In-plane anisotropic and ultra-low-loss polaritons in a natural van der Waals crystal.

Polaritons-hybrid light-matter excitations-enable nanoscale control of light. Particularly large polariton field confinement and long lifetimes can be found in graphene and materials consisting of two-dimensional layers bound by weak van der Waals forces1,2 (vdW materials). These polaritons can be tuned by electric fields3,4 or by material thickness5, leading to applications including nanolasers6, tunable infrared and terahertz detectors7, and molecular sensors8. Polaritons with anisotropic propagation along the surface of vdW materials have been predicted, caused by in-plane anisotropic structural and electronic properties9. In such materials, elliptic and hyperbolic in-plane polariton dispersion can be expected (for example, plasmon polaritons in black phosphorus9), the latter leading to an enhanced density of optical states and ray-like directional propagation along the surface. However, observation of anisotropic polariton propagation in natural materials has so far remained elusive. Here we report anisotropic polariton propagation along the surface of α-MoO3, a natural vdW material. By infrared nano-imaging and nano-spectroscopy of semiconducting α-MoO3 flakes and disks, we visualize and verify phonon polaritons with elliptic and hyperbolic in-plane dispersion, and with wavelengths (up to 60 times smaller than the corresponding photon wavelengths) comparable to those of graphene plasmon polaritons and boron nitride phonon polaritons3-5. From signal oscillations in real-space images we measure polariton amplitude lifetimes of 8 picoseconds, which is more than ten times larger than that of graphene plasmon polaritons at room temperature10. They are also a factor of about four larger than the best values so far reported for phonon polaritons in isotopically engineered boron nitride11 and for graphene plasmon polaritons at low temperatures12. In-plane anisotropic and ultra-low-loss polaritons in vdW materials could enable directional and strong light-matter interactions, nanoscale directional energy transfer and integrated flat optics in applications ranging from bio-sensing to quantum nanophotonics.

Dual-Band Coupling of Phonon and Surface Plasmon Polaritons with Vibrational and Electronic Excitations in Molecules.

Strong coupling (SC) between light and matter excitations bears intriguing potential for manipulating material properties. Typically, SC has been achieved between mid-infrared (mid-IR) light and molecular vibrations or between visible light and excitons. However, simultaneously achieving SC in both frequency bands remains unexplored. Here, we introduce polaritonic nanoresonators (formed by h-BN layers on Al ribbons) hosting surface plasmon polaritons (SPPs) at visible frequencies and phonon polaritons (PhPs) at mid-IR frequencies, which simultaneously couple to excitons and molecular vibrations in an adjacent layer of CoPc molecules, respectively. Employing near-field optical nanoscopy, we demonstrate the colocalization of near fields at both visible and mid-IR frequencies. Far-field transmission spectroscopy of the nanoresonator structure covered with a layer of CoPc molecules shows clear mode splittings in both frequency ranges, revealing simultaneous SPP-exciton and PhP-vibron coupling. Dual-band SC may offer potential for manipulating coupling between exciton and molecular vibration in future optoelectronics, nanophotonics, and quantum information applications.

Broad spectral tuning of ultra-low-loss polaritons in a van der Waals crystal by intercalation.

Phonon polaritons-light coupled to lattice vibrations-in polar van der Waals crystals are promising candidates for controlling the flow of energy on the nanoscale due to their strong field confinement, anisotropic propagation and ultra-long lifetime in the picosecond range1-5. However, the lack of tunability of their narrow and material-specific spectral range-the Reststrahlen band-severely limits their technological implementation. Here, we demonstrate that intercalation of Na atoms in the van der Waals semiconductor α-V2O5 enables a broad spectral shift of Reststrahlen bands, and that the phonon polaritons excited show ultra-low losses (lifetime of 4 ± 1 ps), similar to phonon polaritons in a non-intercalated crystal (lifetime of 6 ± 1 ps). We expect our intercalation method to be applicable to other van der Waals crystals, opening the door for the use of phonon polaritons in broad spectral bands in the mid-infrared domain.

Twisted Nano-Optics: Manipulating Light at the Nanoscale with Twisted Phonon Polaritonic Slabs.

Recent discoveries have shown that, when two layers of van der Waals (vdW) materials are superimposed with a relative twist angle between them, the electronic properties of the coupled system can be dramatically altered. Here, we demonstrate that a similar concept can be extended to the optics realm, particularly to propagating phonon polaritons-hybrid light-matter interactions. To do this, we fabricate stacks composed of two twisted slabs of a vdW crystal (α-MoO3) supporting anisotropic phonon polaritons (PhPs), and image the propagation of the latter when launched by localized sources. Our images reveal that, under a critical angle, the PhPs isofrequency curve undergoes a topological transition, in which the propagation of PhPs is strongly guided (canalization regime) along predetermined directions without geometric spreading. These results demonstrate a new degree of freedom (twist angle) for controlling the propagation of polaritons at the nanoscale with potential for nanoimaging, (bio)-sensing, or heat management.

Strain-Tunable Single Photon Sources in WSe2 Monolayers.

The appearance of single photon sources in atomically thin semiconductors holds great promises for the development of a flexible and ultracompact quantum technology in which elastic strain engineering can be used to tailor their emission properties. Here, we show a compact and hybrid two-dimensional semiconductor-piezoelectric device that allows for controlling the energy of single photons emitted by quantum emitters localized in wrinkled WSe2 monolayers. We demonstrate that strain fields exerted by the piezoelectric device can be used to tune the energy of localized excitons in WSe2 up to 18 meV in a reversible manner while leaving the single photon purity unaffected over a wide range. Interestingly, we find that the magnitude and, in particular, the sign of the energy shift as a function of stress is emitter dependent. With the help of finite element simulations we suggest a simple model that explains our experimental observations and, furthermore, discloses that the type of strain (tensile or compressive) experienced by the quantum emitters strongly depends on their localization across the wrinkles. Our findings are of strong relevance for the practical implementation of single photon devices based on two-dimensional materials as well as for understanding the effects of strain on their emission properties.

Thermoelectric detection and imaging of propagating graphene plasmons.

Controlling, detecting and generating propagating plasmons by all-electrical means is at the heart of on-chip nano-optical processing. Graphene carries long-lived plasmons that are extremely confined and controllable by electrostatic fields; however, electrical detection of propagating plasmons in graphene has not yet been realized. Here, we present an all-graphene mid-infrared plasmon detector operating at room temperature, where a single graphene sheet serves simultaneously as the plasmonic medium and detector. Rather than achieving detection via added optoelectronic materials, as is typically done in other plasmonic systems, our device converts the natural decay product of the plasmon-electronic heat-directly into a voltage through the thermoelectric effect. We employ two local gates to fully tune the thermoelectric and plasmonic behaviour of the graphene. High-resolution real-space photocurrent maps are used to investigate the plasmon propagation and interference, decay, thermal diffusion, and thermoelectric generation.

Optical nano-imaging of gate-tunable graphene plasmons.

The ability to manipulate optical fields and the energy flow of light is central to modern information and communication technologies, as well as quantum information processing schemes. However, because photons do not possess charge, a way of controlling them efficiently by electrical means has so far proved elusive. A promising way to achieve electric control of light could be through plasmon polaritons­coupled excitations of photons and charge carriers­in graphene. In this two-dimensional sheet of carbon atoms, it is expected that plasmon polaritons and their associated optical fields can readily be tuned electrically by varying the graphene carrier density. Although evidence of optical graphene plasmon resonances has recently been obtained spectroscopically, no experiments so far have directly resolved propagating plasmons in real space. Here we launch and detect propagating optical plasmons in tapered graphene nanostructures using near-field scattering microscopy with infrared excitation light. We provide real-space images of plasmon fields, and find that the extracted plasmon wavelength is very short­more than 40 times smaller than the wavelength of illumination. We exploit this strong optical field confinement to turn a graphene nanostructure into a tunable resonant plasmonic cavity with extremely small mode volume. The cavity resonance is controlled in situ by gating the graphene, and in particular, complete switching on and off of the plasmon modes is demonstrated, thus paving the way towards graphene-based optical transistors. This successful alliance between nanoelectronics and nano-optics enables the development of active subwavelength-scale optics and a plethora of nano-optoelectronic devices and functionalities, such as tunable metamaterials, nanoscale optical processing, and strongly enhanced light­matter interactions for quantum devices and biosensing applications.

Terahertz Nanofocusing with Cantilevered Terahertz-Resonant Antenna Tips.

We developed THz-resonant scanning probe tips, yielding strongly enhanced and nanoscale confined THz near fields at their tip apex. The tips with length in the order of the THz wavelength (λ = 96.5 µm) were fabricated by focused ion beam (FIB) machining and attached to standard atomic force microscopy (AFM) cantilevers. Measurements of the near-field intensity at the very tip apex (25 nm radius) as a function of tip length, via graphene-based (thermoelectric) near-field detection, indicate their first and second order geometrical antenna resonances for tip length of 33 and 78 µm, respectively. On resonance, we find that the near-field intensity is enhanced by one order of magnitude compared to tips of 17 µm length (standard AFM tip length), which is corroborated by numerical simulations that further predict remarkable intensity enhancements of about 107 relative to the incident field. Because of the strong field enhancement and standard AFM operation of our tips, we envision manifold and straightforward future application in scattering-type THz near-field nanoscopy and THz photocurrent nanoimaging, nanoscale nonlinear THz imaging, or nanoscale control and manipulation of matter employing ultrastrong and ultrashort THz pulses.

Intrinsic Plasmon-Phonon Interactions in Highly Doped Graphene: A Near-Field Imaging Study.

As a two-dimensional semimetal, graphene offers clear advantages for plasmonic applications over conventional metals, such as stronger optical field confinement, in situ tunability, and relatively low intrinsic losses. However, the operational frequencies at which plasmons can be excited in graphene are limited by the Fermi energy EF, which in practice can be controlled electrostatically only up to a few tenths of an electronvolt. Higher Fermi energies open the door to novel plasmonic devices with unprecedented capabilities, particularly at mid-infrared and shorter-wave infrared frequencies. In addition, this grants us a better understanding of the interaction physics of intrinsic graphene phonons with graphene plasmons. Here, we present FeCl3-intercalated graphene as a new plasmonic material with high stability under environmental conditions and carrier concentrations corresponding to EF > 1 eV. Near-field imaging of this highly doped form of graphene allows us to characterize plasmons, including their corresponding lifetimes, over a broad frequency range. For bilayer graphene, in contrast to the monolayer system, a phonon-induced dipole moment results in increased plasmon damping around the intrinsic phonon frequency. Strong coupling between intrinsic graphene phonons and plasmons is found, supported by ab initio calculations of the coupling strength, which are in good agreement with the experimental data.

Highly confined low-loss plasmons in graphene-boron nitride heterostructures.

Graphene plasmons were predicted to possess simultaneous ultrastrong field confinement and very low damping, enabling new classes of devices for deep-subwavelength metamaterials, single-photon nonlinearities, extraordinarily strong light-matter interactions and nano-optoelectronic switches. Although all of these great prospects require low damping, thus far strong plasmon damping has been observed, with both impurity scattering and many-body effects in graphene proposed as possible explanations. With the advent of van der Waals heterostructures, new methods have been developed to integrate graphene with other atomically flat materials. In this Article we exploit near-field microscopy to image propagating plasmons in high-quality graphene encapsulated between two films of hexagonal boron nitride (h-BN). We determine the dispersion and plasmon damping in real space. We find unprecedentedly low plasmon damping combined with strong field confinement and confirm the high uniformity of this plasmonic medium. The main damping channels are attributed to intrinsic thermal phonons in the graphene and dielectric losses in the h-BN. The observation and in-depth understanding of low plasmon damping is the key to the development of graphene nanophotonic and nano-optoelectronic devices.

Strong plasmon reflection at nanometer-size gaps in monolayer graphene on SiC.

We employ tip-enhanced infrared near-field microscopy to study the plasmonic properties of epitaxial quasi-free-standing monolayer graphene on silicon carbide. The near-field images reveal propagating graphene plasmons, as well as a strong plasmon reflection at gaps in the graphene layer, which appear at the steps between the SiC terraces. When the step height is around 1.5 nm, which is two orders of magnitude smaller than the plasmon wavelength, the reflection signal reaches 20% of its value at graphene edges, and it approaches 50% for step heights as small as 5 nm. This intriguing observation is corroborated by numerical simulations and explained by the accumulation of a line charge at the graphene termination. The associated electromagnetic fields at the graphene termination decay within a few nanometers, thus preventing efficient plasmon transmission across nanoscale gaps. Our work suggests that plasmon propagation in graphene-based circuits can be tailored using extremely compact nanostructures, such as ultranarrow gaps. It also demonstrates that tip-enhanced near-field microscopy is a powerful contactless tool to examine nanoscale defects in graphene.

Attitudes towards natural wines among Spanish winemakers: Relationship with environmental awareness.

There is an important movement in the wine industry towards the production of alternative and more sustainable wines. Natural wine (NW) is a controversial category of alternative wines, which needs to be further explored. Given the role of technical experts as opinion leaders, the present work aims to explore the attitudes of Spanish winemakers towards NW and their relationship with their overall environmental awareness. Therefore, 307 Spanish winemakers completed a questionnaire to evaluate: (1) their attitudes towards NW by scoring their agreement with 31 statements, (2) their ecological awareness by evaluating 11 items, (3) their frequency of consumption and interest towards NW, and (4) their sociodemographic profile and general information about wine production. PCA with varimax rotation calculated on 28 of the 31 statements related to their attitudes showed six independent dimensions. Further hierarchical cluster analysis calculated with the six dimensions showed five clusters of wine experts with different attitudes towards NW. Results show that there is a major negative attitude towards the flavour of NW, their ageing capacity and their quality-price ratio, but a positive one in terms of economic impact for the wine industry. Aspects related to the role of NW in tradition, social identity, ecology, health, artisanal production and economic feasibility mark differential attitudes. Interestingly, the dimension related to winemakers attitude towards tradition, social identity, and ecology of NW was positively correlated with their overall ecological awareness and thus their life style. This paper sheds light in the understanding of the behaviour of Spanish winemakers regarding ecological transition and provides tools for policymaking regarding NW certification.

Observation of naturally canalized phonon polaritons in LiV2O5 thin layers.

Polariton canalization is characterized by intrinsic collimation of energy flow along a single crystalline axis. This optical phenomenon has been experimentally demonstrated at the nanoscale by stacking and twisting van der Waals (vdW) layers of α-MoO3, by combining α-MoO3 and graphene, or by fabricating an h-BN metasurface. However, these material platforms have significant drawbacks, such as complex fabrication and high optical losses in the case of metasurfaces. Ideally, it would be possible to canalize polaritons "naturally" in a single pristine layer. Here, we theoretically predict and experimentally demonstrate naturally canalized phonon polaritons (PhPs) in a single thin layer of the vdW crystal LiV2O5. In addition to canalization, PhPs in LiV2O5 exhibit strong field confinement ( λ p ~ λ 0 27 ), slow group velocity (0.0015c), and ultra-low losses (lifetimes of 2 ps). Our findings are promising for the implementation of low-loss optical nanodevices where strongly directional light propagation is needed, such as waveguides or optical routers.

Visualizing the near-field coupling and interference of bonding and anti-bonding modes in infrared dimer nanoantennas.

We directly visualize and identify the capacitive coupling of infrared dimer antennas in the near field by employing scattering-type scanning near-field optical microscopy (s-SNOM). The coupling is identified by (i) resolving the strongly enhanced nano-localized near fields in the antenna gap and by (ii) tracing the red shift of the dimer resonance when compared to the resonance of the single antenna constituents. Furthermore, by modifying the illumination geometry we break the symmetry, providing a means to excite both the bonding and the "dark" anti-bonding modes. By spectrally matching both modes, their interference yields an enhancement or suppression of the near fields at specific locations, which could be useful in nanoscale coherent control applications.

Terahertz Twistoptics-Engineering Canalized Phonon Polaritons.

The terahertz (THz) frequency range is key to studying collective excitations in many crystals and organic molecules. However, due to the large wavelength of THz radiation, the local probing of these excitations in smaller crystalline structures or few-molecule arrangements requires sophisticated methods to confine THz light down to the nanometer length scale, as well as to manipulate such a confined radiation. For this purpose, in recent years, taking advantage of hyperbolic phonon polaritons (HPhPs) in highly anisotropic van der Waals (vdW) materials has emerged as a promising approach, offering a multitude of manipulation options, such as control over the wavefront shape and propagation direction. Here, we demonstrate the THz application of twist-angle-induced HPhP manipulation, designing the propagation of confined THz radiation between 8.39 and 8.98 THz in the vdW material α-molybdenum trioxide (α-MoO3), hence extending twistoptics to this intriguing frequency range. Our images, recorded by near-field optical microscopy, show the frequency- and twist-angle-dependent changes between hyperbolic and elliptic polariton propagation, revealing a polaritonic transition at THz frequencies. As a result, we are able to allocate canalization (highly collimated propagation) of confined THz radiation by carefully adjusting these two parameters, i.e. frequency and twist angle. Specifically, we report polariton canalization in α-MoO3 at 8.67 THz for a twist angle of 50°. Our results demonstrate the precise control and manipulation of confined collective excitations at THz frequencies, particularly offering possibilities for nanophotonic applications.

Real-space mapping of Fano interference in plasmonic metamolecules.

An unprecedented control of the spectral response of plasmonic nanoantennas has recently been achieved by designing structures that exhibit Fano resonances. This new insight is paving the way for a variety of applications, such as biochemical sensing and surface-enhanced Raman spectroscopy. Here we use scattering-type near-field optical microscopy to map the spatial field distribution of Fano modes in infrared plasmonic systems. We observe in real space the interference of narrow (dark) and broad (bright) plasmonic resonances, yielding intensity and phase toggling between different portions of the plasmonic metamolecules when either their geometric sizes or the illumination wavelength is varied.

Negative reflection of nanoscale-confined polaritons in a low-loss natural medium.

Negative reflection occurs when light is reflected toward the same side of the normal to the boundary from which it is incident. This exotic optical phenomenon is not only yet to be visualized in real space but also remains unexplored, both at the nanoscale and in natural media. Here, we directly visualize nanoscale-confined polaritons negatively reflecting on subwavelength mirrors fabricated in a low-loss van der Waals crystal. Our near-field nanoimaging results unveil an unconventional and broad tunability of both the polaritonic wavelength and direction of propagation upon negative reflection. On the basis of these findings, we introduce a device in nano-optics: a hyperbolic nanoresonator, in which hyperbolic polaritons with different momenta reflect back to a common point source, enhancing the intensity. These results pave way to realize nanophotonics in low-loss natural media, providing an efficient route to control nanolight, a key for future on-chip optical nanotechnologies.

Germanium Monosulfide as a Natural Platform for Highly Anisotropic THz Polaritons.

Terahertz (THz) electromagnetic radiation is key to access collective excitations such as magnons (spins), plasmons (electrons), or phonons (atomic vibrations), thus bridging topics between optics and solid-state physics. Confinement of THz light to the nanometer length scale is desirable for local probing of such excitations in low-dimensional systems, thereby circumventing the large footprint and inherently low spectral power density of far-field THz radiation. For that purpose, phonon polaritons (PhPs) in anisotropic van der Waals (vdW) materials have recently emerged as a promising platform for THz nanooptics. Hence, there is a demand for the exploration of materials that feature not only THz PhPs at different spectral regimes but also host anisotropic (directional) electrical, thermoelectric, and vibronic properties. To that end, we introduce here the semiconducting vdW-material alpha-germanium(II) sulfide (GeS) as an intriguing candidate. By employing THz nanospectroscopy supported by theoretical analysis, we provide a thorough characterization of the different in-plane hyperbolic and elliptical PhP modes in GeS. We find not only PhPs with long lifetimes (τ > 2 ps) and excellent THz light confinement (λ0/λ > 45) but also an intrinsic, phonon-induced anomalous dispersion as well as signatures of naturally occurring, substrate-mediated PhP canalization within a single GeS slab.

Active control of micrometer plasmon propagation in suspended graphene.

Due to the two-dimensional character of graphene, the plasmons sustained by this material have been invariably studied in supported samples so far. The substrate provides stability for graphene but often causes undesired interactions (such as dielectric losses, phonon hybridization, and impurity scattering) that compromise the quality and limit the intrinsic flexibility of graphene plasmons. Here, we demonstrate the visualization of plasmons in suspended graphene at room temperature, exhibiting high-quality factor Q~33 and long propagation length > 3 µm. We introduce the graphene suspension height as an effective plasmonic tuning knob that enables in situ change of the dielectric environment and substantially modulates the plasmon wavelength, propagation length, and group velocity. Such active control of micrometer plasmon propagation facilitates near-unity-order modulation of nanoscale energy flow that serves as a plasmonic switch with an on-off ratio above 14. The suspended graphene plasmons possess long propagation length, high tunability, and controllable energy transmission simultaneously, opening up broad horizons for application in nano-photonic devices.

Active and Passive Tuning of Ultranarrow Resonances in Polaritonic Nanoantennas.

Optical nanoantennas are of great importance for photonic devices and spectroscopy due to their capability of squeezing light at the nanoscale and enhancing light-matter interactions. Among them, nanoantennas made of polar crystals supporting phonon polaritons (phononic nanoantennas) exhibit the highest quality factors. This is due to the low optical losses inherent in these materials, which, however, hinder the spectral tuning of the nanoantennas due to their dielectric nature. Here, active and passive tuning of ultranarrow resonances in phononic nanoantennas is realized over a wide spectral range (≈35 cm-1 , being the resonance linewidth ≈9 cm-1 ), monitored by near-field nanoscopy. To do that, the local environment of a single nanoantenna made of hexagonal boron nitride is modified by placing it on different polar substrates, such as quartz and 4H-silicon carbide, or covering it with layers of a high-refractive-index van der Waals crystal (WSe2 ). Importantly, active tuning of the nanoantenna polaritonic resonances is demonstrated by placing it on top of a gated graphene monolayer in which the Fermi energy is varied. This work presents the realization of tunable polaritonic nanoantennas with ultranarrow resonances, which can find applications in active nanooptics and (bio)sensing.