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Understanding resonant coupling in plasmonic nanoassemblies is a challenging scientific endeavor, especially for particles with complex nanoarchitectures. Our ability to both model and measure this...

Multiphoton microscopy using short-wave infrared (SWIR) radiation offers nondestructive and high-resolution imaging through tissue. Two-photon fluorescence (TPF), for example, is commonly employed to increase the penetration depth and spatial resolution of SWIR imaging, but the broad spectral peaks limit its multiplexing capabilities. Hyper-Raman scattering, the vibrational analog of TPF, yields spectral features on the order of 20 cm-1 and reporter-functionalized noble metal nanoparticles (NPs) provide a platform for both hyper-Raman signal enhancement and selective targeting in biological media. Herein we report the first tissue imaging study employing surface-enhanced resonance hyper-Raman scattering (SERHRS), the two-photon analog of surface-enhanced resonance Raman scattering. Specifically, we employ multicore gold-silica NPs (Au@SiO2 NPs) functionalized with a near infrared-resonant cyanine dye, 3,3'-diethylthiatricarbocyanine iodide as a SERHRS reporter. SWIR SERHRS spectra are efficiently acquired from mouse spleen tissue. SWIR SERHRS combines two-photon imaging advantages with narrow vibrational peak widths, presenting future applications of multitargeted bioimaging.

Author(s): Liberko, JJ; Busche, JA; Seils, R; Bechtel, HA; Rack, PD; Masiello, DJ; Camden, JP | Abstract: Spectroscopic interrogation of materials in the midinfrared with nanometer spatial resolution is inherently difficult due to the long wavelengths involved, reduced detector efficiencies, and limited availability of spectrally bright, coherent light sources. Technological advances are driving techniques that overcome these challenges, enabling material characterization in this relatively unexplored spectral regime. Synchrotron infrared nanospectroscopy (SINS) is an imaging technique that provides local sample information of nanoscale target specimens in an experimental energy window between 330 and 5000 cm-1. Using SINS, we analyzed a series of individual gold nanorods patterned on a SiO2 substrate and on a flake of hexagonal boron nitride. The SINS spectra reveal interactions between the nanorod photonic Fabry-Perot resonances and the surface phonon polaritons of each substrate, which are characterized as avoided crossings. A coupled oscillator model of the hybrid system provides a deeper understanding of the coupling and provides a theoretical framework for future exploration.

The unique optical properties of surface plasmon resonances in nanostructured materials have attracted considerable attention, broadly impacting both fundamental research and applied technologies r...

A new optical delivery system has been developed for the (scanning) transmission electron microscope. Here we describe the in situ and “rapid ex situ” photothermal heating modality of the system, which delivers >200 mW of optical power from a fiber-coupled laser diode to a 3.7 μm radius spot on the sample. Selected thermal pathways can be accessed via judicious choices of the laser power, pulse width, number of pulses, and radial position. The long optical working distance mitigates any charging artifacts and tremendous thermal stability is observed in both pulsed and continuous wave conditions, notably, no drift correction is applied in any experiment. To demonstrate the optical delivery system’s capability, we explore the recrystallization, grain growth, phase separation, and solid state dewetting of a Ag0.5Ni0.5 film. Finally, we demonstrate that the structural and chemical aspects of the resulting dewetted films was assessed.

Leveraging recent advances in electron energy monochromation and aberration correction, we record the spatially resolved infrared plasmon spectrum of individual tin-doped indium oxide nanocrystals using electron energy-loss spectroscopy (EELS). Both surface and bulk plasmon responses are measured as a function of tin doping concentration from 1-10 atomic percent. These results are compared to theoretical models, which elucidate the spectral detuning of the same surface plasmon resonance feature when measured from aloof and penetrating probe geometries. We additionally demonstrate a unique approach to retrieving the fundamental dielectric parameters of individual semiconductor nanocrystals via EELS. This method, devoid from ensemble averaging, illustrates the potential for electron-beam ellipsometry measurements on materials that cannot be prepared in bulk form or as thin films.

Limited approaches exist for imaging and recording spectra of individual nanostructures in the midinfrared region. Here we use infrared photothermal heterodyne imaging (IR-PHI) to interrogate single, high aspect ratio Au nanowires (NWs). Spectra recorded between 2,800 and 4,000 cm(−1) for 2.5–3.9-μm-long NWs reveal a series of resonances due to the Fabry–Pérot modes of the NWs. Crucially, IR-PHI images show structure that reflects the spatial distribution of the NW absorption, and allow the resonances to be assigned to the m = 3 and m = 4 Fabry–Pérot modes. This far-field optical measurement has been used to image the mode structure of plasmon resonances in metal nanostructures, and is made possible by the superresolution capabilities of IR-PHI. The linewidths in the NW spectra range from 35 to 75 meV and, in several cases, are significantly below the limiting values predicted by the bulk Au Drude damping parameter. These linewidths imply long dephasing times, and are attributed to reduction in both radiation damping and resistive heating effects in the NWs. Compared to previous imaging studies of NW Fabry–Pérot modes using electron microscopy or near-field optical scanning techniques, IR-PHI experiments are performed under ambient conditions, enabling detailed studies of how the environment affects mid-IR plasmons.

In this work, we in situ monitor the laser annealing of template-fabricated silver substrates using surface-enhanced Raman scattering (SERS) and 4-mercaptobenzoic acid (4-MBA) as a molecular probe. The annealing process, which exhibits a strong dependence on the laser power, yields a large (>50×) increase in the SERS of the immobilized 4-MBA. This increased SERS response is correlated with the changing substrate morphology using optical and scanning electron microscope images. We attribute the large enhancement to the formation of nanogaps facilitated by binding of the 4-MBA through both thiol and COO(−) groups in a sandwich structure, resulting in both electromagnetic and chemical enhancement. This annealing effect, associated with the continuous increase of SERS intensity, was not limited to the AgNP arrays but included Ag films deposited on a variety of nanoporous templates. This study provides a simple strategy for in situ optimization of plasmonic SERS substrates.

Facile control of the radiative and nonradiative properties of plasmonic nanostructures is of practical importance to a wide range of applications in the biological, chemical, optical, information, and energy sciences. For example, the ability to easily tune not only the plasmon spectrum but also the degree of coupling to light and/or heat, quality factor, and optical mode volume would aid the performance and function of nanophotonic devices and molecular sensors that rely upon plasmonic elements to confine and manipulate light at nanoscopic dimensions. While many routes exist to tune these properties, identifying new approaches-especially when they are simple to apply experimentally-is an important task. Here, we demonstrate the significant and underappreciated effects that substrate thickness and dielectric composition can have upon plasmon hybridization as well as downstream properties that depend upon this hybridization. We find that even substrates as thin as ∼10 nm can nontrivially mix free-space plasmon modes, imparting bright character to those that are dark (and vice versa) and, thereby, modifying the plasmonic density of states as well as the system's near- and far-field optical properties. A combination of electron energy-loss spectroscopy (EELS) experiment, numerical simulation, and analytical modeling is used to elucidate this behavior in the finite substrate-induced mixing of dipole, quadrupole, and octupole corner-localized plasmon resonances of individual silver nanocubes.

Electron energy loss spectroscopy (EELS) performed in a scanning transmission electron microscope (STEM) has demonstrated unprecedented power in the characterization of surface plasmons. The subangstrom spatial resolution achieved in EELS and its capability of exciting the full set of localized surface plasmon resonance (LSPR) modes supported by a metallic nanostructure makes STEM/EELS an ideal tool in the study of LSPRs. The plasmonic properties characterized using EELS can be associated with geometric or structural features collected simultaneously in a STEM to achieve a deeper understanding of the plasmonic response. In this review, we provide the reader a thorough experimental description of EELS as a LSPR characterization tool and summarize the exciting recent progress in the field of STEM/EELS plasmon characterization.

In this Letter, we exploit recent breakthroughs in monochromated aberration-corrected scanning transmission electron microscopy (STEM) to resolve infrared plasmonic Fano antiresonances in individual nanofabricated disk-rod dimers. Using a combination of electron energy-loss spectroscopy (EELS) and theoretical modeling, we investigate and characterize a subspace of the weak coupling regime between quasi-discrete and quasi-continuum localized surface plasmon resonances where infrared plasmonic Fano antiresonances appear. This work illustrates the capability of STEM instrumentation to experimentally observe nanoscale plasmonic responses that were previously the domain only of higher resolution infrared spectroscopies.

Electron energy-loss spectroscopy (EELS) offers a window to view nanoscale properties and processes. When performed in a scanning transmission electron microscope, EELS can simultaneously render images of nanoscale objects with sub-nanometer spatial resolution and correlate them with spectroscopic information of $\sim10 - 100$ meV spectral resolution. Consequently, EELS is a near-perfect tool for understanding the optical and electronic properties of individual and few-particle plasmonic metal nanoparticles assemblies, which are significant in a wide range of fields. This review presents an overview of basic plasmonics and EELS theory and highlights several recent noteworthy experiments involving the electron-beam interrogation of plasmonic metal nanoparticle systems., When citing this paper, please use the following: Cherqui C, Thakkar N, Li G, Camden JP, Masiello DJ. 2015. Characterizing localized surface plasmons using electron energy-loss spectroscopy. Annu. Rev. Phys. Chem. 67: Submitted. Doi: 10.1146/annurev-physchem-040214-121612

We report the self-assembly of ultrasmooth AuxAg1–x nanoparticles with homogeneous composition via pulsed laser-induced dewetting (PLiD). The nanoparticles are truncated nanospheres that sustain unique plasmonic features. For the first time an electron energy loss spectroscopy (EELS) study elucidating the size and composition effects on the plasmonic modes of truncated AuxAg1–x nanospheres is carried out. EELS characterization captures a linear red-shift in both bright and dark modes as a function of the atomic fraction of Au and a progressive red-shift of all modes as the size increases. The results are interpreted in the context of Mie theory and electron beam simulations. Armed with the full plasmonic spectrum of the AuxAg1–x system, the truncated spheres and their ordered arrays synthesized via PLiD have promise as elements in advanced photonic devices.

Motivated to explore the ultimate limits of surface-enhanced nonlinear spectroscopies, we report on the first observation of molecular second hyper-Raman scattering with the aid of surface enhancement and provide a new theoretical framework for first-principles calculations of the second hyper-Raman effect. Second hyper-Raman enhancement factors, determined to be a minimum of 10(5) times stronger than those in Raman scattering, demonstrate a clear trend toward larger enhancements for nonlinear phenomena, and the nearly quantitative agreement between simulation and experiment provides a unique spectroscopic window into higher-order molecular responses.

Owing to its extreme sensitivity and easy execution, surface-enhanced Raman spectroscopy (SERS) now finds application for a wide variety of problems requiring sensitive and targeted analyte detection. This widespread application has prompted a proliferation of different SERS-based sensors, suggesting the need for a framework to classify existing methods and guide the development of new techniques. After a brief discussion of the general SERS modalities, we classify SERS-based sensors according the origin of the signal. Three major categories emerge from this analysis: surface-affinity strategy, SERS-tag strategy, and probe-mediated strategy. For each case, we describe the mechanism of action, give selected examples, and point out general misconceptions to aid the construction of new devices. We hope this review serves as a useful tutorial guide and helps readers to better classify and design practical and effective SERS-based sensors.

Motivated by the need to study the size dependence of nanoparticle-substrate systems, we present a combined experimental and theoretical electron energy loss spectroscopy (EELS) study of the plasmonic spectrum of substrate-supported truncated silver nanospheres. This work spans the entire classical range of plasmonic behavior probing particles of 20-1000 nm in diameter, allowing us to map the evolution of localized surface plasmons into surface plasmon polaritons and study the size dependence of substrate-induced mode splitting. This work constitutes the first nanoscopic characterization and imaging of these effects in truncated nanospheres, setting the stage for the systematic study of plasmon-mediated energy transfer in nanoparticle-substrate systems.

The Fano interference phenomenon between localized surface plasmon resonances (LSPRs) of individual silver nanocubes is investigated using dark-field optical microscopy and electron-energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). By computing the polarization induced by the electron beam, we show that the hybridized modes responsible for this Fano interference are the same as those present in the resonance-Rayleigh scattering spectrum of an individual nanocube on a substrate.

Surface enhanced Raman scattering (SERS) is undergoing a renaissance, spurred largely by developments in the burgeoning field of plasmonics. This paper reviews the current status and future directions in plasmonic nanostructures for SERS. We show that engineered plasmonic nanostructures enable exciting new functionalities, including beamed Raman scattering and highly reproducible chips for single molecule SERS. We furthermore show that silicon photonics enables SERS to be performed using optically trapped Ag nanoparticle clusters.

Controlling light from single emitters is an overarching theme of nano-optics. Antennas are routinely used to modify the angular emission patterns of radio wave sources. "Optical antennas" translate these principles to visible and infrared wavelengths and have been recently used to modify fluorescence from single quantum dots and single molecules. Understanding the properties of single molecules, however, would be advanced were one able to observe their vibrational spectra through Raman scattering in a very reproducible manner but it is a hugely challenging task, as Raman scattering cross sections are very weak. Here we measure for the first time the highly directional emission patterns of Raman scattering from single molecules in the feed gaps of optical antennas fabricated on a chip. More than a thousand single molecule events are observed, revealing that an unprecedented near-unity fraction of optical antennas have single molecule sensitivity.

Plasmonics is a rapidly growing field, yet imaging of the plasmonic modes in complex nanoscale architectures is extremely challenging. Here we obtain spatial maps of the localized surface plasmon modes of high-aspect-ratio silver nanorods using electron energy loss spectroscopy (EELS) and correlate to optical data and classical electrodynamics calculations from the exact same particles. EELS mapping is thus demonstrated to be an invaluable technique for elucidating complex and overlapping plasmon modes.

The electromagnetic scattering properties of Ag nanoparticle aggregates known to be antennas for single-molecule surface-enhanced Raman scattering are investigated from a continuum electrodynamics perspective. High-resolution mappings of the spatial, spectral, and polarization dependence of the volumes of the aggregate’s electromagnetic hot spots reveal multiple active regions for enhanced Raman scattering activity by molecular chromophores. Further analysis of these regions using maps of polarization surface-charge density shows that some hot spots are due to the collective and phase-coherent excitation of localized surface-plasmon resonances, whereas others derive from interfering plasmonic excitations resulting from scattering from gaps and surfaces. The latter are still capable of generating intense local fields at certain excitation energies, whereas the former tend to provide the most spatially delocalized regions of high electromagnetic-field strength.

The surface-enhanced hyper-Raman scattering (SEHRS) of three analyte molecules has been obtained with excitation wavelengths at 1.55 and 1.8 μm. At 1.55 μm, excellent signal-to-noise ratios under modest experimental parameters demonstrate compelling potential for practical applications in chemical analysis and molecular imaging.

A large number of optical phenomena rely on the excitation of localized surface plasmon resonances (LSPR) in metallic nanostructures. Electron-energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) has emerged as a technique capable of mapping plasmonic properties on length scales 100 times smaller than optical wavelengths. While this technique is promising, the connection between electron-driven plasmons, encountered in EELS, and photon-driven plasmons, encountered in plasmonic devices, is not well understood. This Perspective highlights some of the contributions that have been made in correlating optical scattering and STEM/EELS from the exact same nanostructures. The experimental observations are further elucidated by comparison with theoretical calculations obtained from the electron-driven discrete dipole approximation, which provides a method to calculate EEL spectra for nanoparticles of arbitrary shape. Applications of plasmon mapping to the electromagnetic hot-spots encountered in single-molecule surface-enhanced Raman scattering and electron beam induced damage in silver nanocubes are discussed. It is anticipated that the complementarity of both techniques will address issues in fundamental and applied plasmonics going forward.

Energy transfer from plasmonic nanoparticles to semiconductors can expand the available spectrum of solar energy-harvesting devices. Here, we spatially and spectrally resolve the interaction between single Ag nanocubes with insulating and semiconducting substrates using electron energy-loss spectroscopy, electrodynamics simulations, and extended plasmon hybridization theory. Our results illustrate a new way to characterize plasmon–semiconductor energy transfer at the nanoscale and bear impact upon the design of next-generation solar energy-harvesting devices.

The last decade has seen an explosion in the study of plasmonic materials, with current applications including surface-enhanced spectroscopy, imaging beyond the diffraction limit, solar energy harvesting, and ultrasensitive detection. This proposal utilizes electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) to explore the near-field enhancements encountered upon excitation of the localized surface plasmon resonance. In particular we have studied Fano interferences using optical and electron energy-loss spectroscopies (EELS). Single silver nanocubes were utilized in this study due to the substrate-mediated hybridization of the primitive dipolar and quadrupolar plasmon modes that give rise to the Fano phenomenon. The cube at substrate system provides a unique opportunity to study the plasmonic energy transfer from metallic nanoparticles to neighboring materials, which is an essential component of plasmon-enhanced solar harvesting devices.

The ability to detect molecules at low concentrations is highly desired for applications that range from basic science to healthcare. Considerable interest also exists for ultrathin materials with high optical absorption, e.g. for microbolometers and thermal emitters. Metal nanostructures present opportunities to achieve both purposes. Metal nanoparticles can generate gigantic field enhancements, sufficient for the Raman spectroscopy of single molecules. Thin layers containing metal nanostructures (“metasurfaces”) can achieve near-total power absorption at visible and near-infrared wavelengths. Thus far, however, both aims (i.e. single molecule Raman and total power absorption) have only been achieved using metal nanostructures produced by techniques (high resolution lithography or colloidal synthesis) that are complex and/or difficult to implement over large areas. Here, we demonstrate a metasurface that achieves the near-perfect absorption of visible-wavelength light and enables the Raman spectroscopy of single molecules. Our metasurface is fabricated using thin film depositions, and is of unprecedented (wafer-scale) extent.

A major component of this proposal is to elucidate the connection between optical and electron excitation of plasmon modes in metallic nanostructures. These accomplishments are reported: developed a routine protocol for obtaining spatially resolved, low energy EELS spectra, and resonance Rayleigh scattering spectra from the same nanostructures.; correlated optical scattering spectra and plasmon maps obtained using STEM/EELS.; and imaged electromagnetic hot spots responsible for single-molecule surface-enhanced Raman scattering (SMSERS).

The study of plasmons is at the core of Surface‐Enhanced Raman Spectroscopy (SERS). Surface plasmons are generated from the interaction of light with the electrons on the surface of a metal and are responsible for the electromagnetic enhancement mechanism in SERS. It is believed that the different modes that are observed in plasmon resonances depend on the shape of the nanoparticles [1].The goal of this project is to correlate the optical measurements of nanostructures generated by the surface plasmons using Resonant Rayleigh Scattering, with high resolution structural information obtained by using Scanning Transmission Electron Microscopy (STEM). This technique will also reveal the different localized surface plasmon modes in the nanostructure as well as the relationship between the optical surface plasmons and the plasmons generated from the inelastic scattering of the electron beam. The measurement of the surface plasmon excitations in a STEM is called Electron Energy Loss Spectroscopy (EELS).The succe...

Extended abstract of a paper presented at Microscopy and Microanalysis 2011 in Nashville, Tennessee, USA, August 7–August 11, 2011.