Plasmons in strongly coupled metallic nanostructures.

CONTENTS 1. Introduction 1.1. Fundamental Theory of Surface-Enhanced Raman Scattering 1.2. Optical Properties of SERS Tags 2. Synthesis of SERS Tags 2.1. Noble Metal Nanosubstrates 2.1.1. Single Particle-Based SERS Substrates 2.1.2. Nanoparticle Cluster-Based Substrates 2.2. Raman Reporter Molecules 2.2.1. Selection Principles and Reporter Types 2.2.2. Self-Assembled Monolayer Coverage Strategy 2.3. Surface Coating for Protection 2.3.1. Biomolecule Coating 2.3.2. Polymer Coating 2.3.3. Liposome Coating 2.3.4. Silica Coating 2.4. Attachment of Targeting Molecules 3. Bioanalysis Applications 3.1. Ionic and Molecular Detection 3.2. Pathogen Detection 3.3. Live-Cell Imaging 3.3.1. Cancer Marker Detection 3.3.2. Intercellular Microenvironment Sensing 3.4. Tissue SERS Imaging 3.5. In Vivo SERS Imaging 4. Challenges and Perspectives 4.1. Reproducible Signal of SERS Tags 4.1.1. Precisely Controlled Hot Spots for Nanosubstrates 4.1.2. Calibration of SERS Intensities and Enhancements 4.2. Improving Multiplexing Capability 4.3. Reduced Size for Subcellular Imaging 4.4. Development of Multifunctional Nanoplatforms 4.4.1. Magnetic SERS Dots 4.4.2. Multimodal Imaging Dots 4.4.3. SERS Tag-Based Therapeutic Systems 4.5. Biocompatibility 5. Conclusions and Remarks

SERS Tags: Novel Optical Nanoprobes for Bioanalysis

Templated Techniques for the Synthesis and Assembly of Plasmonic Nanostructures

Metals support surface plasmons at optical wavelengths and have the ability to localize light to subwavelength regions. The field enhancements that occur in these regions set the ultimate limitations on a wide range of nonlinear and quantum optical phenomena. We found that the dominant limiting factor is not the resistive loss of the metal, but rather the intrinsic nonlocality of its dielectric response. A semiclassical model of the electronic response of a metal places strict bounds on the ultimate field enhancement. To demonstrate the accuracy of this model, we studied optical scattering from gold nanoparticles spaced a few angstroms from a gold film. The bounds derived from the models and experiments impose limitations on all nanophotonic systems.

https://science.sciencemag.org/content/sci/337/6098/1072.full.pdf

Probing the Ultimate Limits of Plasmonic Enhancement

Surface-enhanced Raman spectroscopy (SERS) and related spectroscopies are powered primarily by the concentration of the electromagnetic (EM) fields associated with light in or near appropriately nanostructured electrically-conducting materials, most prominently, but not exclusively high-conductivity metals such as silver and gold. This field concentration takes place on account of the excitation of surface-plasmon (SP) resonances in the nanostructured conductor. Optimizing nanostructures for SERS, therefore, implies optimizing the ability of plasmonic nanostructures to concentrate EM optical fields at locations where molecules of interest reside, and to enhance the radiation efficiency of the oscillating dipoles associated with these molecules and nanostructures. This review summarizes the development of theories over the past four decades pertinent to SERS, especially those contributing to our current understanding of SP-related SERS. Special emphasis is given to the salient strategies and theoretical approaches for optimizing nanostructures with hotspots as efficient EM near-field concentrating and far-field radiating substrates for SERS. A simple model is described in terms of which the upper limit of the SERS enhancement can be estimated. Several experimental strategies that may allow one to approach, or possibly exceed this limit, such as cascading the enhancement of the local and radiated EM field by the multiscale EM coupling of hierarchical structures, and generating hotspots by hybridizing an antenna mode with a plasmonic waveguide cavity mode, which would result in an increased local field enhancement, are discussed. Aiming to significantly broaden the application of SERS to other fields, and especially to material science, we consider hybrid structures of plasmonic nanostructures and other material phases and strategies for producing strong local EM fields at desired locations in such hybrid structures. In this vein, we consider some of the numerical strategies for simulating the optical properties and consequential SERS performance of particle-on-substrate systems that might guide the design of SERS-active systems. Finally, some current theoretical attempts are briefly discussed for unifying EM and non-EM contribution to SERS.

Electromagnetic theories of surface-enhanced Raman spectroscopy

The strongly enhanced and localized optical fields that occur within the gaps between metallic nanostructures can be leveraged for a wide range of functionality in nanophotonic and optical metamaterial applications. Here, we introduce a means of precise control over these nanoscale gaps through the application of a molecular spacer layer that is self-assembled onto a gold film, upon which gold nanoparticles (NPs) are deposited electrostatically. Simulations using a three-dimensional finite element model and measurements from single NPs confirm that the gaps formed by this process, between the NP and the gold film, are highly reproducible transducers of surface-enhanced resonant Raman scattering. With a spacer layer of roughly 1.6 nm, all NPs exhibit a strong Raman signal that decays rapidly as the spacer layer is increased.

/pdf/leveraging-nanoscale-plasmonic-modes-to-achieve-reproducible-32ulntl5fw.pdf

Leveraging nanoscale plasmonic modes to achieve reproducible enhancement of light.

Molecular control of plasmon coupling is investigated in sub-100 nm assemblies composed of 13 nm gold “satellite” particles tethered by reconfigurable DNA nanostructures to a 50 nm gold “core” particle. Reconfiguration of the DNA nanostructures from a compact to an extended state results in blue shifting of the assembly plasmon resonance, indicating reduced interparticle coupling and lengthening of the core−satellite tether. Scattering spectra of the core−satellite assemblies before and after reconfiguration are compared with spectra calculated using a structural model that incorporates the core/satellite ratio determined by TEM imaging and estimates of tether length based upon prior measurements of interparticle separation in DNA linked nanoparticle networks. A strong correspondence between measured and simulated difference spectra validates the structural models that link the observed plasmon modulation with DNA nanostructure reconfiguration.

Reconfigurable Core−Satellite Nanoassemblies as Molecularly-Driven Plasmonic Switches

Progress in the development and application of nanoengineered systems is limited by the availability of quantitative measurement techniques. For the engineering of nanoparticle (NP)-based systems, single NP characterization is essential, but existing methods are slow and low thoughput. We demonstrate a flow spectroscopy technique capable of analyzing hundreds of nanoparticles per second and use this technique for the high throughput analysis of nanoparticle surface-enhanced resonant Raman scattering (SERRS) tags. By measuring Rayleigh and Raman scattering from thousands of individual tags, tag preparations can be characterized based on their brightness and uniformity. The rapid analysis of individual nanoparticles using high spectral resolution flow spectroscopy will be useful in many areas of nanoengineering.

/pdf/high-throughput-single-nanoparticle-spectroscopy-3e0hkm23da.pdf

High throughput single nanoparticle spectroscopy.

An approach for studying steady-state nanoparticle concentration gradients arising in magnetic nanoparticle suspensions in response to strong magnetic field gradient is presented. The experimental approach makes use of microscopic optical absorption measurements of ferrofluid interacting with arrays of patterned magnets. Experimental results are found to be consistent with a simple theoretical description that predicts the local nanoparticle concentration over a wide range of magnetic field conditions and ferrofluid volume fractions.

Magnetic field induced concentration gradients in magnetic nanoparticle suspensions: Theory and experiment

Plasmon coupling is investigated in aqueous phase nanoassemblies composed of 13 nm gold “satellite” particles tethered by duplex DNA to a 50 nm gold “core” particle. The structures are comprised of a large core nanoparticle and small satellite particles such that formation of core-satellite assemblies can be detected through measurement of scattering spectra, even when an excess of unbound satellite particles are present. Rayleigh scattering spectra collected from bulk samples reveal enhanced scattering and/or red shifting of the plasmon resonance upon formation of assemblies, with the extent and character of the response determined by the number of base pairs in the duplex DNA tether. Distance-dependence of the coupling is investigated also through simulation using structural models based upon observed satellite coverage and prior measurements of interparticle separation in DNA-linked nanoparticle materials. Spectral differences between scattering from linked and unlinked assemblies are found to differ s...

David S. Sebba

Papers

Leveraging nanoscale plasmonic modes to achieve reproducible enhancement of light.

Reconfigurable Core−Satellite Nanoassemblies as Molecularly-Driven Plasmonic Switches

High throughput single nanoparticle spectroscopy.

Magnetic field induced concentration gradients in magnetic nanoparticle suspensions: Theory and experiment

Robust Detection of Plasmon Coupling in Core-Satellite Nanoassemblies Linked by DNA