Spatiotemporal beating and vortices of van der Waals hyperbolic polaritons.

In conventional thin materials, the diffraction limit of light constrains the number of waveguide modes that can exist at a given frequency. However, layered van der Waals (vdW) materials, such as hexagonal boron nitride (hBN), can surpass this limitation due to their dielectric anisotropy, exhibiting positive permittivity along one optic axis and negativity along the other. This enables the propagation of hyperbolic rays within the material bulk and an unlimited number of subdiffractional modes characterized by hyperbolic dispersion. By employing time-domain near-field interferometry to analyze ultrafast hyperbolic ray pulses in thin hBN, we showed that their zigzag reflection trajectories bound within the hBN layer create an illusion of backward-moving and leaping behavior of pulse fringes. These rays result from the coherent beating of hyperbolic waveguide modes but could be mistakenly interpreted as negative group velocities and backward energy flow. Moreover, the zigzag reflections produce nanoscale (60 nm) and ultrafast (40 fs) spatiotemporal optical vortices along the trajectory, presenting opportunities to chiral spatiotemporal control of light-matter interactions. Supported by experimental evidence, our simulations highlight the potential of hyperbolic ray reflections for molecular vibrational absorption nanospectroscopy. The results pave the way for miniaturized, on-chip optical spectrometers, and ultrafast optical manipulation.

High-quality nanocavities through multimodal confinement of hyperbolic polaritons in hexagonal boron nitride.

Compressing light into nanocavities substantially enhances light-matter interactions, which has been a major driver for nanostructured materials research. However, extreme confinement generally comes at the cost of absorption and low resonator quality factors. Here we suggest an alternative optical multimodal confinement mechanism, unlocking the potential of hyperbolic phonon polaritons in isotopically pure hexagonal boron nitride. We produce deep-subwavelength cavities and demonstrate several orders of magnitude improvement in confinement, with estimated Purcell factors exceeding 108 and quality factors in the 50-480 range, values approaching the intrinsic quality factor of hexagonal boron nitride polaritons. Intriguingly, the quality factors we obtain exceed the maximum predicted by impedance-mismatch considerations, indicating that confinement is boosted by higher-order modes. We expect that our multimodal approach to nanoscale polariton manipulation will have far-reaching implications for ultrastrong light-matter interactions, mid-infrared nonlinear optics and nanoscale sensors.

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.

Amplitude- and Phase-Resolved Infrared Nanoimaging and Nanospectroscopy of Polaritons in a Liquid Environment.

Polaritons allow for strong light-matter coupling and for highly sensitive analysis of (bio)chemical substances and processes. Nanoimaging of the polaritons' evanescent fields is critically important for experimental mode identification and field confinement studies. Here we describe two setups for polariton nanoimaging and spectroscopy in liquid. We first demonstrate the mapping of localized plasmon polaritons in metal antennas with a transflection infrared scattering-type scanning near-field optical microscope (s-SNOM), where the tip acts as a near-field scattering probe. We then demonstrate a total internal reflection (TIR)-based setup, where the tip is both launching and probing ultraconfined polaritons in van der Waals materials (here phonon polaritons in hexagonal boron nitride flakes), laying the foundation for s-SNOM-based polariton interferometry in liquid. Our results promise manifold applications, for example, in situ studies of strong coupling between polaritons and molecular vibrations or chemical reactions at the bare or functionalized surfaces of polaritonic materials.

Total Internal Reflection Peak Force Infrared Microscopy.

Total internal reflection (TIR) infrared spectroscopy is a convenient measurement tool for collecting spectra for chemical identification. However, TIR infrared microscopy lacks high spatial resolution due to the optical diffraction limit and difficulty to preserve a high-quality wave front for focus. In this article, we present the peak force infrared microscopy in the TIR geometry to achieve a 10 nm spatial resolution. Instead of optical detection, photothermal responses of the sample are collected in the peak force tapping mode of atomic force microscopy. We demonstrate the technique on two representative samples: structured polymers for soft matters and a hexagonal boron nitride flake for two-dimensional materials. As an extension of the apparatus, we also demonstrate nanoinfrared imaging with the TIR excitation for photoinduced force microscopy. The combination of TIR geometry with nanoinfrared microscopies simplifies the optical alignment, providing alternative instrument-designing principles for atomic force microscopy-based infrared microscopy.

Probing Mid-Infrared Phonon Polaritons in the Aqueous Phase.

Phonon polaritons (PhPs) are collective phonon oscillations with hybridized electromagnetic fields, which concentrate mid-infrared optical fields that can match molecular vibrations. The utilization of PhPs holds the promise for chemical sensing tools and polariton-enhanced nanospectroscopy. However, investigations and innovations on PhPs in the aqueous phase remain stagnant because of the lack of in situ mid-infrared nanoimaging methods in water. Strong infrared absorption from water prohibits optical delivery and detection in the mid-infrared for scattering-type near-field microscopy. Here, we present our solution: the detection of photothermal responses caused by the excitation of PhPs by liquid phase peak force infrared (LiPFIR) microscopy. Characteristic interference fringes of PhPs in 10B isotope-enriched h-BN were measured in the aqueous phase and their dispersion relationship extracted. LiPFIR enables the measurement of mid-infrared PhPs in the fluid phase, opening possibilities and facilitating the development of mid-IR phonon polaritonics in water.

Atomic-force-microscopy-based time-domain two-dimensional infrared nanospectroscopy.

For decades, infrared (IR) spectroscopy has advanced on two distinct frontiers: enhancing spatial resolution and broadening spectroscopic information. Although atomic force microscopy (AFM)-based IR microscopy overcomes Abbe's diffraction limit and reaches sub-10 nm spatial resolutions, time-domain two-dimensional IR spectroscopy (2DIR) provides insights into molecular structures, mode coupling and energy transfers. Here we bridge the boundary between these two techniques and develop AFM-2DIR nanospectroscopy. Our method offers the spatial precision of AFM in combination with the rich spectroscopic information provided by 2DIR. This approach mechanically detects the sample's photothermal responses to a tip-enhanced femtosecond IR pulse sequence and extracts spatially resolved spectroscopic information via FFTs. In a proof-of-principle experiment, we elucidate the anharmonicity of a carbonyl vibrational mode. Further, leveraging the near-field photons' high momenta from the tip enhancement for phase matching, we photothermally probe hyperbolic phonon polaritons in isotope-enriched h10BN. Our measurements unveil an energy transfer between phonon polaritons and phonons, as well as among different polariton modes, possibly aided by scattering at interfaces. The AFM-2DIR nanospectroscopy enables the in situ investigations of vibrational anharmonicity, coupling and energy transfers in heterogeneous materials and nanostructures, especially suitable for unravelling the relaxation process in two-dimensional materials at IR frequencies.

Boron and Nitrogen Isotope Effects on Hexagonal Boron Nitride Properties.

The unique physical, mechanical, chemical, optical, and electronic properties of hexagonal boron nitride (hBN) make it a promising 2D material for electronic, optoelectronic, nanophotonic, and quantum devices. Here, the changes in hBN's properties induced by isotopic purification in both boron and nitrogen are reported. Previous studies on isotopically pure hBN have focused on purifying the boron isotope concentration in hBN from its natural concentration (≈20 at% 10 B, 80 at% 11 B) while using naturally abundant nitrogen (99.6 at% 14 N, 0.4 at% 15 N), that is, almost pure 14 N. In this study, the class of isotopically purified hBN crystals to 15 N is extended. Crystals in the four configurations, namely h10 B14 N, h11 B14 N, h10 B15 N, and h11 B15 N, are grown by the metal flux method using boron and nitrogen single isotope (> 99%) enriched sources, with nickel plus chromium as the solvent. In-depth Raman and photoluminescence spectroscopies demonstrate the high quality of the monoisotopic hBN crystals with vibrational and optical properties of the 15 N-purified crystals at the state-of-the-art of currently available 14 N-purified hBN. The growth of high-quality h10 B14 N, h11 B14 N, h10 B15 N, and h11 B15 N opens exciting perspectives for thermal conductivity control in heat management, as well as for advanced functionalities in quantum technologies.

Hexagonal Boron Nitride Slab Waveguides for Enhanced Spectroscopy of Encapsulated 2D Materials.

The layered insulator hexagonal boron nitride (hBN) is a critical substrate that brings out the exceptional intrinsic properties of two-dimensional (2D) materials such as graphene and transition metal dichalcogenides (TMDs). In this work, the authors demonstrate how hBN slabs tuned to the correct thickness act as optical waveguides, enabling direct optical coupling of light emission from encapsulated layers into waveguide modes. Molybdenum selenide (MoSe2 ) and tungsten selenide (WSe2 ) are integrated within hBN-based waveguides and demonstrate direct coupling of photoluminescence emitted by in-plane and out-of-plane transition dipoles (bright and dark excitons) to slab waveguide modes. Fourier plane imaging of waveguided photoluminescence from MoSe2 demonstrates that dry etched hBN edges are an effective out-coupler of waveguided light without the need for oil-immersion optics. Gated photoluminescence of WSe2 demonstrates the ability of hBN waveguides to collect light emitted by out-of-plane dark excitons.Numerical simulations explore the parameters of dipole placement and slab thickness, elucidating the critical design parameters and serving as a guide for novel devices implementing hBN slab waveguides. The results provide a direct route for waveguide-based interrogation of layered materials, as well as a way to integrate layered materials into future photonic devices at arbitrary positions whilst maintaining their intrinsic properties.

Isotope engineering for spin defects in van der Waals materials.

Spin defects in van der Waals materials offer a promising platform for advancing quantum technologies. Here, we propose and demonstrate a powerful technique based on isotope engineering of host materials to significantly enhance the coherence properties of embedded spin defects. Focusing on the recently-discovered negatively charged boron vacancy center ([Formula: see text]) in hexagonal boron nitride (hBN), we grow isotopically purified h10B15N crystals. Compared to [Formula: see text] in hBN with the natural distribution of isotopes, we observe substantially narrower and less crowded [Formula: see text] spin transitions as well as extended coherence time T2 and relaxation time T1. For quantum sensing, [Formula: see text] centers in our h10B15N samples exhibit a factor of 4 (2) enhancement in DC (AC) magnetic field sensitivity. For additional quantum resources, the individual addressability of the [Formula: see text] hyperfine levels enables the dynamical polarization and coherent control of the three nearest-neighbor 15N nuclear spins. Our results demonstrate the power of isotope engineering for enhancing the properties of quantum spin defects in hBN, and can be readily extended to improving spin qubits in a broad family of van der Waals materials.

Tunable Phonon Polariton Hybridization in a van der Waals Hetero-Bicrystal.

Phonon polaritons, the hybrid quasiparticles resulting from the coupling of photons and lattice vibrations, have gained significant attention in the field of layered van der Waals heterostructures. Particular interest has been paid to hetero-bicrystals composed of molybdenum oxide (MoO3) and hexagonal boron nitride (hBN), which feature polariton dispersion tailorable via avoided polariton mode crossings. In this work, we systematically study the polariton eigenmodes in MoO3-hBN hetero-bicrystals self-assembled on ultrasmooth gold using synchrotron infrared nanospectroscopy. We experimentally demonstrate that the spectral gap in bicrystal dispersion and corresponding regimes of negative refraction can be tuned by material layer thickness, and we quantitatively match these results with a simple analytic model. We also investigate polaritonic cavity modes and polariton propagation along "forbidden" directions in our microscale bicrystals, which arise from the finite in-plane dimension of the synthesized MoO3 micro-ribbons. Our findings shed light on the unique dispersion properties of polaritons in van der Waals heterostructures and pave the way for applications leveraging deeply sub-wavelength mid-infrared light matter interactions. This article is protected by copyright. All rights reserved.

Coupled Tamm Phonon and Plasmon Polaritons for Designer Planar Multiresonance Absorbers.

Wavelength-selective absorbers (WS-absorbers) are of interest for various applications, including chemical sensing and light sources. Lithography-free fabrication of WS-absorbers can be realized via Tamm plasmon polaritons (TPPs) supported by distributed Bragg reflectors (DBRs) on plasmonic materials. While multifrequency and nearly arbitrary spectra can be realized with TPPs via inverse design algorithms, demanding and thick DBRs are required for high quality-factors (Q-factors) and/or multiband TPP-absorbers, increasing the cost and reducing fabrication error tolerance. Here, high Q-factor multiband absorption with limited DBR layers (3 layers) is experimentally demonstrated by Tamm hybrid polaritons (THPs) formed by coupling TPPs and Tamm phonon polaritons when modal frequencies are overlapped. Compared to the TPP component, the Q-factors of THPs are improved twofold, and the angular broadening is also reduced twofold, facilitating applications where narrow-band and nondispersive WS-absorbers are needed. Moreover, an open-source algorithm is developed to inversely design THP-absorbers consisting of anisotropic media and exemplify that the modal frequencies can be assigned to desirable positions. Furthermore, it is demonstrated that inversely designed THP-absorbers can realize same spectral resonances with fewer DBR layers than a TPP-absorber, thus reducing the fabrication complexity and enabling more cost-effective, lithography-free, wafer-scale WS-absorberss for applications such as free-space communications and gas sensing.

Anomalous isotope effect on mechanical properties of single atomic layer Boron Nitride.

The ideal mechanical properties and behaviors of materials without the influence of defects are of great fundamental and engineering significance but considered inaccessible. Here, we use single-atom-thin isotopically pure hexagonal boron nitride (hBN) to demonstrate that two-dimensional (2D) materials offer us close-to ideal experimental platforms to study intrinsic mechanical phenomena. The highly delicate isotope effect on the mechanical properties of monolayer hBN is directly measured by indentation: lighter 10B gives rise to higher elasticity and strength than heavier 11B. This anomalous isotope effect establishes that the intrinsic mechanical properties without the effect of defects could be measured, and the so-called ultrafine and normally neglected isotopic perturbation in nuclear charge distribution sometimes plays a more critical role than the isotopic mass effect in the mechanical and other physical properties of materials.

Water-Induced Bandgap Engineering in Nanoribbons of Hexagonal Boron Nitride.

Different from hexagonal boron nitride (hBN) sheets, the bandgap of hBN nanoribbons (BNNRs) can be changed by spatial/electrostatic confinement. It is predicted that a transverse electric field can narrow the bandgap and even cause an insulator-metal transition in BNNRs. However, experimentally introducing an overhigh electric field across the BNNR remains challenging. Here, it is theoretically and experimentally demonstrated that water adsorption greatly reduces the bandgap of zigzag-oriented BNNRs (zBNNRs). Ab initio calculations show that water molecules can be favorably assembled within the trench between two adjacent BNNRs to form a polar ice layer, which induces a transverse equivalent electric field of over 2 V nm-1 accounting for the bandgap reduction. Field-effect transistors are successfully fabricated from zBNNRs with different widths. The conductance of water-adsorbed zBNNRs can be tuned over 3 orders in magnitude via modulation of the equivalent electrical field at room temperature. Furthermore, photocurrent response measurements are taken to determine the optical bandgaps of zBNNRs with water adsorption. The zBNNR with increased width can exhibit a bandgap down to 1.17 eV. This study offers fundamental insights into new routes toward realizing electronic/optoelectronic devices and circuits based on hexagonal boron nitride.

Transverse Hypercrystals Formed by Periodically Modulated Phonon Polaritons.

Photonic crystals and metamaterials are two overarching paradigms for manipulating light. By combining these approaches, hypercrystals can be created, which are hyperbolic dispersion metamaterials that undergo periodic modulation and mix photonic-crystal-like aspects with hyperbolic dispersion physics. Despite several attempts, there has been limited experimental realization of hypercrystals due to technical and design constraints. In this work, hypercrystals with nanoscale lattice constants ranging from 25 to 160 nm were created. The Bloch modes of these crystals were then measured directly using scattering near-field microscopy. The dispersion of the Bloch modes was extracted from the frequency dependence of the Bloch modes, revealing a clear switch from positive to negative group velocity. Furthermore, spectral features specific to hypercrystals were observed in the form of sharp density of states peaks, which are a result of intermodal coupling and should not appear in ordinary polaritonic crystals with an equivalent geometry. These findings are in agreement with theoretical predictions that even simple lattices can exhibit a rich hypercrystal bandstructure. This work is of both fundamental and practical interest, providing insight into nanoscale light-matter interactions and the potential to manipulate the optical density of states.

Polariton design and modulation via van der Waals/doped semiconductor heterostructures.

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.