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      Quantum mechanical effects in plasmonic structures with subnanometre gaps

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          Abstract

          Metallic structures with nanogap features have proven highly effective as building blocks for plasmonic systems, as they can provide a wide tuning range of operating frequencies and large near-field enhancements. Recent work has shown that quantum mechanical effects such as electron tunnelling and nonlocal screening become important as the gap distances approach the subnanometre length-scale. Such quantum effects challenge the classical picture of nanogap plasmons and have stimulated a number of theoretical and experimental studies. This review outlines the findings of many groups into quantum mechanical effects in nanogap plasmons, and discusses outstanding challenges and future directions.

          Abstract

          Recent work has shown that quantum mechanical effects in plasmonic nanogap structures become important as the gap distances approach the subnanometre length-scale. Here, the authors review the major findings which challenge the classical picture of these structures and discuss future directions for the field.

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          Most cited references66

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          Biosensing with plasmonic nanosensors.

          Recent developments have greatly improved the sensitivity of optical sensors based on metal nanoparticle arrays and single nanoparticles. We introduce the localized surface plasmon resonance (LSPR) sensor and describe how its exquisite sensitivity to size, shape and environment can be harnessed to detect molecular binding events and changes in molecular conformation. We then describe recent progress in three areas representing the most significant challenges: pushing sensitivity towards the single-molecule detection limit, combining LSPR with complementary molecular identification techniques such as surface-enhanced Raman spectroscopy, and practical development of sensors and instrumentation for routine use and high-throughput detection. This review highlights several exceptionally promising research directions and discusses how diverse applications of plasmonic nanoparticles can be integrated in the near future.
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            Chemical mapping of a single molecule by plasmon-enhanced Raman scattering.

            Visualizing individual molecules with chemical recognition is a longstanding target in catalysis, molecular nanotechnology and biotechnology. Molecular vibrations provide a valuable 'fingerprint' for such identification. Vibrational spectroscopy based on tip-enhanced Raman scattering allows us to access the spectral signals of molecular species very efficiently via the strong localized plasmonic fields produced at the tip apex. However, the best spatial resolution of the tip-enhanced Raman scattering imaging is still limited to 3-15 nanometres, which is not adequate for resolving a single molecule chemically. Here we demonstrate Raman spectral imaging with spatial resolution below one nanometre, resolving the inner structure and surface configuration of a single molecule. This is achieved by spectrally matching the resonance of the nanocavity plasmon to the molecular vibronic transitions, particularly the downward transition responsible for the emission of Raman photons. This matching is made possible by the extremely precise tuning capability provided by scanning tunnelling microscopy. Experimental evidence suggests that the highly confined and broadband nature of the nanocavity plasmon field in the tunnelling gap is essential for ultrahigh-resolution imaging through the generation of an efficient double-resonance enhancement for both Raman excitation and Raman emission. Our technique not only allows for chemical imaging at the single-molecule level, but also offers a new way to study the optical processes and photochemistry of a single molecule.
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              Nanostructured plasmonic sensors.

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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                03 June 2016
                2016
                : 7
                : 11495
                Affiliations
                [1 ]Center for Nanoscale Science and Technology, National Institute of Standards and Technology , Gaithersburg, Maryland 20899, USA
                [2 ]Maryland Nano-Center, University of Maryland, College Park , Maryland 20742, USA
                [3 ]Material Physics Center CSIC-UPV/EHU and Donostia International Physics Center DIPC , Paseo Manuel de Lardizabal 5, Donostia-San Sebastián 20018, Spain
                [4 ]Institut des Sciences Moléculaires d′Orsay - UMR 8214 , CNRS-Université Paris Sud, Bâtiment 351, Orsay 91405, France
                [5 ]Nanophotonics Centre, Cavendish Laboratory, University of Cambridge , Cambridge CB3 0HE, UK
                [6 ]Department of Physics, MS61, Laboratory for Nanophotonics, Rice University , Houston, Texas 77005, USA
                [7 ]School of Physics, University of Melbourne , Victoria 3010, Australia
                [8 ]Department of Electrical and Electronic Engineering, University of Melbourne , Victoria 3010, Australia
                Author notes
                Author information
                http://orcid.org/0000-0002-9606-9488
                Article
                ncomms11495
                10.1038/ncomms11495
                4895716
                27255556
                6e789b67-3caf-42b0-a37f-fab15e3a0a6c
                Copyright © 2016, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 21 June 2015
                : 29 March 2016
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