Super-Resolution Surface-Enhanced Raman Scattering: Perspectives on the Past, Present, and Future.

Super-resolution surface-enhanced Raman scattering (SERS) allows researchers to overcome the resolution limit of far field optical microscopy and peer into electromagnetic hot spots with nanoscale resolution. By localizing the signal from single (or few) molecules on the surface of plasmonic nanoparticle aggregates, relationships between the spatial origin of the SERS signal, local electromagnetic field enhancements, and SERS intensity can be determined. This Perspective describes the successes and challenges of super-resolution SERS, from the earliest mapping of single-molecule SERS hot spots to the current state-of-the-art, while highlighting open questions and future opportunities to advance the field.

High-Throughput All-Optical Determination of Nanorod Size and Orientation.

As a single-particle characterization technique, optical microscopy has transformed our understanding of structure-function relationships of plasmonic nanoparticles, but the need for -correlated electron microscopy to obtain structural information handicaps an otherwise exceptional high-throughput technique. Here, we present an all-optical alternative to electron microscopy to accurately and quickly extract structural information about single gold nanorods (Au NRs) using calcite-assisted localization and kinetics (CLocK) microscopy. Color CLocK images of single Au NRs allow scattering from the longitudinal and transverse plasmon modes to be imaged simultaneously, encoding spectral data in CLocK images that can then be extracted to obtain Au NR size and orientation.

Nonlinear effects in single-particle photothermal imaging.

Although photothermal imaging was originally designed to detect individual molecules that do not emit or small nanoparticles that do not scatter, the technique is now being applied to image and spectroscopically characterize larger and more sophisticated nanoparticle structures that scatter light strongly. Extending photothermal measurements into this regime, however, requires revisiting fundamental assumptions made in the interpretation of the signal. Herein, we present a theoretical analysis of the wavelength-resolved photothermal image and its extension to the large particle scattering regime, where we find the photothermal signal to inherit a nonlinear dependence upon pump intensity, together with a contraction of the full-width-at-half-maximum of its point spread function.

Potential Dependent Spectroelectrochemistry of Electrofluorogenic Dyes on Indium-Tin Oxide.

Indium-tin oxide (ITO) is used in a variety of applications due to its electrical conductivity and optical transparency. Moreover, ITO coated glass is a common working electrode for spectroelectrochemistry. Thus, the ITO substrates should exhibit well-understood spectroscopic characteristics.

Calcite-Assisted Localization and Kinetics (CLocK) Microscopy.

Localization-based super-resolution imaging techniques have improved the spatial resolution of optical microscopy well below the diffraction limit, yet encoding additional information into super-resolved images, such as anisotropy and orientation, remains a challenge. Here we introduce calcite-assisted localization and kinetics (CLocK) microscopy, a multiparameter super-resolution imaging technique easily integrated into any existing optical microscope setup at low cost and with straightforward analysis. By placing a rotating calcite crystal in the infinity space of an optical microscope, CLocK microscopy provides immediate polarization and orientation information while maintaining the ability to localize an emitter/scatterer with <10 nm resolution.

Toward Quantitative Nanothermometry Using Single-Molecule Counting.

Photothermal heating of nanoparticles has applications in nanomedicine, photocatalysis, photoelectrochemistry, and data storage, but accurate measurements of temperature at the nanoparticle surface are lacking. Here we demonstrate progress toward a super-resolution DNA nanothermometry technique capable of reporting the surface temperature on single plasmonic nanoparticles. Gold nanoparticles are functionalized with double-stranded DNA, and the extent of DNA denaturation under heating conditions serves as a reporter of temperature.

Wavelength-Dependent Photothermal Imaging Probes Nanoscale Temperature Differences among Subdiffraction Coupled Plasmonic Nanorods.

Plasmonic structures confine electromagnetic energy at the nanoscale, resulting in local, inhomogeneous, controllable heating, but reading out the temperature using optical techniques poses a difficult challenge. Here, we report on the optical thermometry of individual gold nanorod trimers that exhibit multiple wavelength-dependent plasmon modes resulting in measurably different local temperature distributions. Specifically, we demonstrate how photothermal microscopy encodes different wavelength-dependent temperature profiles in the asymmetry of the photothermal image point spread function.

Special topic on emerging directions in plasmonics.

Plasmonics enables a wealth of applications, including photocatalysis, photoelectrochemistry, photothermal heating, optoelectronic devices, and biological and chemical sensing, while encompassing a broad range of materials, including coinage metals, doped semiconductors, metamaterials, 2D materials, bioconjugates, and chiral assemblies. Applications in plasmonics benefit from the large local electromagnetic field enhancements generated by plasmon excitation, as well as the products of plasmon decay, including photons, hot charge carriers, and heat. This special topic highlights recent work in both theory and experiment that advance our fundamental understanding of plasmon excitation and decay mechanisms, showcase new applications enabled by plasmon excitation, and highlight emerging classes of materials that support plasmon excitation.

Present and Future of Surface-Enhanced Raman Scattering.

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products.

Active Far-Field Control of the Thermal Near-Field Plasmon Hybridization.

The ability to control and manipulate temperature at nanoscale dimensions has the potential to impact applications including heat-assisted magnetic recording, photothermal therapies, and temperature-driven reactivity. One challenge with controlling temperature at nanometer dimensions is the need to mitigate heat diffusion, such that the temperature only changes in well-defined nanoscopic regions of the sample. Here we demonstrate the ability to use far-field laser excitation to actively shape the thermal near-field in individual gold nanorod heterodimers by resonantly pumping either the in-phase or out-of-phase hybridized dipole plasmon modes.

Supercharging Superlocalization Microscopy: How Electrochemical Charging of Plasmonic Nanostructures Uncovers Hidden Heterogeneity.

Superlocalization microscopy enables the position of single plasmonic nanoparticles to be determined with <25 nm precision, enabling single-nanoparticle tracking and super-resolution imaging experiments to be conducted with sub-diffraction-limited spatial resolution. In many of these applications, the superlocalized position of the nanoparticle is assumed to correspond to the geometric center of the nanoparticle. However, work reported by Wang and co-workers in this issue of ACS Nano suggests that this assumption can be incorrect, based on studies in which electrochemically charging a nanoparticle leads to reproducible shifts in its scattering center.

Plasmon Heating Promotes Ligand Reorganization on Single Gold Nanorods.

Single-molecule fluorescence microscopy is used to follow dynamic ligand reorganization on the surface of single plasmonic gold nanorods. Fluorescently labeled DNA is attached to gold nanorods via a gold-thiol bond using a low-pH loading method. No fluorescence activity is initially observed from the fluorescent labels on the nanorod surface, which we attribute to a collapsed geometry of DNA on the metal.

Quantifying Wavelength-Dependent Plasmonic Hot Carrier Energy Distributions at Metal/Semiconductor Interfaces.

Hot carriers generated from the nonradiative decay of localized surface plasmons are capable of driving charge-transfer reactions at the surfaces of metal nanostructures. Photocatalytic devices utilizing plasmonic hot carriers are often based on metal nanoparticle/semiconductor heterostructures owing to their efficient electron-hole separation ability. The rapid thermalization of hot carriers generated at the metal nanoparticles yields a distribution of carrier energies that determines the capability of the photocatalytic device to drive redox reactions.

Quantifying photothermal heating at plasmonic nanoparticles by scanning electrochemical microscopy.

Photothermal heating at metal nanoparticles results from the non-radiative decay of localized surface plasmons. The local heat generation enhances the mass transport rate of redox molecules and causes a shift in their formal potential, both of which can impact an electrochemical process at the nanoparticle interface. Here we present a methodology for probing the surface temperature at a plasmonic nanoparticle substrate using scanning electrochemical microscopy (SECM).

Three-Dimensional Super-resolution Imaging of Single Nanoparticles Delivered by Pipettes.

Controlled three-dimensional positioning of nanoparticles is achieved by delivering single fluorescent nanoparticles from a nanopipette and capturing them at well-defined regions of an electrified substrate. To control the position of single nanoparticles, the force of the pressure-driven flow from the pipette is balanced by the attractive electrostatic force at the substrate, providing a strategy by which nanoparticle trajectories can be manipulated in real time. To visualize nanoparticle motion, a resistive-pulse electrochemical setup is coupled with an optical microscope, and nanoparticle trajectories are tracked in three dimensions using super-resolution fluorescence imaging to obtain positional information with precision in the tens of nanometers.

Tunable electroresistance and electro-optic effects of transparent molecular ferroelectrics.

Recent progress in molecular ferroelectrics (MOFEs) has been overshadowed by the lack of high-quality thin films for device integration. We report a water-based air-processable technique to prepare large-area MOFE thin films, controlled by supersaturation growth at the liquid-air interface under a temperature gradient and external water partial pressure. We used this technique to fabricate ImClO thin films and found a large, tunable room temperature electroresistance: a 20-fold resistance variation upon polarization switching.

Super-Resolution Imaging and Plasmonics.

This review describes the growing partnership between super-resolution imaging and plasmonics, by describing the various ways in which the two topics mutually benefit one another to enhance our understanding of the nanoscale world. First, localization-based super-resolution imaging strategies, where molecules are modulated between emissive and nonemissive states and their emission localized, are applied to plasmonic nanoparticle substrates, revealing the hidden shape of the nanoparticles while also mapping local electromagnetic field enhancements and reactivity patterns on their surface. However, these results must be interpreted carefully due to localization errors induced by the interaction between metallic substrates and single fluorophores.