In the field of molecular polaritonics, stronger coupling between vibrational modes and cavity systems is highly sought after. The coupling strength in these systems scales inversely with cavity mode volumes (Vm), yet traditional Fabry-Perot cavities are diffraction-limited. To overcome this limitation, we employ hyperbolic hexagonal boron nitride (hBN) to enable subdiffractional Fabry-Perot-like modes. In this work, we use scattering-type scanning near-field optical microscopy (s-SNOM) to directly image polariton propagation and quantify vibrational strong coupling to weak C-H bending modes in poly(methyl methacrylate) (PMMA). The isotopic composition of the hBN layer dictates the frequency range of the material's Reststrahlen band, with the strongest coupling arising when the TO phonon is closest in energy to the molecular vibrational mode. We further characterize how coupling strengths scale with the thickness of the PMMA and hBN layers, as the PMMA layer thickness dictates the number of molecules available to fill an evanescent mode volume and the thickness of the hBN dictates the size of the evanescent mode volume. Ultimately, this study demonstrates that reduced mode volumes and a more complete understanding of the coupling mechanisms to tune and control the interactions are crucial to advancement in the field.

Thermal transport across solid-solid interfaces is vital for advanced electronic and photonic applications, yet conventional conduction pathways often restrict performance. In polar crystals, hybridized vibrational modes called phonon polaritons offer a promising avenue to overcome the limitations of intrinsic phonon heat conduction. Here our work demonstrates that volume-confined hyperbolic phonon polariton (HPhP) modes can transfer energy across solid-solid interfaces at rates far exceeding phonon-phonon conduction. Using pump-probe thermoreflectance with a mid-infrared, tunable probe pulse with subpicosecond resolution, we remotely and selectively observe HPhP modes in hexagonal boron nitride (hBN) via broadband radiative heating from a gold source. Our measurements ascertain that hot electrons impinging at the interface radiate directly into the HPhPs of hBN in the near field, bypassing the phonon-phonon transport pathway. Such polaritonic coupling enables thermal transport speeds in solids orders of magnitude faster than possible through diffusive phonon processes. We thereby showcase a pronounced thermal transport enhancement across the gold-hBN interface via phonon-polariton coupling, advancing the limits of interfacial heat transfer.

AbstractPolariton 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 ($${{{{{{\boldsymbol{\lambda }}}}}}}_{{{{{{\bf{p}}}}}}} \sim \frac{{{{{{{\boldsymbol{\lambda }}}}}}}_{{{{{{\bf{0}}}}}}}}{{{{{{\bf{27}}}}}}}$$ 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.

Structural anisotropy in crystals is crucial for controlling light propagation, particularly in the infrared spectral regime where optical frequencies overlap with crystalline lattice resonances, enabling light-matter coupled quasiparticles called phonon polaritons (PhPs). Exploring PhPs in anisotropic materials like hBN and MoO3 has led to advancements in light confinement and manipulation. In a recent study, PhPs in the monoclinic crystal β-Ga2O3 (bGO) were shown to exhibit strongly asymmetric propagation with a frequency dispersive optical axis. Here, using scanning near-field optical microscopy (s-SNOM), we directly image the symmetry-broken propagation of hyperbolic shear polaritons in bGO. Further, we demonstrate the control and enhancement of shear-induced propagation asymmetry by varying the incident laser orientation and polariton momentum using different sizes of nano-antennas. Finally, we observe significant rotation of the hyperbola axis by changing the frequency of incident light. Our findings lay the groundwork for the widespread utilization and implementation of polaritons in low-symmetry crystals.

Hyperbolic phonon polaritons (HPhPs) can be supported in materials where the real parts of their permittivities along different directions are opposite in sign. HPhPs offer confinements of long-wavelength light to deeply subdiffractional scales, while the evanescent field allows for interactions with substrates, enabling the tuning of HPhPs by altering the underlying materials. Yet, conventionally used noble metal and dielectric substrates restrict the tunability of this approach. To overcome this challenge, here we show that doped semiconductor substrates, e.g., InAs and CdO, enable a significant tuning effect and dynamic modulations. We elucidated HPhP tuning with the InAs plasma frequency in the near-field, with a maximum difference of 8.3 times. Moreover, the system can be dynamically modulated by photo-injecting carriers into the InAs substrate, leading to a wavevector change of ~20%. Overall, the demonstrated hBN/doped semiconductor platform offers significant improvements towards manipulating HPhPs, and potential for engineered and modulated polaritonic systems.

Abstract Structural anisotropy in a crystal is one of the key tools for controlling light propagation. The correlation between crystalline structure and the interaction with light is strongest in the infrared spectral regime, where optical frequencies overlap with anisotropic lattice resonances of materials, thereby enabling light-matter coupling through quasiparticles called phonon polaritons (PhPs). In recent years, the exploration of PhPs in anisotropic materials has yielded new levels of confinement and manipulation of light. The strongly anisotropic bonds in materials such as hBN and MoO3 lead to hyperbolic phonon polaritons that exhibit even stronger light confinement and propagation directionality than conventional polaritons. Recently, we showed that the enhanced anisotropy and non-orthogonal structure of the monoclinic crystal β-Ga2O3 (bGO) induces a remarkable rotation of the optical axis with frequency ("axial dispersion") associated to nano- to microscopic shear phenomena, resulting in hyperbolic PhPs that exhibit dramatic propagation asymmetry along the hyperbolic polaritonic branches. Here, we employ a Free-Electron Laser (FEL) coupled to a scattering-type scanning near-field optical microscope (s-SNOM) to enable direct imaging of the symmetry-broken propagation patterns of hyperbolic shear polaritons in bGO within the far-infrared. Further, we demonstrate how we can control and enhance the shear-induced propagation asymmetry of nano-antenna-launched shear polaritons, by varying the incidence direction with respect to the crystal orientation, as well as by momentum selection using different sizes of nano-antennas. Finally, we also observe significant rotation of the hyperbola axis as we change the incident light frequency. Our work thereby paves a foundation for widespread utilization and device implementation of polaritons in low-symmetry crystals.

Polar dielectrics are key materials of interest for infrared (IR) nanophotonic applications due to their ability to host phonon-polaritons that allow for low-loss, subdiffractional control of light. The properties of phonon-polaritons are limited by the characteristics of optical phonons, which are nominally fixed for most "bulk" materials. Superlattices composed of alternating atomically thin materials offer control over crystal anisotropy through changes in composition, optical phonon confinement, and the emergence of new modes. In particular, the modified optical phonons in superlattices offer the potential for so-called crystalline hybrids whose IR properties cannot be described as a simple mixture of the bulk constituents. To date, however, studies have primarily focused on identifying the presence of new or modified optical phonon modes rather than assessing their impact on the IR response. This study focuses on assessing the impact of confined optical phonon modes on the hybrid IR dielectric function in superlattices of GaSb and AlSb. Using a combination of first principles theory, Raman, FTIR, and spectroscopic ellipsometry, the hybrid dielectric function is found to track the confinement of optical phonons, leading to optical phonon spectral shifts of up to 20 cm-1 . These results provide an alternative pathway toward designer IR optical materials.

The polar nature of calcite results in lattice vibrations that can be stimulated through gratings and nanostructures to design spatially and spectrally coherent thermal radiation patterns. In order to obtain optimal design control over such patterned materials, it is first necessary to understand the fundamental emissivity properties of the lattice vibrations themselves. Because calcite is a uniaxial material, when the optic axis (OA) is tilted with respect to the crystal surface, the surface wave solutions to Maxwell’s equations and vibrational modes that are permitted will change due to the crystal’s structural anisotropy. This implies that the OA orientation can play a critical role in dictating which modes can be harnessed when designing a narrowband or angular thermal emitter. Here we explore the angle and polarization dependence of the bulk far-field emissivity of unpatterned calcite with tilted OA. We show that by manipulating the OA orientation via crystallographic off-cut, polarization, and sample rotation, the emissivity at a given frequency can vary by as much as 0.8. These results suggest that, in addition to serving as a basis for modifying the behavior of the relevant phonon polaritons, OA orientation can be used to alter the thermal emission pattern without the need for complex lithographic patterning.

The lattice symmetry of a crystal is one of the most important factors in determining its physical properties. Particularly, low-symmetry crystals offer powerful opportunities to control light propagation, polarization and phase 1–4 . Materials featuring extreme optical anisotropy can support a hyperbolic response, enabling coupled light–matter interactions, also known as polaritons, with highly directional propagation and compression of light to deeply sub-wavelength scales 5 . Here we show that monoclinic crystals can support hyperbolic shear polaritons, a new polariton class arising in the mid-infrared to far-infrared due to shear phenomena in the dielectric response. This feature emerges in materials in which the dielectric tensor cannot be diagonalized, that is, in low-symmetry monoclinic and triclinic crystals in which several oscillators with non-orthogonal relative orientations contribute to the optical response 6,7 . Hyperbolic shear polaritons complement previous observations of hyperbolic phonon polaritons in orthorhombic 1,3,4 and hexagonal 8,9 crystal systems, unveiling new features, such as the continuous evolution of their propagation direction with frequency, tilted wavefronts and asymmetric responses. The interplay between diagonal loss and off-diagonal shear phenomena in the dielectric response of these materials has implications for new forms of non-Hermitian and topological photonic states. We anticipate that our results will motivate new directions for polariton physics in low-symmetry materials, which include geological minerals 10 , many common oxides 11 and organic crystals 12 , greatly expanding the material base and extending design opportunities for compact photonic devices.

As the length scales of materials decrease, the heterogeneities associated with interfaces become almost as important as the surrounding materials. This has led to extensive studies of emergent electronic and magnetic interface properties in superlattices 1 – 9 . However, the interfacial vibrations that affect the phonon-mediated properties, such as thermal conductivity 10 , 11 , are measured using macroscopic techniques that lack spatial resolution. Although it is accepted that intrinsic phonons change near boundaries 12 , 13 , the physical mechanisms and length scales through which interfacial effects influence materials remain unclear. Here we demonstrate the localized vibrational response of interfaces in strontium titanate–calcium titanate superlattices by combining advanced scanning transmission electron microscopy imaging and spectroscopy, density functional theory calculations and ultrafast optical spectroscopy. Structurally diffuse interfaces that bridge the bounding materials are observed and this local structure creates phonon modes that determine the global response of the superlattice once the spacing of the interfaces approaches the phonon spatial extent. Our results provide direct visualization of the progression of the local atomic structure and interface vibrations as they come to determine the vibrational response of an entire superlattice. Direct observation of such local atomic and vibrational phenomena demonstrates that their spatial extent needs to be quantified to understand macroscopic behaviour. Tailoring interfaces, and knowing their local vibrational response, provides a means of pursuing designer solids with emergent infrared and thermal responses.

Heterostructures including the members of the 6.1{\AA} semiconductor family (AlSb, GaSb, and InAs) are used in infrared optoelectronic devices as well as a variety of other applications. Short-period superlattices of these materials are also of interest for creating composite materials with designer infrared dielectric functions. The conditions needed to create sharp InAs/GaSb and InAs/AlSb interfaces are well known, but the AlSb/GaSb interface is much less well-understood. In this article, we test a variety of interventions designed to improve interface sharpness in AlSb/GaSb short-period superlattices. These interventions include substrate temperature, III:Sb flux ratio, and the use of a bismuth surfactant. Superlattices are characterized by high-resolution x-ray diffraction and infrared spectroscopy. We find that AlSb/GaSb short-period superlattices have a wide growth window over which sharp interfaces can be obtained.

Natural hyperbolic materials with dielectric permittivities of opposite signs along different principal axes can confine long-wavelength electromagnetic waves down to the nanoscale, well below the diffraction limit. Confined electromagnetic waves coupled to phonons in hyperbolic dielectrics including hexagonal boron nitride (hBN) and α-MoO3 are referred to as hyperbolic phonon polaritons (HPPs). HPP dissipation at ambient conditions is substantial, and its fundamental limits remain unexplored. Here, we exploit cryogenic nanoinfrared imaging to investigate propagating HPPs in isotopically pure hBN and naturally abundant α-MoO3 crystals. Close to liquid-nitrogen temperatures, losses for HPPs in isotopic hBN drop significantly, resulting in propagation lengths in excess of 8 μm, with lifetimes exceeding 5 ps, thereby surpassing prior reports on such highly confined polaritonic modes. Our nanoscale, temperature-dependent imaging reveals the relevance of acoustic phonons in HPP damping and will be instrumental in mitigating such losses for miniaturized mid-infrared technologies operating at liquid-nitrogen temperatures.

Hyperbolic phonon polaritons (HPhPs) enable strong confinements, low losses, and intrinsic beam steering capabilities determined by the refractive index anisotropy-providing opportunities from hyperlensing to flat optics and other applications. Here, two scanning-probe techniques, photothermal induced resonance (PTIR) and scattering-type scanning near-field optical microscopy (s-SNOM), are used to map infrared (6.4-7.4μm) HPhPs in large (up to 120×250μm2 near-monoisotopic >99%B10) hexagonal boron nitride (hBN) flakes. Wide (≈40μm) PTIR and s-SNOM scans on such large flakes avoid interference from polaritons launched from different asperities (edges, folds, surface defects, etc.) and together with Fourier analyses 0.05μm-1 resolution) enable precise measurements of HPhP lifetimes (up to ≈4.2ps and propagation lengths (up to ≈25 and ≈17μm for the first- and second-order branches, respectively). With respect to naturally abundant hBN, we report an eightfold improved, record-high (for hBN) propagating figure of merit (i.e., with both high confinement and long lifetime) in ≈99%B10 hBN, achieving, finally, theoretically predicted values. We show that wide near-field scans critically enable accurate estimates of the polaritons' lifetimes and propagation lengths and that the incidence angle of light, with respect to both the sample plane and the flake edge, needs to be considered to extract correctly the dispersion relation from the near-field polaritons maps. Overall, the measurements and data analyses employed here elucidate details pertaining to polaritons' propagation in isotopically enriched hBN and pave the way for developing high-performance HPhP-based devices.

The hyperbolic phonon polaritons supported in hexagonal boron nitride (hBN) with long scattering lifetimes are advantageous for applications such as super-resolution imaging via hyperlensing. Yet, hyperlens imaging is challenging for distinguishing individual and closely spaced objects and for correlating the complicated hyperlens fields with the structure of an unknown object underneath. Here, we make significant strides to overcome each of these challenges. First, we demonstrate that monoisotopic h11BN provides significant improvements in spatial resolution, experimentally resolving structures as small as 44 nm and those with sub 25 nm spacings at 6.76 μm free-space wavelength. We also present an image reconstruction algorithm that provides a structurally accurate, visual representation of the embedded objects from the complex hyperlens field. Further, we offer additional insights into optimizing hyperlens performance on the basis of material properties, with an eye toward realizing far-field imaging modalities. Thus, our results significantly advance label-free, high-resolution, spectrally selective hyperlens imaging and image reconstruction methodologies.

Phonon polaritons (PhPs) enable a variety of applications, yet it requires PhPs supported in the desired frequency range. The two BN allotropes (cubic and hexagonal, cBN and hBN) are of particular interest, as their optic phonons fall within the so-called molecular-fingerprint region (~ 1000–1610 cm−1). However, there remains a spectral gap between PhPs covered by these two, limiting applications. Thus, we isotopically engineered hBN and cBN and examined the optic phonons. For hBN, enhancement of the optic phonon lifetimes and shifted frequencies are observed. However, lifetimes are observed to decrease with the enrichment of cBN by 10B, 11B, and 15N. We propose that the reduced lifetimes are not due to intrinsic loss, but rather increased defect concentrations resulting from the modified growth, supported by first-principles calculations. Thus, reducing the extrinsic defects in isotopically engineered cBN may present a path toward overcoming these restrictions for applications in the molecular-fingerprint region.

In article number 1908176, Joshua D. Caldwell, Alexey Y. Nikitin, Pablo Alonso-González, and co-workers extract the IR permittivity of the biaxial crystal α-MoO3 by correlative far- and near-field measurements, using FTIR reflectance spectroscopy and s-SNOM polariton interferometry, thus providing both an accurate permittivity model and a novel approach to extracting dielectric functions of nanomaterials. Moreover, through density functional theory, insights into the vibrational states dictating such permittivity are revealed.

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.

The anisotropy of hexagonal boron nitride (hBN) gives rise to hyperbolic phonon-polaritons (HPhPs), notable for their volumetric frequency-dependent propagation and strong confinement. For frustum (truncated nanocone) structures, theory predicts five, high-order HPhPs, sets, but only one set was observed previously with far-field reflectance and scattering-type scanning near-field optical microscopy. In contrast, the photothermal induced resonance (PTIR) technique has recently permitted sampling of the full HPhP dispersion and observing such elusive predicted modes; however, the mechanism underlying PTIR sensitivity to these weakly-scattering modes, while critical to their understanding, has not yet been clarified. Here, by comparing conventional contact- and newly developed tapping-mode PTIR, we show that the PTIR sensitivity to those weakly-scattering, high-Q (up to ≈280) modes is, contrary to a previous hypothesis, unrelated to the probe operation (contact or tapping) and is instead linked to PTIR ability to detect tip-launched dark, volumetrically-confined polaritons, rather than nanostructure-launched HPhPs modes observed by other techniques. Furthermore, we show that in contrast with plasmons and surface phonon-polaritons, whose Q-factors and optical cross-sections are typically degraded by the proximity of other nanostructures, the high-Q HPhP resonances are preserved even in high-density hBN frustum arrays, which is useful in sensing and quantum emission applications.

The field of nanophotonics has long sought to identify mechanisms to realize dynamical control of optical modes. In most approaches, the magnitude of tuning is dependent upon the degree to which the optical permittivity is malleable upon some material change, such as carrier concentration. Here, through a multiwavelength Raman spectroscopic examination of 4H-SiC nanopillars, momentum is identified as an alternative means to enhance spectral tunability of nanophotonic modes, owing to the spatial dispersion implicit in the infrared (IR) optical permittivity of polar semiconductors. Experimentally, this is deduced through the observation of a "forbidden" Raman mode at approximate to 780 cm(-1) and the emergence of the surface-optical phonon polariton at approximate to 950 cm(-1), which evolved with intensities dependent upon the nanopillar diameter and the wavelength of the incident light. The evolution of these modes is accompanied by a redshift and spectral narrowing of the longitudinal-optical plasmon coupled (LOPC) mode exhibiting a similar wavelength and diameter dependence. Mie resonances, identified using ultraviolet-visible spectroscopy and excited by the visible laser excitation of the Raman experiment, acted to vary the momentum sampled during the Raman experiment leading to these spectral dependencies. This was deduced by fitting the Raman response accounting for both the presence of the surface phonon and the overdamped LOPC mode under the Lindhard-Mermin approximation. This fitting not only explains the Raman response, but also clearly exhibits the spatially disperse permittivity of the SiC, which is shown to have a momentum-dependent sensitivity to carrier concentration. Such sensitivity, in turn, highlights the potential of spatial dispersion as a means to accentuate the performance of active IR nanophotonic approaches employing phonon polaritons.