Tip-enhanced Raman spectroscopy (TERS) in air and ultra-high vacuum (UHV) has been refined over the years through the study of various adsorbates in different experimental configurations. Developing the technique toward more realistic working conditions would render possible the investigation of more complex solid/liquid systems like bio-membranes or energy conversion and storage devices, providing a powerful tool to characterize nanoscale electrochemical processes occurring at the interface with high sensitivity and resolution. However, the extension to solid/liquid interfaces and electrochemical conditions still remains a challenge and few reports have been published. We have built an electrochemical TERS setup with side-illumination geometry that adapts easily to different experimental conditions such as opacity, shape and dimensions of the sample. The instrument features a specially designed solid/liquid sample holder that is implemented in a standard commercial STM. The experimental scheme can, in principle, be adapted to upgrade classic air TERS setups for work in liquids. Here, we show potential-dependent EC-TER spectra of a monolayer of adenine adsorbed on Au(111). The intensity of the ring-breathing mode at 735 cm-1 decreases with increasing sample potential and is recovered again upon potential reversal. The intensity variation is attributed to orientational changes of adenine upon (dis)charging of the Au substrate.
Natalia Martín Sabanés and Katrin F. Domke, "Electrochemical tip-enhanced Raman spectroscopy
(Conference Presentation)," Proc. SPIE 9925, Nanoimaging and Nanospectroscopy IV, 992508 (Presented at SPIE Nanoscience + Engineering: August 28, 2016; Published: 11 November 2016); https://doi.org/10.1117/12.2239026.5161498103001.
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