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

Since 2000, there has been an explosion of activity in the field of plasmon-enhanced Raman spectroscopy (PERS), including surface-enhanced Raman spectroscopy (SERS), tip-enhanced Raman spectroscopy (TERS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In this Review, we explore the mechanism of PERS and discuss PERS hotspots — nanoscale regions with a strongly enhanced local electromagnetic field — that allow trace-molecule detection, biomolecule analysis and surface characterization of various materials. In particular, we discuss a new generation of hotspots that are generated from hybrid structures combining PERS-active nanostructures and probe materials, which feature a strong local electromagnetic field on the surface of the probe material. Enhancement of surface Raman signals up to five orders of magnitude can be obtained from materials that are weakly SERS active or SERS inactive. We provide a detailed overview of future research directions in the field of PERS, focusing on new PERS-active nanomaterials and nanostructures and the broad application prospect for materials science and technology. Assisted by rationally designed novel plasmonic nanostructures, surface-enhanced Raman spectroscopy has presented a new generation of analytical tools (that is, tip-enhanced Raman spectroscopy and shell-isolated nanoparticle-enhanced Raman spectroscopy) with an extremely high surface sensitivity, spatial resolution and broad application for materials science and technology.

Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials

Surface-enhanced Raman spectroscopy (SERS) inherits the rich chemical fingerprint information on Raman spectroscopy and gains sensitivity by plasmon-enhanced excitation and scattering. In particular, most Raman peaks have a narrow width suitable for multiplex analysis, and the measurements can be conveniently made under ambient and aqueous conditions. These merits make SERS a very promising technique for studying complex biological systems, and SERS has attracted increasing interest in biorelated analysis. However, there are still great challenges that need to be addressed until it can be widely accepted by the biorelated communities, answer interesting biological questions, and solve fatal clinical problems. SERS applications in bioanalysis involve the complex interactions of plasmonic nanomaterials with biological systems and their environments. The reliability becomes the key issue of bioanalytical SERS in order to extract meaningful information from SERS data. This review provides a comprehensive over...

Surface-Enhanced Raman Spectroscopy for Bioanalysis: Reliability and Challenges

Creating functional electrical circuits using individual or ensemble molecules, often termed as “molecular-scale electronics”, not only meets the increasing technical demands of the miniaturization of traditional Si-based electronic devices, but also provides an ideal window of exploring the intrinsic properties of materials at the molecular level. This Review covers the major advances with the most general applicability and emphasizes new insights into the development of efficient platform methodologies for building reliable molecular electronic devices with desired functionalities through the combination of programmed bottom-up self-assembly and sophisticated top-down device fabrication. First, we summarize a number of different approaches of forming molecular-scale junctions and discuss various experimental techniques for examining these nanoscale circuits in details. We then give a full introduction of characterization techniques and theoretical simulations for molecular electronics. Third, we highlig...

Molecular-Scale Electronics: From Concept to Function

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

Core–shell nanoparticles are at the leading edge of the hot research topics and offer a wide range of applications in optics, biomedicine, environmental science, materials, catalysis, energy, and so forth, due to their excellent properties such as versatility, tunability, and stability. They have attracted enormous interest attributed to their dramatically tunable physicochemical features. Plasmonic core–shell nanomaterials are extensively used in surface-enhanced vibrational spectroscopies, in particular, surface-enhanced Raman spectroscopy (SERS), due to the unique localized surface plasmon resonance (LSPR) property. This review provides a comprehensive overview of core–shell nanoparticles in the context of fundamental and application aspects of SERS and discusses numerous classes of core–shell nanoparticles with their unique strategies and functions. Further, herein we also introduce the concept of shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) in detail because it overcomes the long...

Core–Shell Nanoparticle-Enhanced Raman Spectroscopy

Surface-enhanced Raman spectroscopy: bottlenecks and future directions

NSF of China [21033007]; Ministry of Scientific and Technological Projects [2010IM040100]; 973 Program [2009CB930703]; NFFTBS [J0630429]

Song-Yuan Ding

Papers

Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials

Electromagnetic theories of surface-enhanced Raman spectroscopy

Core–Shell Nanoparticle-Enhanced Raman Spectroscopy

Surface-enhanced Raman spectroscopy: bottlenecks and future directions

Distinctive Enhanced and Tunable Plasmon Resonant Absorption from Controllable Au@Cu2O Nanoparticles: Experimental and Theoretical Modeling