Interfacial properties are highly important to the performance of some energy-related systems. The in-depth understanding of the interface requires highly sensitive in situ techniques that can provide fingerprint molecular information at nanometer resolution. We developed an electrochemical tip-enhanced Raman spectroscopy (EC-TERS) by introduction of the light horizontally to the EC-STM cell to minimize the optical distortion and to keep the TERS measurement under a well-controlled condition. We obtained potential-dependent EC-TERS from the adsorbed aromatic molecule on a Au(111) surface and observed a substantial change in the molecule configuration with potential as a result of the protonation and deprotonation of the molecule. Such a change was not observable in EC-SERS (surface-enhanced), indicating EC-TERS can more faithfully reflect the fine interfacial structure than EC-SERS. This work will open a new era for using EC-TERS as an important nanospectroscopy tool for the molecular level and nanoscale analysis of some important electrochemical systems including solar cells, lithium ion batteries, fuel cells, and corrosion.

Surface and interfaces play key roles in heterogeneous catalysis, electrochemistry and photo(electro)chemistry. Tip-enhanced Raman spectroscopy (TERS) combines plasmon-enhanced Raman spectroscopy with scanning probe microscopy to simultaneously provide a chemical fingerprint and morphological information for the sample at the nanometer spatial resolution. It is an ideal tool for achieving an in-depth understanding of the surface and interfacial processes, so that the relationship between structure and chemical performance can be established. We begin with the background of surfaces and interfaces and TERS, followed by a detailed discussion on some issues in experimental TERS, including tip preparation and TERS instrument configuration. We then focus on the progress of TERS for studying the surfaces and interfaces under different conditions, from ambient, to UHV, solid-liquid and electrochemical environments, followed by a brief introduction to the current understanding of the unprecedented high spatial resolution and surface selection rules. We conclude by discussing the future challenges for TERS practical applications in surfaces and interfaces.

After over 15 years of development, tip-enhanced Raman spectroscopy (TERS) is now facing a very important stage in its history. TERS offers high detection sensitivity down to single molecules and a high spatial resolution down to sub-nanometers, which make it an unprecedented nanoscale analytical technique offering molecular fingerprint information. The tip is the core element in TERS, as it is the only source through which to support the enhancement effect and provide the high spatial resolution. However, TERS suffers and will continue to suffer from the limited availability of TERS tips with a high enhancement, good stability, and high reproducibility. This review focuses on the tip-related issues in TERS. We first discuss the parameters that influence the enhancement and spatial resolution of TERS and the possibility to optimize the performance of a TERS system via an in-depth understanding of the enhancement mechanism. We then analyze the methods that have been developed for producing TERS tips, including vacuum-based deposition, electrochemical etching, electrodeposition, electroless deposition, and microfabrication, with discussion on the advantages and weaknesses of some important methods. We also tackle the issue of lifetime and protection protocols of TERS tips which are very important for the stability of a tip. Last, some fundamental problems and challenges are proposed, which should be addressed before this promising nanoscale characterization tool can exert its full potential. Graphical Abstract ᅟ.