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Title: Single-Molecule Chemistry with Surface- and Tip-Enhanced Raman Spectroscopy

Journal Article · · Chemical Reviews

Single-molecule (SM) surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS) have emerged as analytical techniques for characterizing molecular systems in nanoscale environments. SERS and TERS use plasmonically enhanced Raman scattering to characterize the chemical information on single molecules. Additionally, TERS can image single molecules with subnanometer spatial resolution. Here, we cover the development and history of SERS and TERS, including the concept of SERS hot spots and the plasmonic nanostructures necessary for SM detection, the past and current methodologies for verifying SMSERS, and investigations into understanding the signal heterogeneities observed with SMSERS. Moving on to TERS, we cover tip fabrication and the physical origins of the subnanometer spatial resolution. Then, we highlight recent advances of SMSERS and TERS in fields such as electrochemistry, catalysis, and SM electronics, which all benefit from the vibrational characterization of single molecules. SMSERS and TERS provide new insights on molecular behavior that would otherwise be obscured in an ensemble-averaged measurement.

Research Organization:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001785; CHE-1414466; FG02-09ER16109; DGE-0824162
OSTI ID:
1534472
Journal Information:
Chemical Reviews, Vol. 117, Issue 11; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 468 works
Citation information provided by
Web of Science

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Observing Single Molecules Complexing with Cucurbit[7]uril through Nanogap Surface-Enhanced Raman Spectroscopy journal February 2016
Visualizing Site-Specific Redox Potentials on the Surface of Plasmonic Nanoparticle Aggregates with Superlocalization SERS Microscopy journal January 2014
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A Raman-atomic force microscope for apertureless-near-field spectroscopy and optical trapping journal March 2002
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Plasmonic nanospheres with a handle—Local electrochemical deposition of Au or Ag at the apex of optically inactive W- or C-tips journal June 2015
Near-field Raman spectroscopy of nanocarbon materials journal January 2015
Electrochemical fabrication of silver tips for tip-enhanced Raman spectroscopy assisted by a machine vision system: Electrochemical fabrication of silver tips for TERS journal February 2016
Optical Origin of Subnanometer Resolution in Tip-Enhanced Raman Mapping journal May 2015
Modification of the Electrochemical Properties of Nile Blue through Covalent Attachment to Gold As Revealed by Electrochemistry and SERS journal June 2016
Variable-Temperature Tip-Enhanced Raman Spectroscopy of Single-Molecule Fluctuations and Dynamics journal December 2015
Enhancement of Single-Molecule Fluorescence Using a Gold Nanoparticle as an Optical Nanoantenna journal July 2006
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Revealing the molecular structure of single-molecule junctions in different conductance states by fishing-mode tip-enhanced Raman spectroscopy journal May 2011
Laterally Resolved and Direct Spectroscopic Evidence of Nanometer-Sized Lipid and Protein Domains on a Single Cell journal December 2010
Locally enhanced Raman spectroscopy with an atomic force microscope journal May 2000
Effects of Atomic Geometry and Electronic Structure of Platinum Surfaces on Molecular Adsorbates Studied by Gap-Mode SERS journal May 2014
Single-Molecule Surface-Enhanced Raman Spectroscopy of Crystal Violet Isotopologues: Theory and Experiment journal March 2011
High NA particle- and tip-enhanced nanoscale Raman spectroscopy with a parabolic-mirror microscope journal February 2008
Surface- and tip-enhanced Raman scattering of DNA components journal January 2006
Large-Scale Hot Spot Engineering for Quantitative SERS at the Single-Molecule Scale journal October 2015
Temperature Dependence of the Homogeneous Broadening of Resonant Raman Peaks Measured by Single-Molecule Surface-Enhanced Raman Spectroscopy journal November 2011
Electrochemical Tip-Enhanced Raman Spectroscopy journal September 2015
Surface-enhanced Raman spectroscopy: a brief retrospective journal January 2005
Overtones and Combinations in Single-Molecule Surface-Enhanced Resonance Raman Scattering Spectra journal March 2003
Metal-Catalyzed Chemical Reaction of Single Molecules Directly Probed by Vibrational Spectroscopy journal March 2016
Resonance Raman Cross-Sections and Vibronic Analysis of Rhodamine 6G from Broadband Stimulated Raman Spectroscopy journal March 2008
Studying the local character of Raman features of single-walled carbon nanotubes along a bundle using TERS journal February 2011
Plasmonic Materials for Surface-Enhanced Sensing and Spectroscopy journal May 2005
Fabrication of silver tips for scanning tunneling microscope induced luminescence journal August 2011
Structure and Composition of Insulin Fibril Surfaces Probed by TERS journal August 2012
Chemical mapping of a single molecule by plasmon-enhanced Raman scattering journal June 2013
Localized enhancement of electric field in tip-enhanced Raman spectroscopy using radially and linearly polarized light journal January 2013
Evidence of Natural Isotopic Distribution from Single-Molecule SERS journal February 2009
Ultrafast Nonradiative Decay Rates on Metallic Surfaces by Comparing Surface-Enhanced Raman and Fluorescence Signals of Single Molecules journal August 2009
Surface Enhanced Raman Spectroscopy: Towards Single Molecule Spectroscopy journal January 2000

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Probing ring contraction and decarboxylation of Rhodizonate and the influence of Cu (II) using surface‐enhanced Raman Scattering
  • Milán‐Garcés, Erix A.; Georgopoulos, Stéfanos Leite; Barros Santos, Patrícia
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Morphology dependent near-field response in atomistic plasmonic nanocavities journal January 2018
Indirect surface-enhanced Raman scattering assay of insulin-like growth factor 2 receptor protein by combining the aptamer modified gold substrate and silver nanoprobes journal February 2020
Rational design and synthesis of bifunctional metal nanocrystals for probing catalytic reactions by surface-enhanced Raman scattering journal January 2018
Electrodeposited surfaces with reversibly switching interfacial properties journal November 2019
Bioscaffold arrays decorated with Ag nanoparticles as a SERS substrate for direct detection of melamine in infant formula journal January 2019
Low cost tips for tip-enhanced Raman spectroscopy fabricated by two-step electrochemical etching of 125 µm diameter gold wires journal January 2018
Transforming Noble‐Metal Nanocrystals into Complex Nanostructures through Facet‐Selective Etching and Deposition journal August 2019
Modulating and probing the dynamic intermolecular interactions in plasmonic molecule-pair junctions journal January 2019
Identifying surface reaction intermediates with photoemission tomography text January 2019
Non-Adiabatic Molecular Dynamics of Molecules in the Presence of Strong Light-Matter Interactions text January 2019
In Situ Nanoscale Investigation of Catalytic Reactions in the Liquid Phase Using Zirconia-Protected Tip-Enhanced Raman Spectroscopy Probes journal March 2019
Reproducible Plasmonic Nanopyramid Array of Various Metals for Highly Sensitive Refractometric and Surface-Enhanced Raman Biosensing journal October 2018
Energetics and Vibrational Signatures of Nucleobase Argyrophilic Interactions journal October 2018
Plasmonic particle-on-film nanocavities: a versatile platform for plasmon-enhanced spectroscopy and photochemistry journal November 2018
A versatile DNA origami based plasmonic nanoantenna for label-free single-molecule SERS preprint August 2020

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