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Attainment of spatial resolutions far below diffraction limits by means of optical methods constitutes a challenging task. Here, we design nonlinear nanorulers that are capable of accomplishing approximately 1 nm resolutions by utilizing the mechanism of plasmon-enhanced second-harmonic generation (PESHG). Through introducing Au@SiO2 (core@shell) shell-isolated nanoparticles, we strive to maneuver electric-field-related gap modes such that a reliable relationship between PESHG responses and gap sizes, represented by "PESHG nanoruler equation", can be obtained. Additionally validated by both experiments and simulations, we have transferred "hot spots" to the film-nanoparticle-gap region, ensuring that retrieved PESHG emissions nearly exclusively originate from this region and are significantly amplified. The PESHG nanoruler can be potentially developed as an ultrasensitive optical method for measuring nanoscale distances with higher spectral accuracies and signal-to-noise ratios.

In this study we use nanophotonic effects of graphene to study DNA hybridization: the z−4 nanoscale distance-dependence of the fluorescence lifetime for fluorophores located in the vicinity of graphene is for the first time used to track a DNA hybridization reaction with nanoscale resolution in real time. First, a nanostaircase with ≈2 nm steps from 0 to a total height of 48 nm is used as a nanoruler to confirm the distance dependence law. We find that the axial sensitivity is suited to determine the nanoscale surface roughness of these samples. The proof-of-concept DNA experiments in aqueous medium involve the hybridization of fluorescently labelled DNA beacons attached to CVD grown graphene with complementary (target) DNA added in solution. We track the conformational changes of the beacons statistically by determining the fluorescence lifetimes of the labelling dye and converting them into nanoscale distances from the graphene. In this way, we are able to monitor the vertical displacement of the label during DNA-beacon unfolding with an axial resolution reaching down to 1 nm. The measured distance increase during the DNA hybridization reaction of about 10 nm matches the length of the target DNA strand. Furthermore, the width of the fluorescence lifetime distributions could be used to estimate the molecular tilt angle of the hybridized ds-DNA configuration. The achieved nanoscale sensitivity opens innovation opportunities in material engineering, genetics, biochemistry and medicine., INL received support for this project from the CCDR-N via the project 'Nanotechnology based functional solutions' (Grant No. NORTE-01-0145-FEDER-000019) and from the Portuguese Foundation for Science and Technology (FCT) via the project 'ON4SupremeSens' PTDC/NAN-OPT/29417/2017. Edite Figueiras received a Marie Curie fellowship via the EU-EC COFUND program 'NanoTRAINforGrowth' (Grant No. 600375). U Minho research was partially supported by the FCT in the framework of the Strategic Funding UID/FIS/04650/2013.

International audience; Förster resonance energy transfer (FRET) plays a key role in biochemistry, organic photovoltaics, and lighting sources. FRET is commonly used as a nanoruler for the short (nanometer) distance between donor and acceptor dyes, yet FRET is equally sensitive to the mutual dipole orientation. The orientation dependence complicates the FRET analysis in biological samples and may even lead to the absence of FRET for perpendicularly oriented donor and acceptor dipoles. Here, we exploit the strongly inhomogeneous and localized fields in plasmonic nanoantennas to open new energy transfer routes, overcoming the limitations from the mutual dipole orientation to ultimately enhance the FRET efficiency. We demonstrate that the simultaneous presence of perpendicular near-field components in the nanoantenna sets favorable energy transfer routes that increase the FRET efficiency up to 50% for nearly perpendicular donor and acceptor dipoles. This new facet of plasmonic nanoantennas enables dipole–dipole energy transfer that would otherwise be forbidden in a homogeneous environment. As such, our approach further increases the applicability of single-molecule FRET over diffraction-limited approaches, with the additional benefits of higher sensitivities and higher concentration ranges toward physiological levels.

We demonstrate a plasmon nanoruler using a coupled film-nanoparticle (film-NP) format that is well suited for investigating the sensitivity extremes of plasmonic coupling. Because it is relatively straightforward to functionalize bulk, surface plasmon supporting films such as gold, we are able to precisely control plasmonic gap dimensions by creating ultra-thin molecular spacer layers on the gold films, on top of which we immobilize plasmon resonant nanoparticles (NPs). Each immobilized NP becomes coupled to the underlying film and functions as a plasmon nanoruler, exhibiting a distance-dependent resonance red-shift in its peak plasmon wavelength as it approaches the film. Due to the uniformity of response from the film-NPs to separation distance, we are able to use extinction and scattering measurements from ensembles of film-NPs to characterize the coupling effect over a series of very short separation distances – ranging from 5 – 20 Å – and combine these measurements with similar data from larger separation distances extending out to 27 nm. We find that the film-NP plasmon nanoruler is extremely sensitive at very short film-NP separation distances, yielding spectral shifts as large as 5 nm for every 1 Å change in separation distance. The film-NP coupling at extremely small spacings is so uniform and reliable that we are able to usefully probe gap dimensions where the classical Drude model of the conducting electrons in the metals is no longer descriptive; for gap sizes smaller than a few nanometers, either quantum or semi-classical models of the carrier response must be employed to predict the observed wavelength shifts. We find that, despite the limitations, large field enhancements and extreme sensitivity persist down to even the smallest gap sizes.

We develop a new method based on the continuous-fraction approach as applied to the electrostatic boundary problem for determining surface plasmon resonances of coupled nanospheres. The resonance frequency dependence on interparticle gap (plasmon nanoruler effect) is determined by avoiding time-consuming numerical calculations even for very small interparticle separations, where known procedures face serious difficulties. Corrections due to retardation effects are accounted for, allowing description of larger nanopairs. Good agreement is demonstrated both with results of numerical calculations and with experimental data.

We design a two-dimensional distance and angle location ruler based on surface plasmon resonance (SPR) effect, whose light-scattering spectra shift when either the distance of two gold nanospheres or the angle between their axis and the polarization is changed.

Simultaneous measurement of surface-enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR) in nanoparticle dimers presents outstanding opportunities in molecular identification and in the elucidation of physical properties, such as the size, distance, and deformation of target species. SERS–LSPR instrumentation exists and has been used under limited conditions, but the extraction of SERS and LSPR readouts from a single measurement is still a challenge. Herein, the extraction of LSPR spectra from SERS signals is reported and a tool for measuring the interparticle distance from Raman enhancement data by the standardization of the SERS signal is proposed. The SERS nanoruler mechanism incorporates two important aspects (the LSPR scattering peak shift and the Raman shift for measuring interparticle distance), and signifies their exact one-to-one correspondence after spectral correction. The developed methodology is applied to calculate the interparticle distance between nanoparticle dimers from SERS signals, to detect and quantify DNA at the single-molecule level in a base-pair-specific manner. It is also shown that the SERS nanoruler concept can be used in structural analysis for the specific detection of the interaction of immunoglobulin G (IgG) with its target from bianalyte Raman signals with identical shaping at single-molecule resolution. The SERS profile shaping approach not only offers a new detection mechanism for single molecules, but also has excellent potential for studying protein interactions and the intracellular detection of mRNA.

The localized surface plasmon resonance (LSPR) spectrum associated with a gold nanoparticle (NP) coupled to a gold film exhibits extreme sensitivity to the nano-gap region where the fields are tightly localized. The LSPR of an ensemble of film-coupled NPs can be observed using an illumination scheme similar to that used to excite the surface plasmon resonance (SPR) of a thin metallic film; however, in the present system, the light is used to probe the highly sensitive distance-dependent LSPR of the gaps between NPs and film rather than the delocalized SPR of the film. We show that the SPR and LSPR spectral contributions can be readily distinguished, and we compare the sensitivities of both modes to displacements in the average gap between a collection of NPs and the gold film. The distance by which the NPs are suspended in solution above the gold film is fixed via a thin molecular spacer layer, and can be further modulated by subjecting the NPs to a quasistatic electric field. The observed LSPR spectral shifts triggered by the applied voltage can be correlated with Angstrom scale displacements of the NPs, suggesting the potential for chip-scale or flow-cell plasmonic nanoruler devices with extreme sensitivity.

The evaluation of distances as small as few nanometers using optical waves Is a very challenging task that can pave the way for the development of new applications in biotechnology and nanotechnology. In this article, we propose a new measurement method based on the control of the nonlinear optical response of plasmonic nanostructures by means of Fano resonances. It is shown that Fano resonances resulting from the coupling between a bright mode and a dark mode at the fundamental wavelength enable unprecedented and direct manipulation of the nonlinear electromagnetic sources at the nanoscale. In the case of second harmonic generation from gold nanodolmens, the different nonlinear sources distributions induced by the different coupling regimes are clearly revealed in the far-field distribution. Hence, the configuration of the nanostructure can be accurately determined In 3-dimensions by recording the wave scattered at the second harmonic wavelength. Indeed, the conformation of the different elements building the system is encoded in the nonlinear far-field distribution, making second harmonic generation a promising tool for reading 3-dimension plasmonic nanorulers. Furthemore, it is shown that 3-dimension plasmonic nanorulers can be implemented with simpler geometries than in the linear regime while providing complete Information on the structure conformation, including the top nanobar position and orientation.