Electrochemical tip-enhanced Raman spectroscopy (EC-TERS), which provides molecular fingerprint information with nanometer-scale spatial resolution, is a promising technique to study the structure-activity relationships of the electrochemical interface. In this work, we developed the electrochemical tip-enhanced Raman spectroscopy (EC-TERS) that possesses high sensitivity and nanoscale spatial resolution, as well as methods to fabricate TERS tips with a high enhancement. Based on the developed systems, we in-situ monitor the plasmon driven decarboxylation reaction. The spatial distribution of the effective hot carriers was visualized by TERS imaging of the nanoscale reaction region, which provides mechanistic insights into plasmon driven reactions.
Tip-enhanced Raman spectroscopy (TERS) can not only provide very high sensitivity but also high spatial resolution, and has found applications in various fields, including surface science, materials, and biology. Most of previous TERS studies were performed in air or in the ultrahigh vacuum. If TERS study can be performed in the electrochemical environment, the electronic properties of the surface can be well controlled so that the interaction of the molecules with the substrate and the configuration of the molecules on the surface can also be well controlled.
However, the EC-TERS is not just a simple combination of electrochemistry with TERS, or the combination of EC-STM with Raman. It is a merge of STM, electrochemistry and Raman spectroscopy, and the mutual interference among these techniques makes the EC-TERS particularly challenge: the light distortion in EC system, the sensitivity, the tip coating to work under EC-STM and retain the TERS activity and cleanliness.
We designed a special spectroelectrochemical cell to eliminate the distortion of the liquid layer to the optical path and obtain TER spectra of reasonably good signal to noise ratio for surface adsorbed molecules under electrochemical potential control. For example, potential dependent TERS signal have been obtained for adsorbed aromatic thiol molecule, and much obvious signal change compared with SERS has been found, manifesting the importance of EC-TERS to reveal the interfacial structure of an electrochemical system.
We further extended EC-TERS to electrochemical redox system, and clear dependence of the species during redox reaction can be identified.
Compared with some precise nanofabrication methods, such as EBL and FIB, holographic lithography (HL) is a convenient way to fabricate periodic structures in a large area and with superb uniformity. In this work, we developed the deep UV HL with 266 nm laser to obtain structure with a periodicity between 100 nm to 1μm, which cannot be achieved by traditional photolithography. We further developed a strategy to fabricate hybrid periodical dimmer arrays by deep UV HL and lift-off process, followed by selectively surface functionalization. Thermal treatment was employed to as an effective approach to tune the gap size, which provides an additionally adjustable factor. By coating the substrate with gold and the obtained nanostructures with gold or silver, we have obtained periodic plasmonic structure with excellent figure of merit based on refractive index change and strong and uniform SER activity. Such a hybrid periodical dimmer arrays can be used as an effective plasmonics structure, and have potential application as a platform for high-efficiency surface- and bio- analysis.
By using Surface-Enhanced Raman Scattering, we studied the orientation of liquid crystal 5CB absorbed on nano-roughened Ag and Au electrodes. Our results firstly suggest that the orientation of LC 5CB absorbed on nano-roughened Ag electrode is different from that of Au electrode. This implies that the interaction between LC 5CB and Ag is different from the interaction between LC 5CB and Au. The conclusion is that the orientation of LC 5CB absorbed on nano-roughened Ag electrode is perpendicular, and the orientation of LC 5CB absorbed on nano-roughened Au electrode is more complicated, including parallel, perpendicular and tilted.
Conference Committee Involvement (12)
Enhanced Spectroscopies and Nanoimaging 2025
3 August 2025 | San Diego, California, United States
Enhanced Spectroscopies and Nanoimaging 2024
18 August 2024 | San Diego, California, United States
Enhanced Spectroscopies and Nanoimaging 2023
20 August 2023 | San Diego, California, United States
Enhanced Spectroscopies and Nanoimaging 2022
21 August 2022 | San Diego, California, United States
Enhanced Spectroscopies and Nanoimaging 2021
2 August 2021 | San Diego, California, United States
Enhanced Spectroscopies and Nanoimaging 2020
24 August 2020 | Online Only, California, United States
Nanoimaging and Nanospectroscopy VI
19 August 2018 | San Diego, California, United States
Nanoimaging and Nanospectroscopy V
6 August 2017 | San Diego, California, United States
Nanoimaging and Nanospectroscopy IV
28 August 2016 | San Diego, California, United States
Nanoimaging and Nanospectroscopy III
9 August 2015 | San Diego, California, United States
Nanoimaging and Nanospectroscopy II
17 August 2014 | San Diego, California, United States
Nanoimaging and Nanospectroscopy
27 August 2012 | San Diego, California, United States
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