Localized surface plasmon resonance (LSPR) spectroscopy of metallic nanoparticles is a powerful technique for chemical and biological sensing experiments. Moreover, the LSPR is responsible for the electromagnetic-field enhancement that leads to surface-enhanced Raman scattering (SERS) and other surface-enhanced spectroscopic processes. This review describes recent fundamental spectroscopic studies that reveal key relationships governing the LSPR spectral location and its sensitivity to the local environment, including nanoparticle shape and size. We also describe studies on the distance dependence of the enhanced electromagnetic field and the relationship between the plasmon resonance and the Raman excitation energy. Lastly, we introduce a new form of LSPR spectroscopy, involving the coupling between nanoparticle plasmon resonances and adsorbate molecular resonances. The results from these fundamental studies guide the design of new sensing experiments, illustrated through applications in which researchers use both LSPR wavelength-shift sensing and SERS to detect molecules of chemical and biological relevance.

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. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

We present the first super-resolution optical images of single-molecule surface-enhanced Raman scattering (SM-SERS) hot spots, using super-resolution imaging as a powerful new tool for understanding the interaction between single molecules and nanoparticle hot spots. Using point spread function fitting, we map the centroid position of SM-SERS with +/-10 nm resolution, revealing a spatial relationship between the SM-SERS centroid position and the highest SERS intensity. We are also able to measure the unique position of the SM-SERS centroid relative to the centroid associated with nanoparticle photoluminescence, which allows us to speculate on the presence of multiple hot spots within a single diffraction-limited spot. These measurements allow us to follow dynamic movement of the SM-SERS centroid position over time as it samples different locations in space and explores regions larger than the expected size of a SM-SERS hot spot. We have proposed that the movement of the SERS centroid is due to diffusion of a single molecule on the surface of the nanoparticle, which leads to changes in coupling between the scattering dipole and the optical near field of the nanoparticle.

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. Second, plasmonic nanoparticles are explored as image contrast agents for both superlocalization and super-resolution imaging, offering benefits such as high photostability, large signal-to-noise, and distance-dependent spectral features but presenting challenges for localizing individual nanoparticles within a diffraction-limited spot. Finally, the use of plasmon-tailored excitation fields to achieve subdiffraction-limited spatial resolution is discussed, using localized surface plasmons and surface plasmon polaritons to create confined excitation volumes or image magnification to enhance spatial resolution.

Nonradiative decay of localized surface plasmons results in the production of hot charge carriers and the generation of heat, both of which can affect the efficiency of plasmon-mediated photoelectrochemical processes. Unfortunately, decoupling the impact of each effect on measured photocurrents is extremely challenging because the relative contribution of the two plasmon decay pathways cannot be controlled or easily measured. Here, we present a methodology for exploring the roles of hot carriers and heat generation on plasmon-mediated photoelectrochemical processes using scanning electrochemical microscopy (SECM). Light is used to drive a redox reaction at a plasmonic substrate, while an ultramicroelectrode tip is positioned close to the substrate to read out both the reaction products and the mass transfer rate of the redox species. By controlling the potential at the tip and substrate electrodes, the roles of photoinduced reactions at the substrate and enhanced mass transport to the tip due to local heating can be isolated and investigated independently. We observe enhanced photo-oxidation at the substrate that is due to both plasmon-generated hot holes as well as a thermal-induced change in the equilibrium potential of the redox molecules. The concentration of the reaction products changes as a function of excitation intensity, showing a linear dependence on hot carrier effects and an exponential dependence for thermal effects, and allowing us to quantify the relative contributions of the two plasmon decay pathways to enhanced photo-oxidation. This SECM approach is suitable for probing a variety of photoactive structures used in photovoltaic and photocatalytic devices.

In order to advance the field of single-molecule surface-enhanced Raman scattering (SM-SERS), a better understanding of colloid morphology and hot spot properties in noble metal nanoparticle aggregates is crucial. We present super-resolution optical studies of surface-enhanced Raman scattering (SERS) from rhodamine 6G (R6G) molecules adsorbed onto silver colloid aggregates correlated with scanning electron microscope (SEM) images of those same aggregates. The scattering intensity maps of the SERS signal, obtained from the super-resolution fits, are overlaid with SEM topographical images of the colloids to map the shape of the SERS hot spot and the spatial origin of SERS intensity fluctuations with sub-5 nm resolution. These results have vital implications for developing reproducible and robust substrates capable of SM-SERS.

Surface-enhanced Raman scattering (SERS) hot spots occur when molecules are positioned near regions of strongly enhanced electromagnetic fields on the surface of nano-featured plasmonic substrates. The emission from the molecule is coupled out into the far field by the plasmon modes of the substrate, but due to the diffraction-limit of light, the properties of this coupled molecule-plasmon emitter cannot be resolved using typical far-field optical microscopy techniques. However, by fitting the emission to a model function such as 2-dimensional Gaussian, the relative position of the emitter can be determined with precision better than 5 nm in a process known as super-resolution imaging. This tutorial review describes the basic principles of super-resolution imaging of SERS hot spots using single molecules to probe local electromagnetic field enhancements. New advances using dipole-based fitting functions and spectrally- and spatially-resolved measurements are described, providing new insight into SERS hot spots and the important roles of both the molecule and the substrate in defining their properties.

Surface-enhanced Raman scattering (SERS) provides vibrational information about molecules that are located within several nanometers of the surface of a metallic nanoparticle. This review describes the various challenges and successes of applying SERS inside living cells in order to gain information about the internal structure and dynamic processes occurring in the intracellular matrix. In particular, the challenges associated with the introduction of metal nanoparticles into cells are described, as well as the complexity of interpreting SERS spectra from within complex biological environments. Strategies for understanding and improving the specificity of SERS in vivo are also presented.