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We study the optical response of individual nm-wide plasmonic nanocavities using a nanoparticle-on-mirror design utilised as an electrode in an electrochemical cell. In this geometry Au nanoparticles are separated from a bulk Au film by an ultrathin molecular spacer, giving intense and stable Raman amplification of 100 molecules. Modulation of the plasmonic spectra and the SERS response is observed with an applied voltage under a variety of electrolytes. Different scenarios are discussed to untangle the various mechanisms that can be involved in the electronic interaction between NPs and electrode surfaces.

Resumen del trabajo presentado al 5th International Topical meeting on Nanophotonics and Metamaterials, celebrado en Seefeld (Austria) del 5 al 8 de enero de 2015., Plasmonically-coupled metal nanoparticles with nanometer-sized gaps produce extremely-localised and strongly enhanced optical fields. We tune gaps and use the fields to detect smallest traces of substances in the gap using spectroscopy and surface-enhance Raman scattering.

This is an open access article published under a Creative Commons Attribution (CC-BY) License.-- et al., Gold nanoparticles are separated above a planar gold film by 1.1 nm thick self-assembled molecular monolayers of different conductivities. Incremental replacement of the nonconductive molecules with a chemically equivalent conductive version differing by only one atom produces a strong 50 nm blue-shift of the coupled plasmon. With modeling this gives a conductance of 0.17G0 per biphenyl-4,4′-dithiol molecule and a total conductance across the plasmonic junction of 30G0. Our approach provides a reliable tool quantifying the number of molecules in each plasmonic hotspot, here, We acknowledge financial support from EPSRC grant EP/G060649/1, EP/I012060/1, EP/L027151/1, EP/K028510/1, ERC grant LINASS 320503. F.B. acknowledges support from the Winton Programme for the Physics of Sustainability. C.T. and J.A. acknowledge financial support from Project FIS2013-41184-P from MINECO, ETORTEK 2014-15 of the Basque Department of Industry and IT756-13 from the Basque consolidated groups.

This is an open access article published under a Creative Commons Attribution (CC-BY) License.-- et al., Nanometer-sized gaps between plasmonically coupled adjacent metal nanoparticles enclose extremely localized optical fields, which are strongly enhanced. This enables the dynamic investigation of nanoscopic amounts of material in the gap using optical interrogation. Here we use impinging light to directly tune the optical resonances inside the plasmonic nanocavity formed between single gold nanoparticles and a gold surface, filled with only yoctograms of semiconductor. The gold faces are separated by either monolayers of molybdenum disulfide (MoS2) or two-unit-cell thick cadmium selenide (CdSe) nanoplatelets. This extreme confinement produces modes with 100-fold compressed wavelength, which are exquisitely sensitive to morphology. Infrared scattering spectroscopy reveals how such nanoparticle-on-mirror modes directly trace atomic-scale changes in real time. Instabilities observed in the facets are crucial for applications such as heat-assisted magnetic recording that demand long-lifetime nanoscale plasmonic structures, but the spectral sensitivity also allows directly tracking photochemical reactions in these 2-dimensional solids., This work was supported by the UK EPSRC grants EP/G060649/1, EP/L027151/1, Defence Science and Technology Laboratory (DSTL), and ERC grant 320503 LINASS. C.T. and J.A. acknowledge financial support from Project FIS2013-41184-P from MINECO, ETORTEK 2014-15 of the Basque Department of Industry and IT756-13 from the Basque consolidated groups.

This work is licensed under a Creative Commons Attribution 4.0 International License.-- et al., Nanomaterials find increasing application in communications, renewable energies, electronics and sensing. Because of its unsurpassed speed and highly tuneable interaction with matter, using light to guide the self-assembly of nanomaterials can open up novel technological frontiers. However, large-scale light-induced assembly remains challenging. Here we demonstrate an efficient route to nano-assembly through plasmon-induced laser threading of gold nanoparticle strings, producing conducting threads 12±2nm wide. This precision is achieved because the nanoparticles are first chemically assembled into chains with rigidly controlled separations of 0.9nm primed for re-sculpting. Laser-induced threading occurs on a large scale in water, tracked via a new optical resonance in the near-infrared corresponding to a hybrid chain/rod-like charge transfer plasmon. The nano-thread width depends on the chain mode resonances, the nanoparticle size, the chain length and the peak laser power, enabling nanometre-scale tuning of the optical and conducting properties of such nanomaterials., We acknowledge financial support from EPSRC grants EP/G060649/1, EP/K028510/1 and EP/L027151/1, ERC grants LINASS 320503 and ASPiRe 240629, and project FIS2010-19609-C02-01 from the Spanish Ministry of Science and Innovation. J.S.B. acknowledges the School of Physical Science, University of Cambridge, for the funding of the transmission electron microscope. S.K. acknowledges funding from the Biochemical Society (Krebs Memorial Scholarship) and the Cambridge Commonwealth Trust.

Increasing Yb3+ absorption efficiency is currently desired in a number of applications including bioimaging, photovoltaics, near infrared driven photocatalysis or ultra-short pulsed solid-state lasers. In this work, silver nanoparticles, which are connected forming disordered networks, have been self-assembled on Yb3+ doped RbTiOPO4 crystals to produce a remarkable enhancement of Yb3+ absorption, and hence in the photoluminescence of this ion. The results are interpreted taking into account the near-field response of the plasmonic networks, which display strong amplification of the electric field at the maximum of Yb3+ excitation at around 900 nm, together with the anisotropic character of the Yb3+ transitions in RbTiOPO4. We show that in the near field regime, the scattering of the plasmonic networks produces additional polarization field components to those of the incident field, which allows access to the largest transition dipolar moment of Yb3+ ions in RbTiOPO4. As a result, a much more efficient route for Yb3+ excitation takes place at the immediacy of the plasmonic networks. This work provides fundamental insights for improving the optical properties of rare earth ions by the suitable design of metallic nanoparticle arrangements, and constitutes a promising step towards the development of new multifunctional solid-state lasers.