully synthesized as high-performance SERS substrates, which have been extensively exploited for the identification of chemical and biological analytes. Among these, Ag nanorods coated with thin metal oxide layers (AgNRs-oxide hybrid array substrates) featuring many outstanding advantages have been proposed as fascinating SERS substrates, and are of particular research interest. The present review provides a systematic overview towards the representative achievements of AgNRs-oxide hybrid array substrates for SERS applications from diverse perspectives, so as to promote the realization of real-world SERS sensors. First, various fabrication approaches of AgNRs-oxide nanostructures are introduced, which are followed by a discussion on the novel merits of AgNRs-oxide arrays, such as superior SERS sensitivity and reproducibility, high thermal stability, long-term activity in air, corrosion resistivity, and intense chemisorption of target molecules. Next, we present recent advances of AgNRs-oxide substrates in terms of practical applications. Intriguingly, the recyclability, qualitative and quantitative analyses, as well as vapor-phase molecule sensing have been achieved on these nanocomposites. We further discuss the major challenges and prospects of AgNRs-oxide substrates for future SERS developments, aiming to expand the versatility of SERS technique.

Semi-quantitative analysis of multiple chemical mixtures in solution at trace level by surface-enhanced Raman Scattering

Surface-enhanced Raman scattering (SERS) technology combines with chemometric method of principal component analysis (PCA) was used to calculate the composition of chemical mixtures in solution. We reported here that there exists composition discrepancy between molecules in solution and molecules adsorbed on Ag@Al2O3 nanorods substrates due to difference in adsorption kinetics of each component. We proposed here a way to calculate the adsorption kinetics factor for each component using a standard sample as the reference, with which one could correct the predictions given by PCA. We demonstrate the validity of this approach in estimating the compositions of mixtures with two, three and four components of 1, 4-Benzenedithiol, 2-Naphthalenethiol, 4-Mercaptobenzoic acid, and 4-Mercaptopyridine molecules, with acceptable errors. Furthermore, a general formula applied to more complex mixtures was proposed to calculate compositions in solution.