Editorial pubs.acs.org/CR
Introduction: Vibrational Nanoscopy
N
presence of a scanning probe microscopy tip. There are review articles on TERS at ambient conditions, on TERS in ultrahigh vacuum, on nanoantennas for near-field Raman microscopy, on the issue of resolution and enhancement in nano-Raman scattering microscopy, on core−shell nanoparticle-enhanced Raman spectroscopy, on stimulated Raman scattering, and on near-field Raman spectroscopy with aperture tips. These reviews with the common theme of Raman scattering are complemented with others on surface-enhanced IR spectroscopy using nanoantennas, on AFM-enabled IR spectroscopy, and on atomic-scale imaging and spectroscopy of electroluminescence at molecular interfaces. I would like to thank all the authors for their contributions, and wish the reader pleasure, enjoyment, and many new insights while immersing in this nice collection of reviews on vibrational nanoscopy!
anotechnology has become part of everyday life, with products such as smart coatings, solar cell materials, medical and cosmetic products, nanotech ski wax, ship masts, tennis rackets, and golf clubs using nanotubes, stink proof nano silver socks, and by now over 1000 others. Nanoscience is the driving force behind this, encompassing areas such as particle production and modification, nanobiotechnology, molecular electronics, the physics of nanotubes, atomically slim 2D and 1D materials, etc. However, the characterization of modern nanomaterials, in particular their detailed chemical analysis, has been lagging behind, because many of the spectroscopic and analytical tools do not have the spatial resolution required. Vibrational spectroscopy on the nanometer scale, or “Vibrational Nanoscopy”, has greatly aided in the characterization of modern nanomaterials, and has also developed into a field of its own, based on plasmonic effects, optical near-field phenomena, nanoantennas, tip-enhanced spectroscopy, and novel kinds of nanoparticles for stimulating local spectroscopic responses. This thematic issue of Chemical Reviews brings together almost a dozen reviews from experts from all over the world on the state of the art of vibrational nanoscopy, which builds on a number of landmark papers in the field, including some quite recent ones (I would like to emphasize that the following picks are skewed by personal taste and knowledge; they are not supposed to give a comprehensive review of the fieldthis is the job of the articles in this issue): the pioneering experiments by Dieter Pohl at IBM Rüschlikon/Zurich in the mid-1980s are considered the birth of the entire field of nearfield optics.1,2 Many of the early experiments were using simple absorption, Rayleigh scattering, or fluorescence emission as the optical contrast mechanism. None of these are very chemically informative, and early attempts with Raman scattering to obtain vibrational spectroscopic information, using aperture probes to deliver the illumination laser to a surface, were plagued with experimental difficulties.3,4 It took 15 years for vibrational spectroscopy to become a viable contrast mechanism for nearfield methods, by the introduction of a plasmonic “antenna” that was scanned within the focus of a laser beam brought to the sample surface via conventional, diffraction-limited optics. In the year 2000, four papers nearly simultaneously introduced tip-enhanced Raman spectroscopy (TERS),5−8 which is considered the birth of vibrational nanoscopy. The field is still developing rapidly, and quite recent examples of interesting advances in this area include the introduction of the so-called SHINERS,9 the chemical mapping of a single molecule by plasmon-enhanced Raman scattering with submolecular spatial resolution,10 and the monitoring of catalytic processes with superb spatial resolution.11,12 Increasingly, nanoscale vibrational spectroscopy is also used in liquids, including aqueous medium,13,14 which is of course of great interest to study chemical reactions and biological systems in situ. The articles in this thematic issue are designed to widen the view further. Vibrational nanoscopy is no longer restricted to Raman scattering, but includes inelastic tunneling, nanoinfrared spectroscopy, and optical emission stimulated by the © 2017 American Chemical Society
Renato Zenobi*
Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland
AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected]. ORCID
Renato Zenobi: 0000-0001-5211-4358 Notes
Views expressed in this editorial are those of the author and not necessarily the views of the ACS. Biography
Renato Zenobi is Professor of Analytical Chemistry at the Organic Chemistry Laboratory of the Swiss Federal Institute of Technology (ETH) Zurich. Born in Zurich, Switzerland in 1961, he received a M.S. degree (with Martin Quack) from the ETH Zurich in 1986, and a Ph.D. at Stanford University (with Richard N. Zare) in 1990. After two postdoctoral appointments at the University of Pittsburgh (with John T. Yates, Jr.) and at the University of Michigan (with Raoul Special Issue: Vibrational Nanoscopy Published: April 12, 2017 4943
DOI: 10.1021/acs.chemrev.7b00107 Chem. Rev. 2017, 117, 4943−4944
Chemical Reviews
Editorial
Kopelman), Zenobi returned to Switzerland in 1992 as a Werner Fellow at the EPFL, Lausanne, where he established his own research group. He became assistant professor at the ETH in 1995, was promoted to associate professor in 1997, and to full professor in 2000. Zenobi has published well over 400 scientific papers in areas that include laser-based analytical chemistry, electrospray and laser-assisted mass spectrometry, ambient mass spectrometry, and near-field optical microscopy and spectroscopy. He is perhaps best known for the invention and development of tip-enhanced Raman spectroscopy (TERS), a spectroscopic methodology with ≈10 nm spatial resolution.
REFERENCES (1) Pohl, D. W.; Denk, W.; Lanz, M. Optical Stethoscopy: Image Recording with Resolution λ/20. Appl. Phys. Lett. 1984, 44, 651−653. (2) Dürig, U.; Pohl, D. W.; Rohner, F. Near-Field Optical-Scanning Microscopy. J. Appl. Phys. 1986, 59, 3318−3327. (3) Tsai, D. P.; Othonos, A.; Moskovits, M.; Uttamchandani, D. Raman-Spectroscopy Using a Fiberoptic Probe with Subwavelength Aperture. Appl. Phys. Lett. 1994, 64, 1768−1770. (4) Jahncke, C. L.; Hallen, H. D.; Paesler, M. A. Nano-Raman Spectroscopy and Imaging with Near-Field Scanning Optical Microscope. J. Raman Spectrosc. 1996, 27, 579−586. (5) Stöckle, R.; Suh, Y. D.; Deckert, V.; Zenobi, R. Nanoscale Chemical Analysis by Tip-Enhanced Raman Scattering. Chem. Phys. Lett. 2000, 318, 131−136. (6) Hayazawa, N.; Inouye, Y.; Sekkat, Z.; Kawata, S. Metallized Tip Amplification of Near-Field Raman Scattering. Opt. Commun. 2000, 183, 333−336. (7) Anderson, M. S. Locally Enhanced Raman Spectroscopy with an Atomic Force Microscope. Appl. Phys. Lett. 2000, 76, 3130−3132. (8) Pettinger, B.; Picardi, G.; Schuster, R.; Ertl, G. Surface Enhanced Raman Spectroscopy: Towards Single Molecule Spectroscopy. Electrochemistry 2000, 68, 942−949. (9) Li, J. F.; Huang, Y. F.; Ding, Y.; Yang, Z. L.; Li, S. B.; Zhou, X. S.; Fan, F. R.; Zhang, W.; Zhou, Z. Y.; Wu, D. Y.; et al. Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy. Nature 2010, 464, 392− 395. (10) Zhang, R.; Zhang, Y.; Dong, Z. C.; Jiang, S.; Zhang, C.; Chen, L. G.; Zhang, L.; Liao, Y.; Aizpurua, J.; Luo, Y.; et al. Chemical Mapping of a Single Molecule by Plasmon-Enhanced Raman Scattering. Nature 2013, 498, 82−86. (11) van Schrojenstein Lantman, E.; Deckert-Gaudig, T.; Mank, A. J. G.; Deckert, V.; Weckhuysen, B. M. Catalytic Processes Monitored at the Nanoscale with Tip-Enhanced Raman Spectroscopy. Nat. Nanotechnol. 2012, 7, 583−586. (12) Zhong, J.-H.; Jin, X.; Meng, L.; Wang, X.; Su, H.-S.; Yang, Z.-L.; Williams, C. T.; Ren, B. Probing the Electronic and Catalytic Properties of a Bimetallic Surface with 3 nm Resolution. Nat. Nanotechnol. 2017, 12, 132−136. (13) Zeng, Z.-C.; Huang, S.-C.; Wu, D.-Y.; Meng, L.-Y.; Li, M.-H.; Huang, T.-X.; Zhong, J.-H.; Wang, X.; Yang, Z.-L.; Ren, B. Electrochemical Tip-Enhanced Raman Spectroscopy. J. Am. Chem. Soc. 2015, 137, 11928−11931. (14) Martín Sabanés, N.; Driessen, L. M. A.; Domke, K. F. Versatile Side-Illumination Geometry for Tip-Enhanced Raman Spectroscopy at Solid/Liquid Interfaces. Anal. Chem. 2016, 88, 7108−7114.
4944
DOI: 10.1021/acs.chemrev.7b00107 Chem. Rev. 2017, 117, 4943−4944
