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Naji, M. |
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Motta, Antonella |
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Aletan, Dirar |
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Mohamed, Tarek |
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Taccardi, Nicola |
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Petrov, R. H. | Madrid |
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Bih, L. |
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Casati, R. |
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Kočí, Jan | Prague |
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Azam, Siraj |
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Ospanova, Alyiya |
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Ali, M. A. |
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Rančić, M. |
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Ollier, Nadège |
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Azevedo, Nuno Monteiro |
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Landes, Michael |
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Chulhai, Dhabih
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article
Intramolecular insight into adsorbate-substrate interactions via low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy
Abstract
<p>Tip-enhanced Raman spectroscopy (TERS) provides chemical information for adsorbates with nanoscale spatial resolution, single-molecule sensitivity, and, when combined with scanning tunneling microscopy (STM), Ångstrom-scale topographic resolution. Performing TERS under ultrahigh-vacuum conditions allows pristine and atomically smooth surfaces to be maintained, while liquid He cooling minimizes surface diffusion of adsorbates across the solid surface, allowing direct STM imaging. Low-temperature TER (LT-TER) spectra differ from room-temperature TER (RT-TER), RT surface-enhanced Raman (SER), and LT-SER spectra because the vibrational lines are narrowed and shifted, revealing additional chemical information about adsorbate-substrate interactions. As an example, we present LT-TER spectra for the rhodamine 6G (R6G)/Ag(111) system that exhibit such unique spectral shifts. The high spectral resolution of LT-TERS provides intramolecular insight in that the shifted modes are associated with the ethylamine moiety of R6G. LT-TERS is a promising approach for unraveling the intricacies of adsorbate-substrate interactions that are inaccessible by other means.</p>