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Non-fullerene acceptors (NFA) have delivered advance in bulk heterojunction organic solar cell efficiencies, with the significant milestone of 20% now in sight. However, these materials challenge the accepted wisdom of how organic solar cells work. In this work we present neat Y6 device with efficiency above 4.5%. We thoroughly investigate mechanisms of charge generation and recombination as well as transport in order to understand what is special about Y6. Our data suggest Y6 generates bulk free charges, with ambipolar mobility, which can be extracted in the presence of transport layers, 11 pages, 5 figures

6 pags., 4 figs., Here, we present and implement a new approach for producing modular inkjet-printable surface-enhanced Raman scattering (SERS) chemosensors. These sensors, combined with a rapid large field-of-view imaging system allow for fast imaging of the chemical characteristics of a sample. The performance of these materials is illustrated by printing a pH sensor on paper and interrogating aqueous solutions at different pH values. Results show single-shot images exceeding 9 mm2 which are readily read out via SERS imaging., M.L. and N.F.v.H. acknowledge support from the Ministry of Science, Innovation, and Universities (MCIU: RTI2018-099957-J-I00 and PGC2018-096875-B-I00). N.F.v.H. acknowledges the financial support from the European Commission (ERC Advanced Grant 670949-LightNet) and the AGAUR (2017SGR1369). This work was partially funded by CEX2019-000910-S [MCIN/ AEI/10.13039/501100011033], Fundació Privada Cellex, Fundació Privada Mir-Puig, and Generalitat de Catalunya through the CERCA program. V.G. acknowledges Ministry of Science, Innovation, and Universities for financial support (FIS2017-91413-EXP and PGC2018-095777-B-C21). I.C, N.P.P., and R.A.A.P. acknowledge support by the Ministry of Science, Innovation, and Universities (PID2020-120306RB-I00 and PDC2021-121787-I00), the AGAUR (2017SGR883), and the Universitat Rovira i Virgili (2021PFR-URV-B2-02).

Conducting materials typically exhibit either diffusive or ballistic charge transport. When electron–electron interactions dominate, a hydrodynamic regime with viscous charge flow emerges1–13. More stringent conditions eventually yield a quantum-critical Dirac-fluid regime, where electronic heat can flow more efficiently than charge14–22. However, observing and controlling the flow of electronic heat in the hydrodynamic regime at room temperature has so far remained elusive. Here we observe heat transport in graphene in the diffusive and hydrodynamic regimes, and report a controllable transition to the Dirac-fluid regime at room temperature, using carrier temperature and carrier density as control knobs. We introduce the technique of spatiotemporal thermoelectric microscopy with femtosecond temporal and nanometre spatial resolution, which allows for tracking electronic heat spreading. In the diffusive regime, we find a thermal diffusivity of roughly 2,000 cm2 s−1, consistent with charge transport. Moreover, within the hydrodynamic time window before momentum relaxation, we observe heat spreading corresponding to a giant diffusivity up to 70,000 cm2 s−1, indicative of a Dirac fluid. Our results offer the possibility of further exploration of these interesting physical phenomena and their potential applications in nanoscale thermal management., Spatiotemporal thermoelectric microscopy enables the observation of electronic heat flow in graphene in diffusive and hydrodynamic regimes at room temperature, as well as a controlled transition from a Fermi liquid to Dirac fluid.

Coherent control is an ingenious tactic to steer a system to a desired optimal state by tailoring the phase of an incident ultrashort laser pulse. A relevant process is the two-photon–induced photoluminescence (TPPL) of nanoantennas, as it constitutes a convenient route to map plasmonic fields, and has important applications in biological imaging and sensing. Unfortunately, coherent control of metallic nanoantennas is impeded by their ultrafast femtosecond dephasing times so far limiting control to polarization and spectral optimization. Here, we report that phase control of the TPPL in resonant gold nanoantennas is possible. We show that, by compressing pulses shorter than the localized surface plasmon dephasing time (

Optical nanoantennas are well-known for the confinement of light into nanoscale hot spots, suitable for emission enhancement and sensing applications. Here, we show how control of the antenna dimensions allows tuning the local optical phase, hence turning a hot spot into a cold spot. We manipulate the local intensity exploiting the interference between driving and scattered field. Using single molecules as local detectors, we experimentally show the creation of subwavelength pockets with full suppression of the driving field. Remarkably, together with the cold excitation spots, we observe inhibition of emission by the phase-tuned nanoantenna. The fluorescence lifetime of a molecule scanned in such volumes becomes longer, showing slow down of spontaneous decay. In conclusion, the spatial phase of a nanoantenna is a powerful knob to tune between enhancement and inhibition in a 3-dimensional subwavelength volume.

Ultrafast light-induced spatiotemporal dynamics in metals in the form of electron and/or phonon heating is a fundamental physical process that has tremendous practical relevance. In particular, understanding the resulting lateral heat transport is of key importance for various (opto)electronic applications and thermal management but has attracted little attention. Here, by using scanning ultrafast thermo-modulation microscopy to track the spatiotemporal electron diffusion in thin gold films, we show that a few picoseconds after the optical pump there is unexpected heat flow from phonons to electrons, accompanied by negative effective thermal diffusion, characterized by shrinking of the spatial region with increased temperature. Peculiarly, this occurs on the intermediate time scale, between the few picosecond long thermalization stage and the many picosecond stage dominated by thermoacoustic vibrations. We accurately reproduced these experimental results by calculating the spatiotemporal photothermal response based on the two-temperature model and an improvement of the standard permittivity model for gold. Our findings facilitate the design of nanoscale thermal management strategies in photonic, optoelectronic, and high-frequency electronic devices.

Identifying, visualising and ultimately tracking dynamically moving non-fluorescent nanoparticles in the presence of non-specific scattering is a long-standing challenge across the nano- and life-sciences. In this work we demonstrate that our recently developed ultrafast holographic transient (UHT) microscope is ideally suited for meeting this challenge. We show that UHT microscopy allows reliably distinguishing off-resonant, dielectric, from resonant, metallic, nanoparticles, based on the phototransient signal: a pre-requisite for single-particle tracking in scattering environments. We then demonstrate the capability of UHT microscopy to holographically localize in 3D single particles over large volumes of view. Ultimately, we combine the two concepts to simultaneously track several tens of freely diffusing gold nanoparticles, within a 110x110x110 $\mu$m volume of view at an integration time of 10 ms per frame, while simultaneously recording their phototransient signals. The combined experimental concepts outlined and validated in this work lay the foundation for background-free 3D single-particle tracking applications or spectroscopy in scattering environments and are immediately applicable to systems as diverse as live cells and tissues or supported heterogeneous catalysts.

Surface-enhanced Raman scattering (SERS) imaging is a powerful technology with unprecedent potential for ultrasensitive chemical analysis. Point-by-point scanning and often excessively long spectral acquisition-times hamper the broad exploitation of the full analytical potential of SERS. Here, we introduce large scale SERS particle screening (LSSPS), a multiplexed widefield screening approach to particle-characterization, which is 500-1000 times faster than typical confocal Raman implementations. Beyond its higher throughput, LSSPS simultaneously quantifies both the sample’s Raman and Rayleigh scattering, allowing for an unprecedented correlation of SERS activity with the particle-size and to directly quantify the fraction of SERS active particles.

Pump-probe microscopy was limited to single-point detection because cameras are too slow for shot-to-shot demodulation. We use off-axis holography to create an all-optical lock-in camera, obtaining pump-probe images spanning 100×100 μm2. We use it to study exciton diffusion in perovskites around 100 diffraction-limited spots.

Understanding heat flow in layered transition metal dichalcogenide (TMD) crystals is crucial for applications exploiting these materials. Despite significant efforts, several basic thermal transport properties of TMDs are currently not well understood, in particular how transport is affected by material thickness and the material's environment. This combined experimental-theoretical study establishes a unifying physical picture of the intrinsic lattice thermal conductivity of the representative TMD MoSe

In the quest to decipher the chain of life from molecules to cells, the biological and biophysical questions being asked increasingly demand techniques that are capable of identifying specific biomolecules in their native environment, and can measure biomolecular interactions quantitatively, at the smallest possible scale in space and time, without perturbing the system under observation. The interaction of light with biomolecules offers a wealth of phenomena and tools that can be exploited to drive this progress. This Roadmap is written collectively by prominent researchers and encompasses selected aspects of bio-nano-photonics, spanning from the development of optical micro/nano-spectroscopy technologies for quantitative bioimaging and biosensing to the fundamental understanding of light–matter interaction phenomena with biomolecules at the nanoscale. It will be of interest to a wide cross-disciplinary audience in the physical sciences and life sciences.

The performance of nonfullerene-acceptor-(NFA)-based organic solar cells is rapidly approaching the efficiency of inorganic cells. The chemical versatility of NFAs extends the light-harvesting range to the infrared, while preserving a considerably high open-circuit- voltage, crucial to achieve power-conversion efficiencies >17%. Such low voltage losses in the charge separation process have been attributed to a low-driving-force and efficient exciton dissociation. Here, we address the nature of the subpicosecond dynamics of electron/hole transfer in PM6/Y6 solar cells. While previous reports focused on active layers only, we developed a photocurrent-detected two-dimensional spectroscopy to follow the charge transfer in fully operating devices. Our measurements reveal an efficient hole-transfer from the Y6- acceptor to the PM6-donor on the subpicosecond time scale. On the contrary, at the same time scale, no electron-transfer is seen from the donor to the acceptor. These findings, putting ultrafast spectroscopy in action on operating optoelectronic devices, provide insight for further enhancing NFA solar cell performance. This research received funding from the Clean Planet Program supported by Fundació Joan Ribas Araquistain (FJRA) and the Ignite program (Q-SPET) supported by the Barcelona Institute of Science and Technology. N.F.v.H. acknowledges the financial support by the European Commission (ERC Advanced Grant 670949-LightNet and Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agree- ment No 713729), the Ministry of Science & Innovations (“Severo Ochoa” program for Centers of Excellence in R&D CEX2019-000910-S and Plan Nacional PGC2018-096875−B- I00), the Catalan AGAUR (2017SGR1369), Fundació Privada Cellex, Fundació Privada Mir-Puig and the Generalitat de Catalunya through the CERCA program. J.M. and F.B. acknowledge the financial support by the European Commis- sion (grant 951843), Spanish Ministry MINECO and FEDER (grant MAT2017-89522-R), the Severo Ochoa program (Grant SEV-2015-0522) and “Agencia Estatal de Investiga- ción” (Grant PRE2018-084881). E.C. acknowledges the financial support of the H2020 FET Project COPAC (766563).

Photosynthetic reactions in plants, algae, and cyanobacteria are driven by photosystem I and photosystem II complexes, which specifically reduce or oxidize partner redox biomolecules. Photosynthetic complexes can also bind synthetic organic molecules, which inhibit their photoactivity and can be used both to study the electron transport chain and as herbicides and algicides. Thus, their development, characterization, and sensing bears fundamental and applied interest. Substantial efforts have been devoted to developing photosensors based on photosystem II to detect compounds that bind to the plastoquinone sites of this complex. In comparison, photosystem I based sensors have received less attention and could be used to identify novel substances displaying phytotoxic effects, including those obtained from natural product extracts. We have developed a robust procedure to functionalize gold electrodes with photo- and redox-active photosystem I complexes based on transparent gold and a thiolate self-assembled monolayer, and we have obtained reproducible electrochemical photoresponses. Chronoamperometric recordings have allowed us to measure photocurrents in the presence of the viologen derivative paraquat at concentrations below 100 nM under lock-in operation and a sensor dynamic range spanning six orders of magnitude up to 100 mM. We have modeled their time course to identify the main electrochemical processes and limiting steps in the electron transport chain. Our results allow us to isolate the contributions from photosystem I and the redox mediator, and evaluate photocurrent features (spectral and power dependence, fast transient kinetics) that could be used as a sensing signal to detect other inhibitors and modulators of photosystem I activity.

Nanotechnology is increasingly being applied in many emerging technologies, ranging from metamaterials to next-generation nanodrugs. A key ingredient for its success is the ability to specifically tailor ultrafast nanoscale light-matter interactions over very large areas. Unfortunately, dynamic imaging by ultrafast nanoscopy so far remains limited to very small 2D areas. This shortcoming prevents connecting single-particle observations with large-scale functionality. Here, we address this experimental challenge by combining concepts of ultrafast spectroscopy, wide-field nanoscopy, and digital holography. We introduce an ultrafast holographic transient microscope for wide-field transient nanoscale imaging with high frequency all-optical signal demodulation. We simultaneously record ultrafast transient dynamics of many individual nano-objects and demonstrate time-resolved spectroscopy of gold nanoparticles over a large volume irrespective of their x-y-z position. Our results pave the way to single-shot 3D microscopy of 2D and 3D materials on arbitrary time scales from femtosecond carrier dynamics in optoelectronic materials to millisecond dynamics in complex tissues.

Many promising optoelectronic devices, such as broadband photodetectors, nonlinear frequency converters, and building blocks for data communication systems, exploit photoexcited charge carriers in graphene. For these systems, it is essential to understand the relaxation dynamics after photoexcitation. These dynamics contain a sub-100 fs thermalization phase, which occurs through carrier-carrier scattering and leads to a carrier distribution with an elevated temperature. This is followed by a picosecond cooling phase, where different phonon systems play a role: graphene acoustic and optical phonons, and substrate phonons. Here, we address the cooling pathway of two technologically relevant systems, both consisting of high-quality graphene with a mobility >10000 cm2 V-1 s-1 and environments that do not efficiently take up electronic heat from graphene: WSe2-encapsulated graphene and suspended graphene. We study the cooling dynamics using ultrafast pump-probe spectroscopy at room temperature. Cooling via disorder-assisted acoustic phonon scattering and out-of-plane heat transfer to substrate phonons is relatively inefficient in these systems, suggesting a cooling time of tens of picoseconds. However, we observe much faster cooling, on a time scale of a few picoseconds. We attribute this to an intrinsic cooling mechanism, where carriers in the high-energy tail of the hot-carrier distribution emit optical phonons. This creates a permanent heat sink, as carriers efficiently rethermalize. We develop a macroscopic model that explains the observed dynamics, where cooling is eventually limited by optical-to-acoustic phonon coupling. These fundamental insights will guide the development of graphene-based optoelectronic devices., We would like to thank Andrea Tomadin for discussions. The authors acknowledge funding from the European Union Horizon 2020 Programme under Grant Agreement No. 881603 Graphene Core 3. ICN2 was supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706). A.P. acknowledges support from the European Commission under the EU Horizon 2020 MSCA-RISE-2019 programme (project 873028 HYDROTRONICS) and from the Leverhulme Trust under grant RPG-2019-363. K.J.T. acknowledges funding from the European Union’s Horizon 2020 research and innovation program under Grant Agreement No. 804349 (ERC StG CUHL), RyC fellowship No. RYC-2017-22330, and IAE project PID2019-111673GB-I00 and financial support through the MAINZ Visiting Professorship. X.J. acknowledges the support from the Max Planck Graduate Center with the Johannes Gutenberg-Universität Mainz (MPGC). J.Z. acknowledges the support from National Natural Science Foundation of China (No. 52072042). Z.L. acknowledges the support from National Natural Science Foundation of China (No. 51520105003). T.S. acknowledges support from the University of Liege under Special Funds for Research, IPD-STEMA Programme. M.J.V. gratefully acknowledges funding from the Belgian Fonds National de la Recherche Scientifique (FNRS) under PDR grant T.0103.19-ALPS. Computational resources were provided by CECI (FRS-FNRS G.A. 2.5020.11) and the Zenobe Tier-1 supercomputer (Gouvernement Wallon G.A. 1117545) and by a PRACE-3IP DECI grant 2DSpin and Pylight on Beskow (G.A. 653838 of H2020). ICFO was supported by the Severo Ochoa program for Centers of Excellence in R&D (CEX2019-000910-S), Fundació Privada Cellex, Fundació Privada Mir-Puig, and the Generalitat de Catalunya through the CERCA program. N.v.H. acknowledges funding by the European Commission (ERC AdG 670949-LightNet), the Spanish Plan Nacional (PGC2018-096875-BI00), and the Catalan AGAUR (2017SGR1369).

Nanoscale phase-control is one of the most powerful approaches to specifically tailor electrical fields in modern nanophotonics. Especially the precise sub-wavelength assembly of many individual nano-building-blocks has given rise to exciting new materials as diverse as metamaterials, for miniaturizing optics, or 3D assembled plasmonic structures for biosensing applications. Despite its fundamental importance, the phase-response of individual nanostructures is experimentally extremely challenging to visualize. Here, we address this shortcoming and measure the quantitative scattering phase of different nanomaterials such as gold nanorods and spheres as well as dielectric nanoparticles. Beyond reporting spectrally resolved responses, with phase-changes close to pi when passing the particles' plasmon resonance, we devise a simple method for distinguishing different plasmonic and dielectric particles purely based on their phase behavior. Finally, we integrate this novel approach in a single-shot two-color scheme, capable of directly identifying different types of nanoparticles on one sample, from a single widefield image.

Fluorescence microscopy is the method of choice in biology for its molecular specificity and super-resolution capabilities. However, it is limited to a narrow z range around one observation plane. Here, we report an imaging approach that recovers the full electric field of fluorescent light with single-molecule sensitivity. We expand the principle of digital holography to fast fluorescent detection by eliminating the need for phase cycling and enable three-dimensional (3D) tracking of individual nanoparticles with an in-plane resolution of 15 nm and a z-range of 8 mm. As a proof-of-concept biological application, we image the 3D motion of extracellular vesicles (EVs) inside live cells. At short time scales (, Science Advances, 6 (45), ISSN:2375-2548

Optical sensing is one of the key-enablers of modern diagnostics. Especially label-free imaging modalities hold great promise as they eliminate labeling procedures prior to analysis. However, scattering signals of nanometric particles scale with their volume-square. This unfavorable scaling makes it extremely difficult to quantitatively characterize intrinsically heterogeneous clinical samples, such as extracellular vesicles, as their signal variation easily exceeds the dynamic range of currently available cameras. Here, we introduce off-axis k-space holography that circumvents this limitation. By imaging the back-focal-plane of our microscope we project the scattering signal of all particles onto all camera pixels thus dramatically boosting the achievable dynamic range to up-to 110 dB. We validate our platform by detecting, and quantitatively sizing, metallic and dielectric particles over a 200x200 $\mu$m field-of-view and demonstrate that independently performed signal calibrations allow correctly sizing particles made from different materials. Finally, we present quantitative size-distributions of extracellular vesicle samples.

Förster Resonance Energy Transfer (FRET) is a widely applied technique in biology to accurately measure intra- and inter-molecular interactions at the nanometre scale. FRET is based on near-field energy transfer from an excited donor to a ground state acceptor emitter. Photonic nanoantennas have been shown to modify the rate, efficiency and extent of FRET, a process that is highly dependent on the near-field gradient of the antenna field as felt by the emitters, and thus, on their relative distance. However, most of the experiments reported to date focus on fixed antennas where the emitters are either immobilized or diffusing in solution, so that the distance between the antenna and the emitters cannot be manipulated. Here, we use scanning photonic nanoantenna probes to directly modulate the FRET efficiency between individual FRET pairs with an unprecedented nanometric lateral precision of 2 nm on the antenna position. We find that the antenna acts as an independent acceptor element, competing with the FRET pair acceptor. We directly map the competition between FRET and donor-antenna transfer as a function of the relative position between the antenna and the FRET donor-acceptor pair. The experimental data are well-described by FDTD simulations, confirming that the modulation of FRET efficiency is due to the spatially dependent coupling of the single FRET pair to the photonic antenna.

Nanometric probes based on surface-enhanced Raman scattering (SERS) are promising candidates for all-optical environmental, biological and technological sensing applications with intrinsic quantitative molecular specificity. However, the effectiveness of SERS probes depends on a delicate trade-off between particle size, stability and brightness that has so far hindered their wide application in SERS imaging methodologies. In this Article, we introduce holographic Raman microscopy, which allows single-shot three-dimensional single-particle localization. We validate our approach by simultaneously performing Fourier transform Raman spectroscopy of individual SERS nanoparticles and Raman holography, using shearing interferometry to extract both the phase and the amplitude of wide-field Raman images and ultimately localize and track single SERS nanoparticles inside living cells in three dimensions. Our results represent a step towards multiplexed single-shot three-dimensional concentration mapping in many different scenarios, including live cell and tissue interrogation and complex anti-counterfeiting applications.

Cavity QED is the art of enhancing light-matter interaction of photon emitters in cavities, with opportunities for sensing, quantum information and energy capture technologies. To boost emitter-cavity interaction, i.e. coupling strength , ultrahigh quality cavities have been concocted yielding photon trapping times of µs to ms. However, such high-Q cavities give poor photon output, hindering applications. To preserve high photon output it is advantageous to strive for highly localised electric fields in radiatively lossy cavities. Nanophotonic antennas are ideal candidates combining low-Q factors with deeply localised mode volumes, allowing large , provided the emitter is positioned exactly right inside the nanoscale mode volume. Here, with nanometre resolution, we map and tune the coupling strength between a dipole nanoantenna-cavity and a single molecule, obtaining a coupling rate of max ~ 200 GHz. Together with accelerated single photon output, this provides ideal conditions for fast and pure non-classical single photon emission with brightness exceeding 10E9 photons/sec. Clearly, nanoantennas acting as “bad” cavities offer an optimal regime for strong coupling , to deliver bright on-demand and ultrafast single photon nanosources for quantum technologies.

Defect centers in two-dimensional hexagonal boron nitride (hBN) are drawing attention as single photon emitters with high photo-stability at room temperature. With their ultra-high photon-stability, hBN single photon emitters are promising for new applications in quantum technologies and for two-dimensional material based optoelectronics. Here, we control the emission rate of hBN-defects by coupling these to resonant plasmonic nanocavities. By deterministic control of the antenna we acquire high-resolution emission maps of the single hBN-defects. Using time-gating, we can discriminate the hBN defect emission from the antenna luminescence. We observe sharp dips (40 nm FWHM) in emission, together with a reduction with the luminescence lifetime. Comparing with FDTD simulations we conclude that both radiative and non-radiative rates are enhanced, which effectively reduce the quantum efficiency. Also, the large refractive index of the hBN largely screens off the local antenna field enhancement. Finally, based on the insight gained, we propose a close-contact design for an order of magnitude brighter hBN single photon emission.

Nanometric probes based on surface-enhanced Raman scattering (SERS) are promising candidates for all-optical environmental, biological and technological sensing applications with intrinsic quantitative molecular specificity. However, the effectiveness of SERS probes depends on a delicate trade-off between particle size, stability and brightness that has so far hindered their wide application in SERS imaging methodologies. In this Article, we introduce holographic Raman microscopy, which allows single-shot three-dimensional single-particle localization. We validate our approach by simultaneously performing Fourier transform Raman spectroscopy of individual SERS nanoparticles and Raman holography, using shearing interferometry to extract both the phase and the amplitude of wide-field Raman images and ultimately localize and track single SERS nanoparticles inside living cells in three dimensions. Our results represent a step towards multiplexed single-shot three-dimensional concentration mapping in many different scenarios, including live cell and tissue interrogation and complex anti-counterfeiting applications.

Excitation spectroscopy gives direct insight in excited state manifold, energy transfer, transient intermediates, vibrations, etc. Unfortunately, excitation spectroscopy of single molecules at ambient conditions has remained challenging. Here, we present excitation spectra alongside emission spectra of the same individual light harvesting complex LH2 of the purple bacteria Rps. acidophila. Acquisition of both the excited and ground state spectra allows to quantify disorder and interband correlations, which are key variables for the interpretation of observed long-lasting coherences. We have overcome the low photostability and small fluorescence quantum yield, inherent to many biologically relevant systems, by combining single molecule Fourier transform spectroscopy, low excitation intensities, and effective data analysis. We find that LH2 complexes show little spectral variation (130-170 cm-1), that their two absorption bands (B800-B850) act uncorrelated, and that the Stokes shift is not constant. The low amount of spectral disorder underlines the protective role of the protein scaffold, benefitting the efficient energy transport throughout the light-harvesting membrane

I will present both deterministic scanning antenna and stochastic localisation mapping of the nanoscale antenna-molecule interaction, towards stronger coupling, bright single photon sources, rate enhancement and spectral control.

Single atomic defects in hexagonal boron nitride (hBN) are particularly interesting due to their stability of emission and absence of blinking and bleaching, at ambient conditions [1]. Furthermore, they show exceptional robustness of emission, even at high temperatures of operation [2]. Therefore, hBN defects have emerged as promising candidates for novel robust single photon sources [1]. Several attempts have been done to induce hBN defects in a controlled manner [3,4]. Because of their ease of accessibility and, due to the nanometer scale thickness of the hBN flakes, these defects are attractive to couple to plasmonic structures in order to increase their photon emission [5,6]. However efficient coupling requires a high precision of positioning (

Electric and magnetic optical fields carry the same amount of energy. Nevertheless, the efficiency with which matter interacts with electric optical fields is commonly accepted to be at least 4 orders of magnitude higher than with magnetic optical fields [1]. Here we experimentally demonstrate that properly designed photonic nanoantennas (figure 1a and b) can selectively manipulate the magnetic versus electric emission of luminescent nanocrystals [2]. In particular, an enhancement of magnetic emission from trivalent europium-doped nanoparticles can only by observed in the vicinity of nanoantennas featuring a magnetic resonance [2,3]. Moreover, by controlling the spatial coupling between emitter and nanoresonator using a Near-field Scanning Optical Microscope (NSOM), local distributions of both magnetic and electric radiative local densities of states can be readily recorded with nanoscale precision (figure 1c and d), revealing the modification of the quantum environment induced by the presence of the nanoantennas. This manipulation and enhancement of magnetic light and matter interactions is a turning point in nanophotonics, opening up new possibilities for the research fields of opto-electronics, chiral optics, nonlinear & nano-optics, spintronics and metamaterials, amongst others.

Tracking excitations Illumination can be used to excite a sample from its ground state to a number of excited states. Typically, however, the details of the excitation dynamics are hidden from view because they decay so fast. Piatkowski et al. combined pump-probe transient absorption and two-pulse photoluminescence correlation spectroscopy, allowing them to assess stimulated emission and ground-state bleaching contributions to the transient absorption signal. This approach provides a window on the excitation dynamics within single nanocrystals and should also be useful for ultrafast nanocharacterization of complex samples. Science , this issue p. 1240

High-index dielectric nanoantennas have recently emerged as promising alternatives to plasmonic nanoantennas for concentrating and manipulating light at the nanoscale. For example, gallium phosphide (GaP) nanoantennas display extremely low losses in the visible range and high nonlinearities, support both electric and magnetic resonances, and are nicely compatible with CMOS fabrication technology. Especially, the low losses and large nonlinearities are promising for ultrafast optical switching and truly all-optical control of GaP nanodevices. Here first we use two- and three-photon excitation of GaP nanodisks to probe the size-dependent resonance enhancement of second-harmonic and bandgap emission. Next, we show, by spectral phase control of broadband pulsed excitation, that GaP nanoantennas outperform their metal counterparts in supporting nonlinear optical coherences.

Over the past 25 years, single-molecule spectroscopy has developed into a widely used tool in multiple disciplines of science. The diversity of routinely recorded emission spectra does underpin the strength of the single-molecule approach in resolving the heterogeneity and dynamics, otherwise hidden in the ensemble. In early cryogenic studies single molecules were identified by their distinct excitation spectra, yet measuring excitation spectra at room temperature remains challenging. Here we present a broadband Fourier approach that allows rapid recording of excitation spectra of individual molecules under ambient conditions and that is robust against blinking and bleaching. Applying the method we show that the excitation spectra of individual molecules exhibit an extreme distribution of solvatochromic shifts and distinct spectral shapes. Importantly, we demonstrate that the sensitivity and speed of the broadband technique is comparable to that of emission spectroscopy putting both techniques side-by-side in single-molecule spectroscopy., In single-molecule spectroscopy typically only emission spectra are recorded. Here, the authors develop a technique to record single-molecule excitation spectra under ambient conditions, which is robust against blinking and bleaching, and reveals a large distribution of spectra across the molecule ensemble.

We address the sensitivity of Interferometric Cross-Polarisation Microscopy by comparing scattering and absorption by spherical 10nm nanoparticles through a combination of modelling and experiment. We show that orthogonality of light in the two polarisation branches of Cross-Polarisation Microscopy ensures that only light that has interacted with a nanoparticle is interferometrically enhanced. As a result background-free shot noise-limited detection is achieved for sub-μW optical powers at the sample. Our modelling in particular shows that in the near-infrared regime, above the plasmon resonance frequency of spherical nanoparticles, the cross-polarisation approach is several orders of magnitude more sensitive than conventional extinction based detection. This enhanced near-infrared sensitivity for spherical nanoparticles is promising for applications requiring low absorption and low power imaging of nanoparticles in cells.

We present the use of fiber-based resonant dipole and nanogap optical nanoantennas for extreme resolution optical microscopy. A typical optical dipole antenna is only $\sim$ 100-nm long, as the wavelength of light is typically a million times smaller than for radio waves. We show how by focused-ion-beam milling of metal-coated tapered optical fibers we overcome the challenge of fabricating resonant antennas at such small-length scales, with an accuracy of $\sim$ 10 nm. The optical fiber provides an ideal interface between the macro- and nanoscales, allowing the manipulation of such a tiny nanoantenna with nanometer precision relative to a sample surface. Imaging single fluorescent molecules and nanobeads, we achieve an optical resolution down to 40 nm (FWHM), far below the Abbe diffraction limit. The strongly localized antenna field results in an enhancement of fluorescence up to 100 $\times$ , while the vectorial nature of the local antenna field allows access to molecules of all orientations. Clearly, dedicated nanofabrication of fiber-based scanning optical antennas is a promising route to push the limits of optical nanoscopy.

International audience; Electric and magnetic optical fields carry the same amount of energy. Nevertheless, the efficiency with which matter interacts with electric optical fields is commonly accepted to be at least 4 orders of magnitude higher than with magnetic optical fields. Here, we experimentally demonstrate that properly designed photonic nanoantennas can selectively manipulate the magnetic versus electric emission of luminescent nanocrystals. In particular, we show selective enhancement of magnetic emission from trivalent europium-doped nanoparticles in the vicinity of a nanoantenna tailored to exhibit a magnetic resonance. Specifically, by controlling the spatial coupling between emitters and an individual nanoresonator located at the edge of a near-field optical scanning tip, we record with nanoscale precision local distributions of both magnetic and electric radiative local densities of states (LDOS). The map of the radiative LDOS reveals the modification of both the magnetic and electric quantum environments induced by the presence of the nanoantenna. This manipulation and enhancement of magnetic light–matter interaction by means of nanoantennas opens up new possibilities for the research fields of optoelectronics, chiral optics, nonlinear and nano-optics, spintronics, and metamaterials, among others.

Plasmonics is a rapidly developing field at the boundary of physical optics and condensed matter physics. It studies phenomena induced by and associated with surface plasmons - elementary polar excitations bound to surfaces and interfaces of good nanostructured metals. This Roadmap is written collectively by prominent researchers in the field of plasmonics. It encompasses selected aspects of nanoplasmonics. Among them are fundamental aspects, such as quantum plasmonics based on the quantum-mechanical properties of both the underlying materials and the plasmons themselves (such as their quantum generator, spaser), plasmonics in novel materials, ultrafast (attosecond) nanoplasmonics, etc. Selected applications of nanoplasmonics are also reflected in this Roadmap, in particular, plasmonic waveguiding, practical applications of plasmonics enabled by novel materials, thermo-plasmonics, plasmonic-induced photochemistry and photo-catalysis. This Roadmap is a concise but authoritative overview of modern plasmonics. It will be of interest to a wide audience of both fundamental physicists and chemists, as well as applied scientists and engineers., J Schötz for financial support by the European Union via the ERC grant ATTOCO, by the DFG via SPP1840.

Nonlinear spectroscopy has revealed long-lasting oscillations in the optical response of a variety of photosynthetic complexes. Different theoretical models which involve the coherent coupling of electronic (excitonic) or electronic-vibrational (vibronic) degrees of freedom have been put forward to explain these observations. The ensuing debate concerning the relevance of either one or the other mechanism may have obscured their potential synergy. To illustrate this synergy, we quantify how the excitonic delocalization in the LH2 unit of Rhodopseudomonas Acidophila purple bacterium, leads to correlations of excitonic energy fluctuations, relevant coherent vibronic coupling and, importantly, a decrease in the excitonic dephasing rates. Combining these effects, we identify a feasible origin for the long-lasting oscillations observed in fluorescent traces from time-delayed two-pulse single molecule experiments performed on this photosynthetic complex., 5 pages main text with 3 figures, 7 pages supporting information with 4 figures

Discussions.-- et al.

Optical nanoantennas have revolutionised the way we manipulate single photons emitted by individual light sources in a nanostructured photonic environment. Complex plasmonic architectures allow for multiscale light control by shortening or stretching the light wavelength for a fixed operating frequency, meeting the size of the emitter and that of propagating modes. Here, we study self-assembled semi-continuous gold films and lithographic gold networks characterised by large local density of optical state (LDOS) fluctuations around the electrical percolation threshold, a regime where the surface is characterised by large metal clusters with fractal topology. We study the formation of plasmonic networks and their effect on light emission from embedded fluorescent probes in these systems. Through fluorescence dynamics experiments we discuss the role of global long-range interactions linked to the degree of percolation and to the network fractality, as well as the local near-field contributions coming from the local electro-magnetic fields and the topology. Our experiments indicate that local properties dominate the fluorescence modification.

Chemistry is all about molecules: control, synthesis, interaction and reaction of molecules. All too easily on a blackboard, one draws molecules, their structures and dynamics, to create an insightful picture. The dream is to see these molecules in reality. This is exactly what “Single Molecule Detection” provides: a look at molecules in action at ambient conditions; a breakthrough technology in chemistry, physics and biology. Within the realms of the Royal Society of Chemistry, the Faraday Discussion on “Single Molecule Microscopy and Spectroscopy” was a very appropriate topic for presentation, deliberation and debate. Undoubtedly, the Faraday Discussions have a splendid reputation in stimulating scientific debates along the traditions set by Michael Faraday. Interestingly, back in the 1830's, Faraday himself pursued an experiment that led to the idea that atoms in a compound were joined by an electrical component. He placed two opposite electrodes in a solution of water containing a dissolved compound, and observed that one of the elements of the compound accumulated on one electrode, while the other was deposited on the opposite electrode. Although Faraday was deeply opposed to atomism, he had to recognize that electrical forces were responsible for the joining of atoms. Probably a direct view on the atoms or molecules in his experiment would have convinced him. As such, Michael Faraday might have liked the gathering at Burlington House in September 2015 (Fig. 1). Surely, with the questioning eyes of his bust on the 1st floor corridor, the non-believer Michael Faraday has incited each passer-by to enter into discussion and search for deeper answers at the level of single molecules. In these concluding remarks, highlights of the presented papers and discussions are summarized, complemented by a conclusion on future perspectives.The Royal Society of Chemistry at Burlington House in London. The entrance and the stained glass window on the stairway towards the first floor corridor where one finds the bronze bust representing Michael Faraday, protagonist of the early-day lively scientific discussions, which have inspired the “Faraday Discussions”.

Single molecule spectroscopy aims at unveiling often hidden but potentially very important contributions of single entities to a system's ensemble response. Albeit contributing tremendously to our ever growing understanding of molecular processes the fundamental question of temporal evolution, or change, has thus far been inaccessible, resulting in a static picture of a dynamic world. Here, we finally resolve this dilemma by performing the first ultrafast time-resolved transient spectroscopy on a single molecule. By tracing the femtosecond evolution of excited electronic state spectra of single molecules over hundreds of nanometres of bandwidth at room temperature we reveal their non-linear ultrafast response in an effective 3-pulse scheme with fluorescence detection. A first excitation pulse is followed by a phase-locked de-excitation pulse-pair, providing spectral encoding with 25 fs temporal resolution. This experimental realisation of true single molecule transient spectroscopy demonstrates that two-dimensional electronic spectroscopy of single molecules is experimentally in reach., Accepted for publication in Nature Photonics

Our understanding of the dynamical processes such as light harvesting or single fission crucially relies on ultrafast nonlinear measurement modalities [1,2]. Such techniques are routinely applied to bulk materials but their extension to individual quantum systems in condensed phase at room temperature has thus far remained elusive but is highly sought after due to the ongoing device miniaturisation down to the single molecule (SM) level [3]. Even the mere detection of a SM under these conditions has only been achieved under great experimental efforts and only recently have nonlinear SM-experiments under cryogenic conditions been reported for the first time [4-6]. Here, we introduce a novel experimental technique that allows for the direct recording of ultrafast transient absorption spectra of SMs in a broadband fashion and a temporal resolution of 25 fs at room temperature in condensed phase.

7 pags., 4 figs. -- Open Access funded by Creative Commons Atribution Licence 4.0, The combination of single particle detection and ultrafast laser pulses is an instrumental method to track dynamics at the femtosecond time scale in single molecules, quantum dots and plasmonic nanoparticles. Optimal control of the extremely short-lived coherences of these individual systems has so far remained elusive, yet its successful implementation would enable arbitrary external manipulation of otherwise inaccessible nanoscale dynamics. In ensemble measurements, such control is often achieved by resorting to a closed-loop optimization strategy, where the spectral phase of a broadband laser field is iteratively optimized. This scheme needs long measurement times and strong signals to converge to the optimal solution. This requirement is in conflict with the nature of single emitters whose signals are weak and unstable. Here we demonstrate an effective closed-loop optimization strategy capable of addressing single quantum dots at room temperature, using as feedback observable the two-photon photoluminescence induced by a phase-controlled broadband femtosecond laser. Crucial to the optimization loop is the use of a deterministic and robust-against-noise search algorithm converging to the theoretically predicted solution in a reduced amount of steps, even when operating at the few-photon level. Full optimization of the single dot luminescence is obtained within ∼100 trials, with a typical integration time of 100 ms per trial. These times are faster than the typical photobleaching times in single molecules at room temperature. Our results show the suitability of the novel approach to perform closed-loop optimizations on single molecules, thus extending the available experimental toolbox to the active control of nanoscale coherences., This research was funded by the European Commission (ERC Adv. Grant 247330-NanoAntennas and ERC Adv. Grant 670949-LightNet), Spanish Severo Ochoa Programme for Centres of Excellence in R&D (SEV-2015-0522), Plan Nacional Project FIS2012-35527, co-funded by FEDER, the Catalan AGAUR (2014 SGR01540) and Fundació CELLEX (Barcelona). PMdR acknowledges financial support from Spanish Government MINECO-FPI grant and European Science Foundation under the PLASMON-BIONANOSENSE Exchange Grant program. MGS acknowledges financial support from grants MICINN TEC2011-22422 and MINECO TEC2014-52642-C2-1-R.