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Journal Article

Single-molecule surface- and tip-enhanced Raman spectroscopy


Pettinger,  Bruno
Physical Chemistry, Fritz Haber Institute, Max Planck Society;

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Pettinger, B. (2010). Single-molecule surface- and tip-enhanced Raman spectroscopy. Molecular Physics, 108(16), 2039-2059. doi:10.1080/00268976.2010.506891.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0010-F51F-B
A review is given on single-molecule surface- and tip-enhanced Raman spectroscopy (SERS and TERS). It sketches the historical development along different routes toward huge near-field enhancements, the basis of single-molecule enhanced Raman spectroscopy; from SNOM to apertureless SNOM to tip-enhanced Raman spectroscopy (TERS) and microscopy; from SERS to single-molecule SERS to single-molecule TERS. The claim of extremely high enhancement factors of 1014 in single-molecule SERS is critically discussed, in particular in the view of recent experimental and theoretical results that limits the electromagnetic enhancement to ≤ 1011. In the field of TERS only very few reports on single-molecule TERS exist: single-molecule TERS on dyes and on a protein (cytochrome c). In the latter case, TERS 'sees' even subunits of this protein, either amino-acids or the heme, depending on the orientation of the protein relative to the tip. The former case concerns the dye brilliant cresyl blue adsorbed either on a Au surface under ambient conditions or on a Au(111) surface in ultra high vacuum. These results indicate that significant progress is to be expected for TERS in general and for single-molecule TERS in particular.