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.

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.

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.

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.

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.

Focusing of in-plane hyperbolic polaritons in van der Waals crystals with tailored infrared nanoantennas.

Phonon polaritons (PhPs)­light coupled to lattice vibrations­with in-plane hyperbolic dispersion exhibit ray-like propagation with large wave vectors and enhanced density of optical states along certain directions on a surface. As such, they have raised a surge of interest, promising unprecedented manipulation of infrared light at the nanoscale in a planar circuitry. Here, we demonstrate focusing of in-plane hyperbolic PhPs propagating along thin slabs of α-MoO3. To that end, we developed metallic nanoantennas of convex geometries for both efficient launching and focusing of the polaritons. The foci obtained exhibit enhanced near-field confinement and absorption compared to foci produced by in-plane isotropic PhPs. Foci sizes as small as λp/4.5 = λ0/50 were achieved (λp is the polariton wavelength and λ0 is the photon wavelength). Focusing of in-plane hyperbolic polaritons introduces a first and most basic building block developing planar polariton optics using in-plane anisotropic van der Waals materials.

Extracting the Infrared Permittivity of SiO2 Substrates Locally by Near-Field Imaging of Phonon Polaritons in a van der Waals Crystal.

Layered materials in which individual atomic layers are bonded by weak van der Waals forces (vdW materials) constitute one of the most prominent platforms for materials research. Particularly, polar vdW crystals, such as hexagonal boron nitride (h-BN), alpha-molybdenum trioxide (α-MoO3) or alpha-vanadium pentoxide (α-V2O5), have received significant attention in nano-optics, since they support phonon polaritons (PhPs)-light coupled to lattice vibrations- with strong electromagnetic confinement and low optical losses. Recently, correlative far- and near-field studies of α-MoO3 have been demonstrated as an effective strategy to accurately extract the permittivity of this material. Here, we use this accurately characterized and low-loss polaritonic material to sense its local dielectric environment, namely silica (SiO2), one of the most widespread substrates in nanotechnology. By studying the propagation of PhPs on α-MoO3 flakes with different thicknesses laying on SiO2 substrates via near-field microscopy (s-SNOM), we extract locally the infrared permittivity of SiO2. Our work reveals PhPs nanoimaging as a versatile method for the quantitative characterization of the local optical properties of dielectric substrates, crucial for understanding and predicting the response of nanomaterials and for the future scalability of integrated nanophotonic devices.

Nanoscale-Confined Terahertz Polaritons in a van der Waals Crystal.

Electromagnetic field confinement is crucial for nanophotonic technologies, since it allows for enhancing light-matter interactions, thus enabling light manipulation in deep sub-wavelength scales. In the terahertz (THz) spectral range, radiation confinement is conventionally achieved with specially designed metallic structures-such as antennas or nanoslits-with large footprints due to the rather long wavelengths of THz radiation. In this context, phonon polaritons-light coupled to lattice vibrations-in van der Waals (vdW) crystals have emerged as a promising solution for controlling light beyond the diffraction limit, as they feature extreme field confinements and low optical losses. However, experimental demonstration of nanoscale-confined phonon polaritons at THz frequencies has so far remained elusive. Here, it is provided by employing scattering-type scanning near-field optical microscopy combined with a free-electron laser to reveal a range of low-loss polaritonic excitations at frequencies from 8 to 12 THz in the vdW semiconductor α-MoO3 . In this study, THz polaritons are visualized with: i) in-plane hyperbolic dispersion, ii) extreme nanoscale field confinement (below λo  /75), and iii) long polariton lifetimes, with a lower limit of >2 ps.

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.

Infrared Permittivity of the Biaxial van der Waals Semiconductor α-MoO3 from Near- and Far-Field Correlative Studies.

The biaxial van der Waals semiconductor α-phase molybdenum trioxide (α-MoO3 ) has recently received significant attention due to its ability to support highly anisotropic phonon polaritons (PhPs)-infrared (IR) light coupled to lattice vibrations-offering an unprecedented platform for controlling the flow of energy at the nanoscale. However, to fully exploit the extraordinary IR response of this material, an accurate dielectric function is required. Here, the accurate IR dielectric function of α-MoO3 is reported by modeling far-field polarized IR reflectance spectra acquired on a single thick flake of this material. Unique to this work, the far-field model is refined by contrasting the experimental dispersion and damping of PhPs, revealed by polariton interferometry using scattering-type scanning near-field optical microscopy (s-SNOM) on thin flakes of α-MoO3 , with analytical and transfer-matrix calculations, as well as full-wave simulations. Through these correlative efforts, exceptional quantitative agreement is attained to both far- and near-field properties for multiple flakes, thus providing strong verification of the accuracy of this model, while offering a novel approach to extracting dielectric functions of nanomaterials. In addition, by employing density functional theory (DFT), insights into the various vibrational states dictating the dielectric function model and the intriguing optical properties of α-MoO3 are provided.

Chemical switching of low-loss phonon polaritons in α-MoO3 by hydrogen intercalation.

Phonon polaritons (PhPs) have attracted significant interest in the nano-optics communities because of their nanoscale confinement and long lifetimes. Although PhP modification by changing the local dielectric environment has been reported, controlled manipulation of PhPs by direct modification of the polaritonic material itself has remained elusive. Here, chemical switching of PhPs in α-MoO3 is achieved by engineering the α-MoO3 crystal through hydrogen intercalation. The intercalation process is non-volatile and recoverable, allowing reversible switching of PhPs while maintaining the long lifetimes. Precise control of the intercalation parameters enables analysis of the intermediate states, in which the needle-like hydrogenated nanostructures functioning as in-plane antennas effectively reflect and launch PhPs and form well-aligned cavities. We further achieve spatially controlled switching of PhPs in selective regions, leading to in-plane heterostructures with various geometries. The intercalation strategy introduced here opens a relatively non-destructive avenue connecting infrared nanophotonics, reconfigurable flat metasurfaces and van der Waals crystals.

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.