Journal
MOLECULAR PHYSICS
Volume 108, Issue 16, Pages 2039-2059Publisher
TAYLOR & FRANCIS LTD
DOI: 10.1080/00268976.2010.506891
Keywords
single-molecule spectroscopy; surface- and tip-enhanced Raman spectroscopy; tip-enhanced Raman spectroscopy and microscopy; fluorescence quenching; photobleaching; brilliant cresyle blue; rhodamine 6g; ultra high vacuum
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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 10(14) in single-molecule SERS is critically discussed, in particular in the view of recent experimental and theoretical results that limits the electromagnetic enhancement <= 10(11). 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.
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