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      Suppression of photo-oxidation of organic chromophores by strong coupling to plasmonic nanoantennas

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          Abstract

          Strong coupling of organic chromophores to plasmonic nanoparticles was shown to markedly improve molecular photostability.

          Abstract

          Intermixed light-matter quasi-particles—polaritons—have unique optical properties owing to their compositional nature. These intriguing hybrid states have been extensively studied over the past decades in a wide range of realizations aiming at both basic science and emerging applications. However, recently, it has been demonstrated that not only optical but also material-related properties, such as chemical reactivity and charge transport, may be significantly altered in the strong coupling regime of light-matter interactions. We show that a nanoscale system, composed of a plasmonic nanoprism strongly coupled to excitons in a J-aggregated form of organic chromophores, experiences modified excited-state dynamics and, therefore, modified photochemical reactivity. Our experimental results reveal that photobleaching, one of the most fundamental photochemical reactions, can be effectively controlled and suppressed by the degree of plasmon-exciton coupling and detuning. In particular, we observe a 100-fold stabilization of organic dyes for the red-detuned nanoparticles. Our findings contribute to understanding of photochemical properties in the strong coupling regime and may find important implications for the performance and improved stability of optical devices incorporating organic dyes.

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          Single-molecule strong coupling at room temperature in plasmonic nanocavities

          Emitters placed in an optical cavity experience an environment that changes their coupling to light. In the weak-coupling regime light extraction is enhanced, but more profound effects emerge in the single-molecule strong-coupling regime where mixed light-matter states form1,2. Individual two-level emitters in such cavities become non-linear for single photons, forming key building blocks for quantum information systems as well as ultra-low power switches and lasers3–6. Such cavity quantum electrodynamics has until now been the preserve of low temperatures and complex fabrication, severely compromising their use5,7,8. Here, by scaling the cavity volume below 40 nm3 and using host-guest chemistry to align 1-10 protectively-isolated methylene-blue molecules, we reach the strong-coupling regime at room temperature and in ambient conditions. Dispersion curves from >50 plasmonic nanocavities display characteristic anticrossings, with Rabi frequencies of 300 meV for 10 molecules decreasing to 90 meV for single molecules, matching quantitative models. Statistical analysis of vibrational spectroscopy time-series and dark-field scattering spectra provide evidence of single-molecule strong coupling. This dressing of molecules with light can modify photochemistry, opening up the exploration of complex natural processes such as photosynthesis9 and pathways towards manipulation of chemical bonds10.
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            Strong coupling between surface plasmon polaritons and emitters: a review

            In this review we look at the concepts and state-of-the-art concerning the strong coupling of surface plasmon-polariton modes to states associated with quantum emitters such as excitons in J-aggregates, dye molecules and quantum dots. We explore the phenomenon of strong coupling with reference to a number of examples involving electromagnetic fields and matter. We then provide a concise description of the relevant background physics of surface plasmon polaritons. An extensive overview of the historical background and a detailed discussion of more recent relevant experimental advances concerning strong coupling between surface plasmon polaritons and quantum emitters is then presented. Three conceptual frameworks are then discussed and compared in depth: classical, semi-classical and fully quantum mechanical; these theoretical frameworks will have relevance to strong coupling beyond that involving surface plasmon polaritons. We conclude our review with a perspective on the future of this rapidly emerging field, one we are sure will grow to encompass more intriguing physics and will develop in scope to be of relevance to other areas of science.
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              Room-temperature polariton lasing in an organic single-crystal microcavity

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                Author and article information

                Journal
                Sci Adv
                Sci Adv
                SciAdv
                advances
                Science Advances
                American Association for the Advancement of Science
                2375-2548
                July 2018
                06 July 2018
                : 4
                : 7
                : eaas9552
                Affiliations
                [1 ]Department of Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden.
                [2 ]Centre of New Technologies, University of Warsaw, Banacha 2c, 02-097 Warsaw, Poland.
                [3 ]Faculty of Physics, University of Warsaw, Pasteura 5, 02-093 Warsaw, Poland.
                Author notes
                [* ]Corresponding author. Email: timurs@ 123456chalmers.se
                Author information
                http://orcid.org/0000-0002-8071-1587
                http://orcid.org/0000-0003-2535-4174
                http://orcid.org/0000-0002-4266-3721
                Article
                aas9552
                10.1126/sciadv.aas9552
                6035039
                29984306
                245e4459-1342-4689-8b3f-1336e0397ec4
                Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

                This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

                History
                : 10 January 2018
                : 23 May 2018
                Funding
                Funded by: doi http://dx.doi.org/10.13039/501100004063, Knut och Alice Wallenbergs Stiftelse;
                Funded by: doi http://dx.doi.org/10.13039/501100004200, Stiftelsen Olle Engkvist Byggmästare;
                Funded by: doi http://dx.doi.org/10.13039/501100004359, Vetenskapsrådet;
                Categories
                Research Article
                Research Articles
                SciAdv r-articles
                Optics
                Physics
                Optics
                Custom metadata
                Jeanelle Ebreo

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