Tip-enhanced Raman spectroscopy (TERS) is a variant of

surface-enhanced Raman spectroscopy Surface-enhanced Raman spectroscopy or surface-enhanced Raman scattering (SERS) is a surface-sensitive technique that enhances Raman scattering by molecules adsorbed on rough metal surfaces or by nanostructures such as plasmonic-magnetic silica ...

(SERS) that combines scanning probe microscopy with Raman spectroscopy. High spatial resolution chemical imaging is possible ''via'' TERS, with routine demonstrations of nanometer spatial resolution under ambient laboratory conditions, or better at ultralow temperatures and high pressure. The maximum resolution achievable using an

optical microscope The optical microscope, also referred to as a light microscope, is a type of microscope that commonly uses visible light and a system of lenses to generate magnified images of small objects. Optical microscopes are the oldest design of microsco ...

, including

Raman microscope The Raman microscope is a laser-based microscopic device used to perform Raman spectroscopy.''Microscopical techniques in the use of the molecular optics laser examiner Raman microprobe'', by M. E. Andersen, R. Z. Muggli, Analytical Chemistry, 19 ...

s, is limited by the

Abbe limit The resolution of an optical imaging system a microscope, telescope, or camera can be limited by factors such as imperfections in the lenses or misalignment. However, there is a principal limit to the resolution of any optical system, due to th ...

, which is approximately half the wavelength of the incident light. Furthermore, with SERS spectroscopy the signal obtained is the sum of a relatively large number of molecules. TERS overcomes these limitations as the

Raman spectrum Raman spectroscopy () (named after Indian physicist C. V. Raman) is a Spectroscopy, spectroscopic technique typically used to determine vibrational modes of Molecule, molecules, although rotational and other low-frequency modes of systems may als ...

obtained originates primarily from the

molecules A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioche ...

within a few tens of nanometers of the tip.

History

The earliest reports of tip enhanced Raman spectroscopy typically used a

coupled with an

atomic force microscope Atomic force microscopy (AFM) or scanning force microscopy (SFM) is a very-high-resolution type of scanning probe microscopy (SPM), with demonstrated resolution on the order of fractions of a nanometer, more than 1000 times better than the diffr ...

. Tip-enhanced Raman spectroscopy coupled with a scanning tunneling microscope (STM-TERS) has also become a reliable technique, since it utilizes the gap mode plasmon between the metallic probe and the metallic substrate.

Equipment

Tip-enhanced Raman spectroscopy requires a

confocal microscope Confocal microscopy, most frequently confocal laser scanning microscopy (CLSM) or laser confocal scanning microscopy (LCSM), is an optical imaging technique for increasing optical resolution and contrast of a micrograph by means of using a sp ...

, and a

scanning probe microscope Scan may refer to: Acronyms * Schedules for Clinical Assessment in Neuropsychiatry (SCAN), a psychiatric diagnostic tool developed by WHO * Shared Check Authorization Network (SCAN), a database of bad check writers and collection agency for bad ...

. The optical microscope is used to align the laser focal point with the tip coated with a SERS active metal. The three typical experimental configurations are bottom illumination, side illumination, and top illumination, depending on which direction the incident laser propagates towards the sample, with respect to the substrate. In the case of STM-TERS, only side and top illumination configurations can be applied, since the substrate is required to be conductive, therefore typically being non-transparent. In this case, the incident laser is usually linearly polarized and aligned parallel to the tip, in order to generate confined surface plasmon at the tip apex. The sample is moved rather than the tip so that the laser remains focused on the tip. The sample can be moved systematically to build up a series of tip enhanced Raman spectra from which a Raman map of the surface can be built allowing for surface heterogeneity to be assessed with up to 1.7 nm resolution. Subnanometer resolution has been demonstrated in certain cases allowing for submolecular features to be resolved. FIFO NSOM Raman

In 2019, Yan group and Liu group at University of California, Riverside developed a lens-free nanofocusing technique, which concentrates the incident light from a tapered optical fiber to the tip apex of a metallic nanowire and collects the Raman signal through the same optical fiber. Fiber-in-fiber-out NSOM-TERS has been developed.

Applications

Several research have used TERS to image single atoms and the internal structure of the molecules. In 2019, the Ara Apkarian group at the

Center for Chemistry at the Space-Time Limit Center for Chemistry at the Space-Time Limit or CaSTL Center is a National Science Foundation Center for Chemical Innovation. The CaSTL Center was established through a cooperative agreement between the National Science Foundation and the Univers ...

University of California, Irvine The University of California, Irvine (UCI or UC Irvine) is a public land-grant research university in Irvine, California. One of the ten campuses of the University of California system, UCI offers 87 undergraduate degrees and 129 graduate and pr ...

imaged vibrational normal modes of single

porphyrin Porphyrins ( ) are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges (=CH−). The parent of porphyrin is porphine, a rare chemical com ...

molecules using TERS. TERS-based DNA sequencing has also been demonstrated.

References

{{Raman spectroscopy Raman scattering Raman spectroscopy Surface science Plasmonics