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"Flash" preparation of strongly coupled metal nanoparticle clusters with sub-nm gaps by Ag+ soldering: toward effective plasmonic tuning of solution-assembled nanomaterials.

ABSTRACT: Noble metal nanoparticle oligomers are important in applications including plasmonics, catalysis, and molecular sensing. These nanostructural units featuring abundant inter-particle junctions are helpful for a physical/chemical understanding of structure-activity relationships of self-assembled metamaterials. A simple, rapid, and potentially general strategy for the preparation of monodisperse nanoparticle clusters in a homogeneous solution is highly desired for fundamental research toward liquid metamaterials and chemical/biological applications, but this is however very challenging. Here we report an Ag+ soldering strategy to prepare strongly coupled plasmonic (Au) and catalytic (Pt, Au@Pd (Au core with a Pd shell)) nanoparticle clusters almost instantly (<1 min) in a solution without special synthetic efforts, complicated surface decorations, or structure-directing templates. The resulting clusters are isolatable by agarose gel electrophoresis, resulting in mechanically stable products in high purity. The optical extinctions of Au nanodimers (the simplest and most basic form of a coupled structure) exhibit prominent longitudinal plasmonic coupling for nanoparticles down to 13.3 nm in diameter. Theoretical simulations attribute the strong coupling to the existence of a sub-nm gap (c.a. 0.76 nm) between soldered particles, suggesting an ideal (stable, soluble, monodisperse, and weakly passivated) substrate for surface enhanced Raman scattering (SERS) applications.

SUBMITTER: Liu M

PROVIDER: S-EPMC6021751 | biostudies-other | 2016 Aug

REPOSITORIES: biostudies-other

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"Flash" preparation of strongly coupled metal nanoparticle clusters with sub-nm gaps by Ag<sup>+</sup> soldering: toward effective plasmonic tuning of solution-assembled nanomaterials.

Liu Miao M Fang Lingling L Li Yulin Y Gong Ming M Xu An A Deng Zhaoxiang Z

Chemical science 20160504 8

Noble metal nanoparticle oligomers are important in applications including plasmonics, catalysis, and molecular sensing. These nanostructural units featuring abundant inter-particle junctions are helpful for a physical/chemical understanding of structure-activity relationships of self-assembled metamaterials. A simple, rapid, and potentially general strategy for the preparation of monodisperse nanoparticle clusters in a homogeneous solution is highly desired for fundamental research toward liqui ...[more]

PMID: 30034682

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Project description:In this work, we have designed highly sensitive plasmonic metasensors based on atomically thin perovskite nanomaterials with a detection limit up to 10-10 refractive index units (RIU) for the target sample solutions. More importantly, we have improved phase singularity detection with the Goos-Hänchen (GH) effect. The GH shift is known to be closely related to optical phase signal changes; it is much more sensitive and sharp than the phase signal in the plasmonic condition, while the experimental measurement setup is much more compact than that of the commonly used interferometer scheme to exact the phase signals. Here, we have demonstrated that plasmonic sensitivity can reach a record-high value of 1.2862 × 109 µm/RIU with the optimum configurations for the plasmonic metasensors. The phase singularity-induced GH shift is more than three orders of magnitude larger than those achievable in other metamaterial schemes, including Ag/TiO2 hyperbolic multilayer metamaterials (HMMs), metal-insulator-metal (MIM) multilayer waveguides with plasmon-induced transparency (PIT), and metasurface devices with a large phase gradient. GH sensitivity has been improved by more than 106 times with the atomically thin perovskite metasurfaces (1.2862 × 109 µm/RIU) than those without (918.9167 µm/RIU). The atomically thin perovskite nanomaterials with high absorption rates enable precise tuning of the depth of the plasmonic resonance dip. As such, one can optimize the structure to reach near zero-reflection at the resonance angle and the associated sharp phase singularity, which leads to a strongly enhanced GH lateral shift at the sensor interface. By integrating the 2D perovskite nanolayer into a metasurface structure, a strong localized electric field enhancement can be realized and GH sensitivity was further improved to 1.5458 × 109 µm/RIU. We believe that this enhanced electric field together with the significantly improved GH shift would enable single molecular or even submolecular detection for hard-to-identify chemical and biological markers, including single nucleotide mismatch in the DNA sequence, toxic heavy metal ions, and tumor necrosis factor-α (TNFα).

Dataset Information

"Flash" preparation of strongly coupled metal nanoparticle clusters with sub-nm gaps by Ag+ soldering: toward effective plasmonic tuning of solution-assembled nanomaterials.

Publications

"Flash" preparation of strongly coupled metal nanoparticle clusters with sub-nm gaps by Ag<sup>+</sup> soldering: toward effective plasmonic tuning of solution-assembled nanomaterials.

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