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.

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Present and Future of Surface-Enhanced Raman Scattering

DOI: 10.1002/admt.201800628 applications (e.g., soft robotics, medical devices).[1–6] Despite state-of-the-art bulkbased planar integrated-circuit devices, their rigid and brittle nature gives rise to the incompatibility with curvilinear and soft human bodies, restricting the development of newborn human-friendly interactive electronics. In contrast, the bendable and flexible wearable electronics could be conformally attached onto human bodies almost without discomfort and succeed in performing a great deal of sensing functionalities. Realization of such promising goals requires the flexible sensor platforms provided with crucial characteristics of light weight, ultrathinness, superior flexibility, stretchability, high sensitivity as well as rapid response.[7–10] Inspired by the perceptive features of human skins, the wearable sensor systems are capable of acquiring abundant information from the external environment with the assistance of sensing modules, such as pressure sensors, strain sensors, temperature sensors, etc.[11] A typical example is their application in prosthetics that could afford the capacity to perceive touch or temperature for the disabled.[12] Additionally, the wearable sensor systems are able to identify physical or chemical signals produced by the human body, providing promising opportunities to evaluate health states.[5,13–15] Conventional skin-like sensor platforms primarily comprise one or two sensing modules, data processing units, and power supplies. Their unitary functionality, however, cannot satisfy the increasing demands of IoTs. Recently, the rapid advances in novel sensing materials, fabrication strategies, and innovative electronic constitution contribute to the development of versatile integration of multimodal sensors, which could synchronously distinguish diverse stimuli from the complex environment and monitor multiple vital signs from the human body.[16,17] In spite of several attempts done in terms of such multimodal sensor systems, one of the cumbersome issues originates from the crosscoupling effect among different categories of signals simultaneously generated by various sensors. Furthermore, the skin-like multiple sensor systems usually suffer from the limited number of repeated use, resulting in their high use-cost. The development of separable versatile devices may address this issue with one layer realized by costeffective materials and fabrication manners for disposable use and the other composed of relatively expensive components for repeatable applications.[18] Additionally, the multiple bending or Skin-inspired wearable devices hold great potentials in the next generation of smart portable electronics owing to their intriguing applications in healthcare monitoring, soft robotics, artificial intelligence, and human–machine interfaces. Despite tremendous research efforts dedicated to judiciously tailoring wearable devices in terms of their thickness, portability, flexibility, bendability as well as stretchability, the emerging Internet of Things demand the skininterfaced flexible systems to be endowed with additional functionalities with the capability of mimicking skin-like perception and beyond. This review covers and highlights the latest advances of burgeoning multifunctional wearable electronics, primarily including versatile multimodal sensor systems, self-healing material-based devices, and self-powered flexible sensors. To render the penetration of human-interactive devices into global markets and households, economical manufacturing techniques are crucial to achieve large-scale flexible systems with high-throughput capability. The booming innovations in this research field will push the scientific community forward and benefit human beings in the near future.

Multifunctional Skin-Inspired Flexible Sensor Systems for Wearable Electronics

Surface-enhanced Raman scattering (SERS) spectroscopy provides a noninvasive and highly sensitive route for fingerprint and label-free detection of a wide range of molecules. Recently, flexible SERS has attracted increasingly tremendous research interest due to its unique advantages compared to rigid substrate-based SERS. Here, the latest advances in flexible substrate-based SERS diagnostic devices are investigated in-depth. First, the intriguing prospect of point-of-care diagnostics is briefly described, followed by an introduction to the cutting-edge SERS technique. Then, the focus is moved from conventional rigid substrate-based SERS to the emerging flexible SERS technique. The main part of this report highlights the recent three categories of flexible SERS substrates, including actively tunable SERS, swab-sampling strategy, and the in situ SERS detection approach. Furthermore, other promising means of flexible SERS are also introduced. The flexible SERS substrates with low-cost, batch-fabrication, and easy-to-operate characteristics can be integrated into portable Raman spectroscopes for point-of-care diagnostics, which are conceivable to penetrate global markets and households as next-generation wearable sensors in the near future.

https://www.onlinelibrary.wiley.com/doi/epdf/10.1002/advs.201900925

Toward Flexible Surface-Enhanced Raman Scattering (SERS) Sensors for Point-of-Care Diagnostics

Localized surface plasmon resonance (LSPR) offers a valuable opportunity to improve the efficiency of photocatalysts. However, plasmonic enhancement of photoconversion is still limited, as most of metal-semiconductor building blocks depend on LSPR contribution of isolated metal nanoparticles. In this contribution, the concept of collective excitation of embedded metal nanoparticles is demonstrated as an effective strategy to enhance the utilization of plasmonic energy. The contribution of Au-nanochain to the enhancement of photoconversion is 3.5 times increase in comparison with that of conventional isolated Au nanoparticles. Experimental characterization and theoretical simulation show that strongly coupled plasmonic nanostructure of Au-nanochain give rise to highly intensive electromagnetic field. The enhanced strength of electromagnetic field essentially boosts the formation rate of electron-hole pair in semiconductor, and ultimately improves photocatalytic hydrogen evolution activity of semiconductor photocatalysts. The concept of embedded coupled-metal nanostructure represents a promising strategy for the rational design of high-performance photocatalysts.

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Collective excitation of plasmon-coupled Au-nanochain boosts photocatalytic hydrogen evolution of semiconductor.

Ambitions to reach atomic resolution with light have been a major force in shaping nano-optics, whereby a central challenge is achieving highly localized optical fields. A promising approach employs plasmonic nanoantennas, but fluorescence quenching in the vicinity of metallic structures often imposes a strict limit on the attainable spatial resolution, and previous studies have reached only 8 nm resolution in fluorescence mapping. Here, we demonstrate spatially and spectrally resolved photoluminescence imaging of a single phthalocyanine molecule coupled to nanocavity plasmons in a tunnelling junction with a spatial resolution down to ∼8 A and locally map the molecular exciton energy and linewidth at sub-molecular resolution. This remarkable resolution is achieved through an exquisite nanocavity control, including tip-apex engineering with an atomistic protrusion, quenching management through emitter–metal decoupling and sub-nanometre positioning precision. Our findings provide new routes to optical imaging, spectroscopy and engineering of light–matter interactions at sub-nanometre scales. Through the use of a plasmon-active atomically sharp tip and an ultrathin insulating film, and precise junction control in a highly confined nanocavity plasmon field at the scanning tunnelling microscope junction, sub-nanometre-resolved single-molecule near-field photoluminescence imaging with a spatial resolution down to ∼8 A is achieved.

Sub-nanometre resolution in single-molecule photoluminescence imaging

CdS core-Au plasmonic satellites nanostructure enhanced photocatalytic hydrogen evolution reaction

Understanding the mechanism of catalytic hydrogenation at the local environment requires chemical and topographic information involving catalytic sites, active hydrogen species, and their spatial distribution. Here we used tip-enhanced Raman spectroscopy (TERS) to study the catalytic hydrogenation of chloronitrobenzenethiol on a well-defined Pd(submonolayer)/Au(111) bimetallic catalyst (
$$p_{\rm{H}_{2}}$$

 = 1.5 bar, 298 K), where the surface topography and chemical fingerprint information were simultaneously mapped with nanoscale resolution (~10 nm). TERS imaging of the surface after catalytic hydrogenation confirms that the reaction occurs beyond the location of Pd sites. The results demonstrate that hydrogen spillover accelerates hydrogenation at Au sites as far as 20 nm from the bimetallic Pd/Au boundary. Density functional theory was used to elucidate the thermodynamics of interfacial hydrogen transfers. We demonstrate TERS to be a powerful analytical tool that provides a unique approach to spatially investigate the local structure–reactivity relationship in catalysis. Visualizing catalytic processes at the nanoscale is crucial to establish structure–activity relations, but remains very challenging. Here, hydrogen spillover is revealed with a 10 nm spatial resolution during hydrogenation of chloronitrobenzenethiol on a bimetallic Pd/Au catalyst by means of tip-enhanced Raman spectroscopy.

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Nanometre-scale spectroscopic visualization of catalytic sites during a hydrogenation reaction on a Pd/Au bimetallic catalyst

Tip-enhanced Raman spectroscopy can provide molecular fingerprint information with ultrahigh spatial resolution, but the tip will be easily contaminated, thus leading to artifacts. It also remains a great challenge to establish tip-enhanced fluorescence because of the quenching resulting from the proximity of the metal tip. Herein, we report shell-isolated tip-enhanced Raman and fluorescence spectroscopies by employing ultrathin shell-isolated tips fabricated by atomic layer deposition. Such shell-isolated tips not only show outstanding electromagnetic field enhancement in TERS but also exclude interference by contaminants, thus greatly promoting applications in solution. Tip-enhanced fluorescence has also been achieved using these shell-isolated tips, with enhancement factors of up to 1.7×103 , consistent with theoretical simulations. Furthermore, tip-enhanced Raman and fluorescence signals are acquired simultaneously, and their relative intensities can be manipulated by changing the shell thickness. This work opens a new avenue for ultrahigh resolution surface analysis using plasmon-enhanced spectroscopies.

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Hao Yin

Papers

CdS core-Au plasmonic satellites nanostructure enhanced photocatalytic hydrogen evolution reaction

Nanometre-scale spectroscopic visualization of catalytic sites during a hydrogenation reaction on a Pd/Au bimetallic catalyst

Shell-Isolated Tip-Enhanced Raman and Fluorescence Spectroscopy.

Shell‐Isolated Nanoparticle‐Enhanced Raman and Fluorescence Spectroscopies: Synthesis and Applications

Plasmon enhanced quantum dots fluorescence and energy conversion in water splitting using shell-isolated nanoparticles