Volume 9, Issue 2 - Special Issue: Proceedings of Surface Plasmon Photonics Conference (SPP9); Guest Editors: N. Asger Mortensen, Pierre Berini, Uriel Levy, Sergey Bozhevolnyi

Vibrational strong coupling (VSC) is currently emerging as a tool to control chemical dynamics. Here we study the impact of strong coupling strength, given by the Rabi splitting energy ( ħ Ω R ), on the thermodynamic parameters associated with the transition state of the desilylation reaction of the model molecule 1-phenyl-2-trimethylsilylacetylene. Under VSC, the enthalpy and entropy of activation determined from the temperature-dependent kinetic studies varied nonlinearly with the coupling strength. The thermodynamic parameters of the noncavity reaction did not show noticeable variation, ruling out concentration effects other than the enhanced ħ Ω R for the changes observed under VSC. The difference between the total free energy change under VSC and in noncavity was relatively smaller possibly because the enthalpy and entropy of activation compensate each other. This thermodynamic study gives more insight into the role of collective strong coupling on the transition state that leads to modified dynamics and branching ratios.

Light-matter strong coupling is defined when the coupling strength exceeds the losses in the system, whereas ultrastrong coupling is not simply strong coupling with even larger coupling strength. Instead, ultrastrong coupling regime arises when the coupling strength is comparable to the transition frequency in the system. At present, ultrastrong light-matter interactions have been achieved in superconducting circuits, semiconductor polaritons, and organic molecules, where these systems are typically at the micrometer scale. In this work, we investigated ultrastrong coupling in a nanoparticle plexcitonic system, i.e. a single gold nanocube coated with quantum emitters and positioned on a gold film. We observed a normalized coupling rate η  ~ 0.12 to the antenna mode in such coated nanocube-on-mirror ( c -NCoM) configuration at the multilayer emitter level. In contrast to the gap mode that squeezes all the optical fields into the gap region, the antenna mode in c -NCoM provides multiple exterior hot spots at the upper corners of the nanocube, which can be exploited for qubit entanglement within a single nanocube. The concurrence between adjacent emitters is estimated up to 0.6. This theoretical study establishes a promising route toward building a scalable quantum network using single plexcitonic nanocubes as quantum nodes.

Plasmonic structures interacting with light provide electromagnetic resonances that result in a high degree of local field confinement, enabling the enhancement of light-matter interaction. Plasmonic structures typically consist of metals, which, however, suffer from very high ohmic losses and heating. High-index dielectrics, meanwhile, can serve as an alternative material due to their low-dissipative nature and strong scattering abilities. We studied the optical properties of a system composed of all-dielectric nanoparticle arrays covered with a film of organic dye molecules (IR-792) and compared these dielectric arrays with metallic nanoparticle arrays. We tuned the light-matter interaction by changing the concentration in the dye film and reported the system to be in the strong coupling regime. We observed a Rabi splitting between the surface lattice resonances of the nanoparticle arrays and the absorption line of the dye molecules of up to 253 and 293 meV, for the dielectric and metallic nanoparticles, respectively. The Rabi splitting depends linearly on the square root of the dye molecule concentration, and we further assessed how the Rabi splitting depends on the film thickness for a low dye molecule concentration. For thinner films of thicknesses up to 260 nm, we observed no visible Rabi splitting. However, a Rabi splitting evolved at thicknesses from 540 to 990 nm. We performed finite-difference time-domain simulations to analyze the near-field enhancements for the dielectric and metallic nanoparticle arrays. The electric fields were enhanced by a factor of 1200 and 400, close to the particles for gold and amorphous silicon, respectively, and the modes extended over half a micron around the particles for both materials.

The spectrum and energy dynamics for a system that comprises a molecule interacting with a cavity photon is analyzed, taking into account the effect of both molecular vibrations and counter-rotating terms (CR) in the dipole Hamiltonian. The CR terms do not have a strong effect on the spectrum even for moderately large values of the exciton-photon interaction. However, it is shown that the polariton subspace is governed by an effective Quantum-Rabi Hamiltonian, where polaritons act as a two-level system and the phonons play the role of cavity photons. The effect of the CR terms is amplified in the dynamics: as the vibrations reduce the effective photon-exciton coupling, small Bloch-Siegert energy shifts can bring the system out of resonance.

Geometrical chirality is a widespread phenomenon that has fundamental implications for discriminating enantiomers of biomolecules. In order to enhance the chiral response of the medium, it has been suggested to couple chiral molecules to resonant optical cavities in order to enhance the circular dichroism (CD) signal at the resonant frequency of the cavity. Here, we studied a distinctly different regime of chiral light-matter interaction, wherein the CD signal of a chiral medium splits into polaritonic modes by reaching the strong coupling regime with an optical microcavity. Specifically, we show that by strongly coupling chiral plasmonic nanoparticles to a non-chiral Fabry-Pérot microcavity one can imprint the mode splitting on the CD spectrum of the coupled system and thereby effectively shift the initial chiral resonance to a different energy. We first examined the effect with the use of analytical transfer-matrix method as well as numerical finite-difference time-domain (FDTD) simulations. Furthermore, we confirmed the validity of theoretical predictions in a proof-of-principle experiment involving chiral plasmonic nanoparticles coupled to a Fabry-Pérot microcavity.

Localised surface plasmons can couple strongly with the electronic transitions of a molecule, inducing new hybridised states of light and matter, the plasmon–exciton polaritons. Furthermore, molecules support vibrational degrees of freedom that interact with the electronic levels, giving rise to inelastic resonant Raman scattering under coherent laser illumination. Here we show the influence of strong plasmon–exciton coupling on resonant Raman processes that populate the vibrational states of the molecule and that lead to the characteristic surface-enhanced Raman scattering spectra. We develop analytical expressions that give insight into these processes for the case of moderate illumination intensity, weak electron–vibration coupling and no dephasing. These expressions help us to elucidate the twofold role of plasmon–exciton polaritons to pump the system efficiently and to enhance the Raman emission. Our results show a close analogy with the optomechanical process described for off-resonant Raman scattering but with a difference in the resonant reservoir. We also use full numerical calculations to study the effects reaching beyond these approximations and discuss the interplay between the fluorescence background and the Raman lines. Our results allow for better understanding and exploitation of the strong coupling regime in vibrational pumping and in the surface-enhanced resonant Raman scattering signal.

Singular graphene metasurfaces, conductivity gratings realized by periodically suppressing the local doping level of a graphene sheet, were recently proposed to efficiently harvest THz light and couple it to surface plasmons over broad absorption bands, thereby achieving remarkably high field enhancement. However, the large momentum wavevectors thus attained are sensitive to the nonlocal behavior of the underlying electron liquid. Here, we extend the theory of singular graphene metasurfaces to account for the full nonlocal optical response of graphene and discuss the resulting impact on the plasmon resonance spectrum. Finally, we propose a simple local-analogue model that is able to reproduce the effect of nonlocality in local-response calculations by introducing a constant conductivity offset, which could prove a valuable tool in the modeling of more complex experimental graphene-based platforms.

Graphene-based photodetectors, taking advantage of the high carrier mobility and broadband absorption in graphene, have recently seen rapid development. However, their performance with respect to responsivity and bandwidth is still limited by the weak light-graphene interaction and large resistance-capacitance product. Here, we demonstrate a waveguide-coupled integrated graphene plasmonic photodetector on a silicon-on-insulator platform. Benefiting from plasmon-enhanced graphene-light interaction and subwavelength confinement of the optical energy, a small-footprint graphene-plasmonic photodetector is achieved working at the telecommunication window, with a large a bandwidth beyond 110 GHz and a high intrinsic responsivity of 360 mA/W. Attributed to the unique electronic band structure of graphene and its ultra-broadband absorption, operational wavelength range extending beyond mid-infrared, and possibly further, can be anticipated. Our results show that the combination of graphene with plasmonic devices has great potential to realize ultra-compact, high-speed optoelectronic devices for graphene-based optical interconnects.

Germanium selenide (GeSe) nanosheets are stable and inexpensive and considered to have a great potential for photovoltaic applications, however we have demonstrated that GeSe nanosheets are also promising for sensing technology, in this paper. By spin-coating the GeSe nanosheets on the surface of noble metal (Au), we have obtained a surface plasmon resonance (SPR) sensor with significantly enhanced sensitivity, and the performance of the sensor is closely related to the thickness of the GeSe film. By detecting different refractive index solutions, we have obtained the optimized sensitivity with 3581.2 nm/RIU (which is nearly 80% improvement compared to traditional SPR sensors) and figure of merit with 14.37 RIU −1 . Moreover, the proposed SPR sensor was vastly superior in sensing Pb 2+ heavy metal ions after coating it with chitosan and GeSe composite. A maximum sensitivity of 30.38 nm/μg/l has been verified, which is nearly six times better than that of conventional SPR sensor. Our results demonstrated that GeSe nanosheets overlayer with modified SPR sensor has its great potential in heavy metal detection and chemical-specific molecular identification.

Exciton (strong electron–hole interactions) and hot carriers (HCs) assisted by surface plasmon polaritons show promise to enhance the photoresponse of nanoelectronic and optoelectronic devices. In the current research, we develop a computational quantum framework to study the effect of coupled exciton and HCs on the photovoltaic energy distribution, scattering process, polarizability, and light emission of two-dimensional (2D) semiconductors. Using a stable 2D semiconductor (semihydrogenated SiB) as our example, we theoretically show that external strain and thermal effect on the SiB can lead to valley polarized plasmon quasiparticles and HC generation. Our results reveal that the electron–phonon and electron–electron (e–e) interactions characterize the correlation between the decay rate, scattering of excitons, and generation of HCs in 2D semiconductors. Moreover, phonon assisted luminescence spectra of SiB suggest that light emission can be enhanced by increasing strain and temperature. The polarized plasmon with strong coupling of electronic and photonics states in SiB makes it as a promising candidate for light harvesting, plasmonic photocurrent devices, and quantum information.

The nonlinear processes of frequency conversion such as second harmonic generation (SHG) usually obey certain selection rules, resulting from the preservation of different kinds of physical quantities, e.g. the angular momentum. For the SHG created by a monolayer of transition-metal dichalcogenides (TMDCs) such as WS 2 , the valley-exciton locked selection rule predicts an SHG signal in the cross-polarization state. By combining plasmonic nanostructures with a monolayer of TMDC, a hybrid metasurface is realized, which affects this nonlinear process because of an additional polarization conversion process. Here, we observe that the plasmonic metasurface modifies the light-matter interaction with the TMDC, resulting in an SHG signal that is co-polarized with respect to the incident field, which is usually forbidden for the monolayers of TMDC. We fabricate such hybrid metasurfaces by placing plasmonic nanorods on top of a monolayer WS 2 and study the valley-exciton locked SHG emission from such system for different parameters, such as wavelength and polarization. Furthermore, we show the potential of the hybrid metasurface for tailoring nonlinear processes by adding additional phase information to the SHG signal using the Pancharatnam-Berry phase effect. This allows direct tailoring of the SHG emission to the far-field.

The ongoing effort to implement compact and cheap optical systems is the main driving force for the recent flourishing research in the field of optical metalenses. Metalenses are a type of metasurface, used for focusing and imaging applications, and are implemented based on the nanopatterning of an optical surface. The challenge faced by metalens research is to reach high levels of performance using simple fabrication methods suitable for mass production. In this paper, we present a Huygens nanoantenna-based metalens, designed for outdoor photographic/surveillance applications in the near infrared. We show that good imaging quality can be obtained over a field of view as large as ±15°. This first successful implementation of metalenses for outdoor imaging applications is expected to provide insight and inspiration for future metalens imaging applications.

In spite of a wide range of applications ranging from particle trapping to optical communication, conventional methods to generate vortex beams suffer from bulky configurations and limited performance. Here, we design, fabricate, and experimentally demonstrate orthogonal linear-polarization conversion and focused vortex-beam generation simultaneously by using gap-surface plasmon metasurfaces that enable high-performance linear-polarization conversion along with the complete phase control over reflected fields, reproducing thereby the combined functionalities of traditional half-wave plates, lenses, and q-plates. The fabricated metasurface sample features the excellent capability of orthogonal linear-polarization conversion and focused vortex-beam generation within the wavelength range of 800–950 nm with an averaged polarization conversion ratio of ~80% and absolute focusing efficiency exceeding 27% under normal illumination with the x -polarized beam. We further show that this approach can be extended to realize a dual-focal metasurface with distinctly engineered intensity profiles by using segmented metasurfaces, where an orthogonal-polarized beam with Gaussian-distributed intensity and a vortex beam with intensity singularity have been experimentally implemented. The proposed multifunctional metasurfaces pave the way for advanced research and applications targeting photonics integration of diversified functionalities.

Metamaterials are mostly designed in the time-harmonic scenario where wave propagation can be spatially manipulated. Tailoring the electromagnetic response of media in time has also gained the attention of the scientific community in order to achieve further control on wave-matter interaction both in space and time. In the present work, a temporally effective medium concept in metamaterial is theoretically investigated as a mechanism to create a medium with a desired effective permittivity. Similar to spatially subwavelength multilayered metamaterials, the proposed “temporal multilayered”, or “multistepped” metamaterial, is designed by alternating in time the permittivity of the medium between two values. In so doing, the temporally periodic medium can be modeled as an effective metamaterial in time with an effective permittivity initiated by a step function. The analogy between the temporal multistepped and the spatial multilayered metamaterials is presented demonstrating the duality between both domains. The proposed temporal metamaterial is analytically and numerically evaluated showing an excellent agreement with the designed parameters. Moreover, it is shown how the effective permittivity can be arbitrarily tailored by changing the duty cycle of the periodic temporal metamaterial. This performance is also connected to the spatial multilayer scenario in terms of the filling fraction of the different materials used to create the multilayered structures.

We fabricate plasmonic heptamer-arranged nanohole (HNH) arrays by helium (He) focused ion beam (HeFIB) milling, which is a resist-free, maskless, direct-write method. The small He + beam spot size and high milling resolution achieved by the gas field-ionization source used in our HeFIB allows the milling of high aspect ratio (4:1) nanoscale features in metal, such as HNHs incorporating 15 nm walls of high verticality between holes in a 55-nm-thick gold film. Drifts encountered during the HeFIB milling of large arrays, due to sample stage vibrations or He beam instability, were compensated by a drift correction technique based on in situ He ion imaging of alignment features. Our drift correction technique yielded 20 nm maximum dislocation of HNHs, with 6.9 and 4.6 nm average dislocations along the horizontal and vertical directions, respectively. The measured optical resonance spectra of the fabricated plasmonic HNH arrays are presented to support the fabrication technique. Defects associated with HeFIB milling are also discussed.

A combination of helium- and gallium-ion beam milling together with a fast and reliable sketch-and-peel technique is used to fabricate gold nanorod dimer antennas with an excellent quality factor and with gap distances of less than 6 nm. The high fabrication quality of the sketch-and-peel technique compared to a conventional ion beam milling technique is proven by polarisation-resolved linear dark-field spectromicroscopy of isolated dimer antennas. We demonstrate a strong coupling of the two antenna arms for both fabrication techniques, with a quality factor of more than 14, close to the theoretical limit, for the sketch-and-peel–produced antennas compared to only 6 for the conventional fabrication process. The obtained results on the strong coupling of the plasmonic dimer antennas are supported by finite-difference time-domain simulations of the light-dimer antenna interaction. The presented fabrication technique enables the rapid fabrication of large-scale plasmonic or dielectric nanostructures arrays and metasurfaces with single-digit nanometer scale milling accuracy.

We observe anomalous visible to near-infrared electromagnetic emission from electrically driven atomic-size point contacts. We show that the number of photons released strongly depends on the quantized conductance steps of the contact. Counterintuitively, the light intensity features an exponential decay dependence with the injected electrical power. We propose an analytical model for the light emission considering an out-of-equilibrium electron distribution. We treat photon emission as a Bremsstrahlung process resulting from hot electrons colliding with the metal boundary, and find qualitative accord with the experimental data.

We demonstrate a metamaterial platform for electrically driven broadband light emission induced by electron tunneling. Both the Fabry-Perot and waveguided modes of the metamaterial slab as well the plasmonic mode of the tunneling gap are identified as contributing to shaping the emission spectrum. This opens up an opportunity to design the spectrum and polarization of the emitted light by tuning the metamaterial modes via the geometric parameters of the nanostructure throughout the visible and near-infrared spectral ranges. The efficient coupling of the tunneling-induced emission to the waveguided modes is beneficial for the development of integrated incoherent light sources, while the outcoupled emission provides a source of free-space radiation. The demonstrated incoherent nanoscale light sources may find applications in the development of integrated opto-electronic circuits, optical sensing platforms, imaging, and metrology.

Through the manipulation of metallic structures, light–matter interaction can enter into the realm of quantum mechanics. For example, intense terahertz pulses illuminating a metallic nanotip can promote terahertz field–driven electron tunneling to generate enormous electron emission currents in a subpicosecond time scale. By decreasing the dimension of the metallic structures down to the nanoscale and angstrom scale, one can obtain a strong field enhancement of the incoming terahertz field to achieve atomic field strength of the order of V/nm, driving electrons in the metal into tunneling regime by overcoming the potential barrier. Therefore, designing and optimizing the metal structure for high field enhancement are an essential step for studying the quantum phenomena with terahertz light. In this review, we present several types of metallic structures that can enhance the coupling of incoming terahertz pulses with the metals, leading to a strong modification of the potential barriers by the terahertz electric fields. Extreme nonlinear responses are expected, providing opportunities for the terahertz light for the strong light–matter interaction. Starting from a brief review about the terahertz field enhancement on the metallic structures, a few examples including metallic tips, dipole antenna, and metal nanogaps are introduced for boosting the quantum phenomena. The emerging techniques to control the electron tunneling driven by the terahertz pulse have a direct impact on the ultrafast science and on the realization of next-generation quantum devices.

The evolution of non-equilibrium carriers excited in the process of decay of surface plasmon polaritons (SPPs) in metal is described for each step – from the generation of carriers to their extraction from the metal. The relative importance of various carrier-generating mechanisms is discussed. It is shown that both the generation of carriers and their decay are inherently quantum processes as, for realistic illumination conditions, no more than a single SPP per nanoparticle exists at a given time. As a result, the distribution of non-equilibrium carriers cannot be described by a single temperature. It is also shown that the originally excited carriers that have not undergone a single electron-electron scattering event are practically the only ones that contribute to the injection. The role of momentum conservation in carrier extraction is discussed, and it is shown that, if all the momentum conservation rules are relaxed, it is the density of states in the semiconductor/dielectric that determines the ultimate injection efficiency. A set of recommendations aimed at improving the efficiency of plasmonic-assisted photodetection and (to a lesser degree) photocatalysis is made in the end.

The large cross sections and strong confinement provided by the plasmon resonances of metallic nanostructures make these systems an ideal platform to implement nanoantennas. Like their macroscopic counterparts, nanoantennas enhance the coupling between deep subwavelength emitters and free radiation, providing, at the same time, an increased directionality. Here, inspired by the recent works in parity-time symmetric plasmonics, we investigate how the combination of conventional plasmonic nanostructures with active materials, which display optical gain when externally pumped, can serve to enhance the performance of metallic nanoantennas. We find that the presence of gain, in addition to mitigating the losses and therefore increasing the power radiated or absorbed by an emitter, introduces a phase difference between the elements of the nanoantenna that makes the optical response of the system directional, even in the absence of geometrical asymmetry. Exploiting these properties, we analyse how a pair of nanoantennas with balanced gain and loss can enhance the far-field interaction between two dipole emitters. The results of this work provide valuable insight into the optical response of nanoantennas made of active and passive plasmonic nanostructures, with potential applications for the design of optical devices capable of actively controlling light at the nanoscale.

Plasmon nanoantennas are extensively used with molecular systems for chemical and biological ultra-sensing, for boosting the molecular emissive and energy transfer properties, for nanoscale catalysis, and for building advanced hybrid nanoarchitectures. In this perspective, we focus on the latest developments of using plasmon nanoantennas for nanoscale chiral chemistry and for advancing molecular magnetism. We overview the decisive role nanoplasmonics and nano-optics can play in achieving chirally selective molecular synthesis and separation and the way such processes might be precisely controlled by potentially merging chirality and magnetism at the molecular scale. We give our view on how these insights might lead to the emergence of exciting new fundamental concepts in nanoscale materials science.

We describe and demonstrate a novel experimental approach to measure broadband, amplitude- and phase-resolved scattering spectra of single nanoparticles with 10-nm spatial resolution. Nanofocusing of surface plasmon polaritons (SPPs) propagating along the shaft of a conical gold taper is used to create a spatially isolated, spectrally broad nanoscale light source at its very apex. The interference between these incident SPPs and SPPs that are backpropagating from the apex leads to the formation of an inherently phase-stable interferogram, which we detect in the far field by partially scattering SPPs off a small protrusion on the taper shaft. We show that these interferograms allow the reconstruction of both the amplitude and phase of the local optical near fields around individual nanoparticles optically coupled to the taper apex. We extract local light scattering spectra of particles and quantify line broadenings and spectral shifts induced by tip-sample coupling. Our experimental findings are supported by corresponding finite-difference time-domain and coupled dipole simulations and show that, in the limit of weak tip-sample coupling, the measurements directly probe the projected local density of optical states of the plasmonic system. The combination of a highly stable inline interferometer with the inherent optical background suppression through nanofocusing makes it a promising tool for the locally resolved study of the spectral and temporal optical response of coupled hybrid nanosystems.

We use mono-crystalline gold platelets with ultra-smooth surfaces and superior plasmonic properties to investigate the formation of interference patterns caused by surface plasmon polaritons (SPPs) with scattering-type scanning near-field microscopy at 521 and 633 nm. By applying a Fourier analysis approach, we can identify and separate several signal channels related to SPPs launched and scattered by the atomic force microscopy tip and the edges of the platelet. Especially at the excitation wavelength of 633 nm, we can isolate a region in the center of the platelets where we find only contributions of SPPs which are launched by the tip and reflected at the edges. These signatures are used to determine the SPP wavelength of λ SPP  = 606 nm in good agreement with theoretical predictions. Furthermore, we were still able to measure SPP signals after 20 µm propagation, which demonstrates impressively the superior plasmonic quality of these mono-crystalline gold platelets.

Periodically arranged metallic nanowires on top of a waveguide layer show a strong coupling between the particle plasmon of the wires and the waveguide mode. By introducing a dielectric spacer layer between the metallic structures and the waveguide layer, this coupling can be reduced. Here, the thickness of this spacer layer is varied and the coupling strength is determined for each spacer layer thickness by fitting an effective energy matrix to the energy positions of the resonance peaks. It is found that the coupling strength can be very well described by the electric field amplitude of the waveguide mode at the location of the nanowires. We carried out experiments and found very good agreement with theory and our simple model. Using this method, we achieved experimentally an extremely small mode splitting as small as 25 meV leading to very sharp spectral features. Our pathway and design for tailoring the coupling strength of plasmonic Fano resonances will enable the design of highly sensitive plasmonic sensor devices and open the door for narrow plasmonic spectral features for nonlinear optics and slow light propagation.

We present results on colors of metal disk arrays viewed under a darkfield microscope and show that the darkfield colors can be manipulated independently of the brightfield colors. We investigate the appearance of colors as disks are clustered to form a new array with double the pitch and a basis of four disks. These structures of aluminum disks on aluminum oxide on aluminum have resonances in the visible spectrum, so by arranging them in small tight clusters, a coupled plasmon resonant mode is produced at shorter wavelengths. This feature causes a reflectance minimum and leads to an increase in the gamut of darkfield colors produced. These colors are tuned by changing the size of the disk and the inter-disk gap within the clusters. Interestingly, the intensities of the reflectance peaks also demonstrate good agreement with the Fourier series coefficients for square waves. Polarization-tunable colors are also demonstrated by designing rectangular arrays that have dissimilar periods along the two orthogonal axes of the array, and a four-level security tag is fabricated that encodes images for viewing under brightfield, darkfield (both x and y polarization), and infrared illumination.