Electroluminescence as a Probe of Strong Exciton-Plasmon Coupling in Few-Layer WSe2.

The manipulation of coupled quantum excitations is of fundamental importance in realizing novel photonic and optoelectronic devices. We use electroluminescence to probe plasmon-exciton coupling in hybrid structures consisting of a nanoscale plasmonic tunnel junction and few-layer two-dimensional transition-metal dichalcogenide transferred onto the junction. The resulting hybrid states act as a novel dielectric environment that affects the radiative recombination of hot carriers in the plasmonic nanostructure. We determine the plexcitonic spectrum from the electroluminescence and find Rabi splittings exceeding 50 meV in the strong coupling regime. Our experimental findings are supported by electromagnetic simulations that enable us to explore systematically and in detail the emergence of plexciton polaritons as well as the polarization characteristics of their far-field emission. Electroluminescence modulated by plexciton coupling provides potential applications for engineering compact photonic devices with tunable optical and electrical properties.

Brownian Motion Governs the Plasmonic Enhancement of Colloidal Upconverting Nanoparticles.

Upconverting nanoparticles are essential in modern photonics due to their ability to convert infrared light to visible light. Despite their significance, they exhibit limited brightness, a key drawback that can be addressed by combining them with plasmonic nanoparticles. Plasmon-enhanced upconversion has been widely demonstrated in dry environments, where upconverting nanoparticles are immobilized, but constitutes a challenge in liquid media where Brownian motion competes against immobilization. This study employs optical tweezers for the three-dimensional manipulation of an individual upconverting nanoparticle, enabling the exploration of plasmon-enhanced upconversion luminescence in water. Contrary to expectation, experiments reveal a long-range (micrometer scale) and moderate (20%) enhancement in upconversion luminescence due to the plasmonic resonances of gold nanostructures. Comparison between experiments and numerical simulations evidences the key role of Brownian motion. It is demonstrated how the three-dimensional Brownian fluctuations of the upconverting nanoparticle lead to an "average effect" that explains the magnitude and spatial extension of luminescence enhancement.

DNA Origami Assembled Nanoantennas for Manipulating Single-Molecule Spectral Emission.

The emission spectrum of a dye is given by the energy of all of the possible radiative transitions weighted by their probability. This spectrum can be altered with optical nanoantennas that are able to manipulate the decay rate of nearby emitters by modifying the local density of photonic states. Here, we make use of DNA origami to precisely place an individual dye at different positions around a gold nanorod and show how this affects the emission spectrum of the dye. In particular, we observe a strong suppression or enhancement of the transitions to different vibrational levels of the excitonic ground state, depending on the spectral overlap with the nanorod resonance. This reshaping can be used to experimentally extract the spectral dependence of the radiative decay rate enhancement. Furthermore, for some cases, we argue that the drastic alteration of the fluorescence spectrum could arise from the violation of Kasha's rule.

Non-Hermitian Anharmonicity Induces Single-Photon Emission.

Single-photon sources are in high demand for quantum information applications. A paradigmatic way to achieve single-photon emission is through anharmonicity in the energy levels, such that the absorption of a single photon from a coherent drive shifts the system out of resonance and prevents absorption of a second one. We identify a novel mechanism for single-photon emission through non-Hermitian anharmonicity, i.e., anharmonicity in the losses instead of in the energy levels. We demonstrate the mechanism in two types of systems, including a feasible setup consisting of a hybrid metallodielectric cavity weakly coupled to a two-level emitter, and show that it induces high-purity single-photon emission at high repetition rates.

Plexcitonic Quantum Light Emission from Nanoparticle-on-Mirror Cavities.

We investigate the quantum-optical properties of the light emitted by a nanoparticle-on-mirror cavity filled with a single quantum emitter. Inspired by recent experiments, we model a dark-field setup and explore the photon statistics of the scattered light under grazing laser illumination. Exploiting analytical solutions to Maxwell's equations, we quantize the nanophotonic cavity fields and describe the formation of plasmon-exciton polaritons (or plexcitons) in the system. This way, we reveal that the rich plasmonic spectrum of the nanocavity offers unexplored mechanisms for nonclassical light generation that are more efficient than the resonant interaction between the emitter natural transition and the brightest optical mode. Specifically, we find three different sample configurations in which strongly antibunched light is produced. Finally, we illustrate the power of our approach by showing that the introduction of a second emitter in the platform can enhance photon correlations further.

DNA-Templated Ultracompact Optical Antennas for Unidirectional Single-Molecule Emission.

Optical antennas are nanostructures designed to manipulate light-matter interactions by interfacing propagating light with localized optical fields. In recent years, numerous devices have been realized to efficiently tailor the absorption and/or emission rates of fluorophores. By contrast, modifying the spatial characteristics of their radiation fields remains challenging. Successful phased array nanoantenna designs have required the organization of several elements over a footprint comparable to the operating wavelength. Here, we report unidirectional emission of a single fluorophore using an ultracompact optical antenna. The design consists of two side-by-side gold nanorods self-assembled via DNA origami, which also controls the positioning of the single-fluorophore. Our results show that when a single fluorescent molecule is positioned at the tip of one nanorod and emits at a frequency capable of driving the antenna in the antiphase mode, unidirectional emission with a forward to backward ratio of up to 9.9 dB can be achieved.

Few-Mode Field Quantization of Arbitrary Electromagnetic Spectral Densities.

We develop a framework that provides a few-mode master equation description of the interaction between a single quantum emitter and an arbitrary electromagnetic environment. The field quantization requires only the fitting of the spectral density, obtained through classical electromagnetic simulations, to a model system involving a small number of lossy and interacting modes. We illustrate the power and validity of our approach by describing the population and electric field spatial dynamics in the spontaneous decay of an emitter placed in a complex hybrid plasmonic-photonic structure.

On the applicability of quantum-optical concepts in strong-coupling nanophotonics.

Rooted in quantum optics and benefiting from its well-established foundations, strong coupling in nanophotonics has experienced increasing popularity in recent years. With nanophotonics being an experiment-driven field, the absence of appropriate theoretical methods to describe ground-breaking advances has often emerged as an important issue. To address this problem, the temptation to directly transfer and extend concepts already available from quantum optics is strong, even if a rigorous justification is not always available. In this review we discuss situations where, in our view, this strategy has indeed overstepped its bounds. We focus on exciton-plasmon interactions, and particularly on the idea of calculating the number of excitons involved in the coupling. We analyse how, starting from an unfounded interpretation of the term N/V that appears in theoretical descriptions at different levels of complexity, one might be tempted to make independent assumptions for what the number N and the volume V are, and attempt to calculate them separately. Such an approach can lead to different, often contradictory results, depending on the initial assumptions (e.g. through different treatments of V as the-ambiguous in plasmonics-mode volume). We argue that the source of such contradictions is the question itself-How many excitons are coupled?, which disregards the true nature of the coupled components of the system, has no meaning and often not even any practical importance. If one is interested in validating the quantum nature of the system-which appears to be the motivation driving the pursuit of strong coupling with small N-one could instead focus on quantities such as the photon emission rate or the second-order correlation function. While many of the issues discussed here may appear straightforward to specialists, our target audience is predominantly newcomers to the field, either students or scientists specialised in different disciplines. We have thus tried to minimise the occurrence of proofs and overly-technical details, and instead provide a qualitative discussion of analyses that should be avoided, hoping to facilitate further growth of this promising area.

Pronounced Photovoltaic Response from Multilayered Transition-Metal Dichalcogenides PN-Junctions.

Transition metal dichalcogenides (TMDs) are layered semiconductors with indirect band gaps comparable to Si. These compounds can be grown in large area, while their gap(s) can be tuned by changing their chemical composition or by applying a gate voltage. The experimental evidence collected so far points toward a strong interaction with light, which contrasts with the small photovoltaic efficiencies η ≤ 1% extracted from bulk crystals or exfoliated monolayers. Here, we evaluate the potential of these compounds by studying the photovoltaic response of electrostatically generated PN-junctions composed of approximately 10 atomic layers of MoSe2 stacked onto the dielectric h-BN. In addition to ideal diode-like response, we find that these junctions can yield, under AM-1.5 illumination, photovoltaic efficiencies η exceeding 14%, with fill factors of ~70%. Given the available strategies for increasing η such as gap tuning, improving the quality of the electrical contacts, or the fabrication of tandem cells, our study suggests a remarkable potential for photovoltaic applications based on TMDs.

Influence of Quadrupolar Molecular Transitions within Plasmonic Cavities.

Optical nanocavities have revolutionized the manipulation of radiative properties of molecular and semiconductor emitters. Here, we investigate the amplified photoluminescence arising from exciting a dark transition of ß-carotene molecules embedded within plasmonic nanocavities. Integrating a molecular monolayer into nanoparticle-on-mirror nanostructures unveils enhancements surpassing 4 orders of magnitude in the initially light-forbidden excitation. Such pronounced enhancements transcend conventional dipolar mechanisms, underscoring the presence of alternative enhancement pathways. Notably, Fourier-plane scattering spectroscopy shows that the photoluminescence excitation resonance aligns with a higher-order plasmonic cavity mode, which supports strong field gradients. Combining quantum chemistry calculations with electromagnetic simulations reveals an important interplay between the Franck-Condon quadrupole and Herzberg-Teller dipole contributions in governing the absorption characteristics of this dark transition. In contrast to free space, the quadrupole moment plays a significant role in photoluminescence enhancement within nanoparticle-on-mirror cavities. These findings provide an approach to access optically inactive transitions, promising advancements in spectroscopy and sensing applications.

Nonlocal propagation and tunnelling of surface plasmons in metallic hourglass waveguides.

The nanofocusing performance of hourglass plasmonic waveguides is studied analytically and numerically. Nonlocal effects in the linearly tapered metal-air-metal stack that makes up the device are taken into account within a hydrodynamical approach. Using this hourglass waveguide as a model structure, we show that spatial dispersion drastically modifies the propagation of surface plasmons in metal voids, such as those generated between touching particles. Specifically, we investigate how nonlocal corrections limit the enormous field enhancements predicted by local electromagnetic treatments of geometric singularities. Finally, our results also indicate the emergence of nonlocality assisted tunnelling of plasmonic modes across hourglass contacts as thick as 0.5 nm.

Theory of three-dimensional nanocrescent light harvesters.

The optical properties of three-dimensional crescent-shaped gold nanoparticles are studied using a transformation optics methodology. The polarization insensitive, highly efficient, and tunable light harvesting ability of singular nanocrescents is demonstrated. We extend our approach to more realistic blunt nanostructures, showing the robustness of their plasmonic performance against geometric imperfections. Finally, we provide analytical and numerical insights into the sensitivity of the device to radiative losses and nonlocal effects. Our theoretical findings reveal an underlying relation between structural bluntness and spatial dispersion in this particular nanoparticle configuration.

Nanoplasmonics: classical down to the nanometer scale.

We push the fabrication limit of gold nanostructures to the exciting sub-nanometer regime, in which light-matter interactions have been anticipated to be strongly affected by the quantum nature of electrons in metals. Doing so allows us to (1) evaluate the validity of classical electrodynamics to describe plasmonic effects at this length scale and (2) witness the gradual (instead of sudden) evolution of plasmon modes when two gold nanoprisms are brought into contact. Using electron energy-loss spectroscopy and transmission electron microscope imaging, we investigated nanoprisms separated by gaps of only 0.5 nm and connected by conductive bridges as narrow as 3 nm. Good agreement of our experimental results with electromagnetic calculations and LC circuit models evidence the gradual evolution of the plasmonic resonances toward the quantum coupling regime. We demonstrate that down to the nanometer length scales investigated classical electrodynamics still holds, and a full quantum description of electrodynamics phenomena in such systems might be required only when smaller gaps of a few angstroms are considered. Our results show also the gradual onset of the charge-transfer plasmon mode and the evolution of the dipolar bright mode into a 3λ/2 mode as one literally bridges the gap between two gold nanoprisms.

Nonlocal effects in the nanofocusing performance of plasmonic tips.

The nanofocusing performance of plasmonic tips is studied analytically and numerically. The effects of electron-electron interactions in the dielectric response of the metal are taken into account through the implementation of a nonlocal, spatially dispersive, hydrodynamic permittivity. We demonstrate that spatial dispersion only slightly modifies the device parameters which maximize its field enhancement capabilities. The interplay between nonlocality, tip bluntness, and surface roughness is explored. We show that, although spatial dispersion reduces the field enhancement taking place at the structure apex, it also diminishes the impact that geometric imperfections have on its performance.

High-resolution mapping of electron-beam-excited plasmon modes in lithographically defined gold nanostructures.

We demonstrate the use of high-resolution electron beam lithography to fabricate complex nanocavities with nanometric spatial and positional control. The plasmon modes of these nanostructures are then mapped using electron energy-loss spectroscopy in a scanning transmission electron microsope. This powerful combination of patterning and plasmon mapping provides direct experimental verification to theoretical predictions of plasmon hybridization theory in complex metal nanostructures and allows the determination of the full mode spectrum of such cavities.

A Theoretical Perspective on Molecular Polaritonics.

In the past decade, much theoretical research has focused on studying the strong coupling between organic molecules (or quantum emitters, in general) and light modes. The description and prediction of polaritonic phenomena emerging in this light-matter interaction regime have proven to be difficult tasks. The challenge originates from the enormous number of degrees of freedom that need to be taken into account, both in the organic molecules and in their photonic environment. On one hand, the accurate treatment of the vibrational spectrum of the former is key, and simplified quantum models are not valid in many cases. On the other hand, most photonic setups have complex geometric and material characteristics, with the result that photon fields corresponding to more than just a single electromagnetic mode contribute to the light-matter interaction in these platforms. Moreover, loss and dissipation, in the form of absorption or radiation, must also be included in the theoretical description of polaritons. Here, we review and offer our own perspective on some of the work recently done in the modeling of interacting molecular and optical states with increasing complexity.

Optical Ultracompact Directional Antennas Based on a Dimer Nanorod Structure.

Controlling directionality of optical emitters is of utmost importance for their application in communication and biosensing devices. Metallic nanoantennas have been proven to affect both excitation and emission properties of nearby emitters, including the directionality of their emission. In this regard, optical directional nanoantennas based on a Yagi-Uda design have been demonstrated in the visible range. Despite this impressive proof of concept, their overall size (~λ2/4) and considerable number of elements represent obstacles for the exploitation of these antennas in nanophotonic applications and for their incorporation onto photonic chips. In order to address these challenges, we investigate an alternative design. In particular, we numerically study the performance of a recently demonstrated "ultracompact" optical antenna based on two parallel gold nanorods arranged as a side-to-side dimer. Our results confirm that the excitation of the antiphase mode of the antenna by a nanoemitter placed in its near-field can lead to directional emission. Furthermore, in order to verify the feasibility of this design and maximize the functionality, we study the effect on the directionality of several parameters, such as the shape of the nanorods, possible defects in the dimer assembly, and different positions and orientations of the nanoemitter. We conclude that this design is robust to structural variations, making it suitable for experimental upscaling.

Few-mode field quantization for multiple emitters.

The control of the interaction between quantum emitters using nanophotonic structures holds great promise for quantum technology applications, while its theoretical description for complex nanostructures is a highly demanding task as the electromagnetic (EM) modes form a high-dimensional continuum. We here introduce an approach that permits a quantized description of the full EM field through a small number of discrete modes. This extends the previous work in ref. (I. Medina, F. J. García-Vidal, A. I. Fernández-Domínguez, and J. Feist, "Few-mode field quantization of arbitrary electromagnetic spectral densities," Phys. Rev. Lett., vol. 126, p. 093601, 2021) to the case of an arbitrary number of emitters, without any restrictions on the emitter level structure or dipole operators. The low computational demand of this method makes it suitable for studying dynamics for a wide range of parameters. We illustrate the power of our approach for a system of three emitters placed within a hybrid metallodielectric photonic structure and show that excitation transfer is highly sensitive to the properties of the hybrid photonic-plasmonic modes.

Nanoscale mapping of optically inaccessible bound-states-in-the-continuum.

Bound-states-in-the-continuum (BIC) is an emerging concept in nanophotonics with potential impact in applications, such as hyperspectral imaging, mirror-less lasing, and nonlinear harmonic generation. As true BIC modes are non-radiative, they cannot be excited by using propagating light to investigate their optical characteristics. In this paper, for the 1st time, we map out the strong near-field localization of the true BIC resonance on arrays of silicon nanoantennas, via electron energy loss spectroscopy with a sub-1-nm electron beam. By systematically breaking the designed antenna symmetry, emissive quasi-BIC resonances become visible. This gives a unique experimental tool to determine the coherent interaction length, which we show to require at least six neighboring antenna elements. More importantly, we demonstrate that quasi-BIC resonances are able to enhance localized light emission via the Purcell effect by at least 60 times, as compared to unpatterned silicon. This work is expected to enable practical applications of designed, ultra-compact BIC antennas such as for the controlled, localized excitation of quantum emitters.

Plasmonic light-harvesting devices over the whole visible spectrum.

On the basis of conformal transformation, a general strategy is proposed to design plasmonic nanostructures capable of an efficient harvesting of light over a broadband spectrum. The surface plasmon modes propagate toward the singularity of these structures where the group velocity vanishes and energy accumulates. A considerable field enhancement and confinement is thus expected. Radiation losses are also investigated when the structure dimension becomes comparable to the wavelength.