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.

Van der Waals quaternary oxides for tunable low-loss anisotropic polaritonics.

The discovery of ultraconfined polaritons with extreme anisotropy in a number of van der Waals (vdW) materials has unlocked new prospects for nanophotonic and optoelectronic applications. However, the range of suitable materials for specific applications remains limited. Here we introduce tellurite molybdenum quaternary oxides-which possess non-centrosymmetric crystal structures and extraordinary nonlinear optical properties-as a highly promising vdW family of materials for tunable low-loss anisotropic polaritonics. By employing chemical flux growth and exfoliation techniques, we successfully fabricate high-quality vdW layers of various compounds, including MgTeMoO6, ZnTeMoO6, MnTeMoO6 and CdTeMoO6. We show that these quaternary vdW oxides possess two distinct types of in-plane anisotropic polaritons: slab-confined and edge-confined modes. By leveraging metal cation substitutions, we establish a systematic strategy to finely tune the in-plane polariton propagation, resulting in the selective emergence of circular, elliptical or hyperbolic polariton dispersion, accompanied by ultraslow group velocities (0.0003c) and long lifetimes (5 ps). Moreover, Reststrahlen bands of these quaternary oxides naturally overlap that of α-MoO3, providing opportunities for integration. As an example, we demonstrate that combining α-MoO3 (an in-plane hyperbolic material) with CdTeMoO6 (an in-plane isotropic material) in a heterostructure facilitates collimated, diffractionless polariton propagation. Quaternary oxides expand the family of anisotropic vdW polaritons considerably, and with it, the range of nanophotonics applications that can be envisioned.

Quantitative in situ synchrotron X-ray analysis of the ALD/MLD growth of transition metal dichalcogenide TiS2 ultrathin films.

We present the results of a full quantitative analysis of X-ray absorption spectroscopy (XAS) performed in situ during the growth of ultrathin titanium disulfide (TiS2) films via an innovative two-step process, i.e. atomic layer deposition/molecular layer deposition (ALD/MLD) followed by annealing. This growth strategy aims at separating the growth process from the crystallization process by first creating an amorphous Ti-thiolate that is converted later to crystalline TiS2via thermal annealing. The simultaneous analysis of Ti and S K-edge XAS spectra, exploiting the insights from density functional theory calculations, allows us to shed light on the chemical and structural mechanisms underlying the main steps of growth. The nature of the bonding at the base of the interface creation with the SiO2 substrate is disclosed in this study. Evidence of a progressive incorporation of S in the amorphous Ti-thiolate is given. Finally, it is shown that the annealing step plays a critical role since the transformation of the Ti-thiolate into nanocrystalline TiS2 and the loss of S are simultaneously induced, validating the two-step synthesis approach, which entails distinct growth and crystallization steps. These observations contribute to a deeper understanding of the bonding mechanism at the interface and provide insights for future research in this field and the generation of ultra-thin layered materials.

Visible to mid-infrared giant in-plane optical anisotropy in ternary van der Waals crystals.

Birefringence is at the heart of photonic applications. Layered van der Waals materials inherently support considerable out-of-plane birefringence. However, funnelling light into their small nanoscale area parallel to its out-of-plane optical axis remains challenging. Thus far, the lack of large in-plane birefringence has been a major roadblock hindering their applications. Here, we introduce the presence of broadband, low-loss, giant birefringence in a biaxial van der Waals materials Ta2NiS5, spanning an ultrawide-band from visible to mid-infrared wavelengths of 0.3-16 µm. The in-plane birefringence Δn ≈ 2 and 0.5 in the visible and mid-infrared ranges is one of the highest among van der Waals materials known to date. Meanwhile, the real-space propagating waveguide modes in Ta2NiS5 show strong in-plane anisotropy with a long propagation length (>20 µm) in the mid-infrared range. Our work may promote next-generation broadband and ultracompact integrated photonics based on van der Waals materials.

Optical nanoimaging of highly-confined phonon polaritons in atomically-thin nanoribbons of α-MoO3.

Phonon polaritons (PhPs), collective modes hybridizing photons with lattice vibrations in polar insulators, enable nanoscale control of light. In recent years, the exploration of in-plane anisotropic PhPs has yielded new levels of confinement and directional manipulation of nano-light. However, the investigation of in-plane anisotropic PhPs at the atomic layer limit is still elusive. Here, we report the optical nanoimaging of highly-confined phonon polaritons in atomically-thin nanoribbons of α-MoO3 (5 atomic layers). We show that narrow α-MoO3 nanoribbons as thin as a few atomic layers can support anisotropic PhPs modes with a high confinement ratio (∼133 times smaller wavelength than that of light). The anisotropic PhPs interference fringe patterns in atomic layers are tunable depending on the PhP wavelength via changing the illumination frequency. Moreover, spatial control over the PhPs interference patterns is also achieved by varying the nanostructures' shape or nanoribbon width of atomically-thin α-MoO3. Our work may serve as an empirical reference point for other anisotropic PhPs that approach the thickness limit and pave the way for applications such as atomically integrated nano-photonics and sensing.

Ultrafast anisotropic dynamics of hyperbolic nanolight pulse propagation.

Polariton pulses-transient light-matter hybrid excitations-traveling through anisotropic media can lead to unusual optical phenomena in space and time. However, studying these pulses presents challenges with their anisotropic, ultrafast, and nanoscale field variations. Here, we demonstrate the creation, observation, and control of polariton pulses, with in-plane hyperbolic dispersion, on anisotropic crystal surfaces by using a time-resolved nanoimaging technique and our developed high-dimensional data processing. We capture and analyze movies of distinctive pulse spatiotemporal dynamics, including curved ultraslow energy flow trajectories, anisotropic dissipation, and dynamical misalignment between phase and group velocities. Our approach enables analysis of polariton pulses in the wave vector time domain, demonstrating a time-domain polaritonic topological transition from lenticular to hyperbolic dispersion contours and the ability to study the polariton-induced time-varying optical forces. Our findings promise to facilitate the study of diverse space-time phenomena at extreme scales and drive advances in ultrafast nanoimaging.

Phonon polaritons in van der Waals polar heterostructures for broadband strong light-matter interactions.

Phonon polaritons in polar crystals have recently gained significant attention due to their remarkable confinement and enhancement of electromagnetic fields, low group velocities, and low losses. However, these unique properties, resulting from the coupling between photons and lattice vibrations, exhibit limited spectral responses that may hinder their practical applications. Here, we propose and experimentally demonstrate that polar van der Waals heterostructures can integrate their polar constituents to enable broadband phonon polariton responses. A polar heterostructure is created by simply transferring thin flakes of two polar van der Waals materials, hexagonal boron nitride (hBN) and α-phase molybdenum trioxide (α-MoO3), onto a polar quartz substrate. Direct infrared nanoimaging experiments show that this integrated heterostructure supports phonon polaritons in a broadband infrared spectral range from 800 to 1700 cm-1. Further, numerical calculations predict vibrational strong coupling for a few molecule monolayers with multiple molecular absorption modes and phonon polaritons in the heterostructure. Our findings suggest that broadband phonon polariton responses in van der Waals integrated heterostructures have the potential to pave the way for the development of broadband and integrated infrared devices of molecular sensing, signal processing, and energy control.

Electronic and Transport Properties of Strained and Unstrained Ge2Sb2Te5: A DFT Investigation.

In recent years, layered chalcogenides have attracted interest for their appealing thermoelectric properties. We investigated the Ge2Sb2Te5 compound in two different stacking sequences, named stacking 1 (S1) and stacking 2 (S2), wherein the Ge and Sb atomic positions can be interchanged in the structure. The compound unit cell, comprising nine atoms, is made of two layers separated by a gap. We show, using the quantum theory of atoms in molecules, that the bonding across the layers has characteristics of transit region bonding, though with a close resemblance to closed-shell bonding. Both S1 and S2 are shown to bear a similar small gap. The full determination of their thermoelectric properties, including the Seebeck coefficient, electrical conductivity and electronic and lattice thermal conductivities, was carried out by solving the Boltzmann transport equation. We show that stacking 1 exhibits a larger Seebeck coefficient and smaller electrical conductivity than stacking 2, which is related to their small electronic gap difference, and that S1 is more suitable for thermoelectric application than S2. Moreover, under certain conditions of temperature and doping level, it could be possible to use S1-Ge2Sb2Te5 as both a p and n leg in a thermoelectric converter. Under biaxial, tensile and compressive strains, we observe that the thermoelectric properties are improved for both S1 and S2. Furthermore, the increase in the power factor of S1 in the cross-plane direction, namely perpendicular to the gap between the layers, shows that strains can counteract the electronic transport hindrance due to the gap.

Observation of directional leaky polaritons at anisotropic crystal interfaces.

Extreme anisotropy in some polaritonic materials enables light propagation with a hyperbolic dispersion, leading to enhanced light-matter interactions and directional transport. However, these features are typically associated with large momenta that make them sensitive to loss and poorly accessible from far-field, being bound to the material interface or volume-confined in thin films. Here, we demonstrate a new form of directional polaritons, leaky in nature and featuring lenticular dispersion contours that are neither elliptical nor hyperbolic. We show that these interface modes are strongly hybridized with propagating bulk states, sustaining directional, long-range, sub-diffractive propagation at the interface. We observe these features using polariton spectroscopy, far-field probing and near-field imaging, revealing their peculiar dispersion, and - despite their leaky nature - long modal lifetime. Our leaky polaritons (LPs) nontrivially merge sub-diffractive polaritonics with diffractive photonics onto a unified platform, unveiling opportunities that stem from the interplay of extreme anisotropic responses and radiation leakage.

Prognostic prediction of subjective cognitive decline in major depressive disorder based on immune biomarkers: a prospective observational study.

OBJECTIVE: Subjective cognitive decline (SCD) is highlighted in patients with major depressive disorder (MDD), which impairs objective cognitive performance and worsens the clinical outcomes. Immune dysregulation is supposed to be the potential mechanism of cognitive impairment. However, the peripheral immune biomarkers in patients troubled with MDD and SCD are not conventionally described. METHODS: A prospective-observational study was conducted for 8 weeks. Subjective cognitive function was measured using the Chinese version of the 20-item perceived deficits questionnaire-depression (PDQ-D) and depression symptoms were evaluated with Hamilton Depression Rating Scale-17 (HDRS-17). Luminex assays were used to measure 48 immune cytokines in plasma at baseline. Integrating these results and clinicopathological features, a logistic regression model was used to develop a prognostic prediction. RESULTS: Totally, 114 patients were enrolled in this study. Among the patients who completed follow-up, 56% (N = 50) had residual subjective cognitive decline, and 44% (N = 50) did not. The plasma levels of FGF basic, INF-γ, IL-1ß, MCP-1, M-CSF and SCF were increased and the levels of IL-9, RANTES and PDGF-BB were decreased in the SCD group. Additionally, Basic FGF, IFN-γ, IL-1ß, and SCF were positively correlated and IL-9, RANTES, and PDGF-BB were negatively correlated with the PDQ-D scores after treatment. Notably, combinations of cytokines (SCF and PDGF-BB) and PDQ-D scores at baseline showed good performance (The area under the receiver operating characteristic curve = 0.818) in the prediction of subjective cognitive decline. CONCLUSION: A prognostic model based on protein concentrations of SCF, PDGF-BB, and scores of PDQ-D showed considerable accuracy in predicting residual subjective cognitive decline in depression.

Real-space nanoimaging of hyperbolic shear polaritons in a monoclinic crystal.

Various optical crystals possess permittivity components of opposite signs along different principal directions in the mid-infrared regime, exhibiting exotic anisotropic phonon resonances. Such materials with hyperbolic polaritons-hybrid light-matter quasiparticles with open isofrequency contours-feature large-momenta optical modes and wave confinement that make them promising for nanophotonic on-chip technologies. So far, hyperbolic polaritons have been observed and characterized in crystals with high symmetry including hexagonal (boron nitride), trigonal (calcite) and orthorhombic (α-MoO3 or α-V2O5) crystals, where they obey certain propagation patterns. However, lower-symmetry materials such as monoclinic crystals were recently demonstrated to offer richer opportunities for polaritonic phenomena. Here, using scanning near-field optical microscopy, we report the direct real-space nanoscale imaging of symmetry-broken hyperbolic phonon polaritons in monoclinic CdWO4 crystals, and showcase inherently asymmetric polariton excitation and propagation associated with the nanoscale shear phenomena. We also introduce a quantitative theoretical model to describe these polaritons that leads to schemes to enhance crystal asymmetry via the damping loss of phonon modes. Ultimately, our findings show that polaritonic nanophotonics is attainable using natural materials with low symmetry, favouring a versatile and general way to manipulate light at the nanoscale.

First-Principle Investigations on the Electronic and Transport Properties of PbBi2Te2X2 (X = S/Se/Te) Monolayers.

This paper reports first-principles calculations on PbBi2Te2S2, PbBi2Te2Se2 and PbBi2Te4 monolayers. The strain effects on their electronic and thermoelectric properties as well as on their stability have been investigated. Without strain, the PbBi2Te4 monolayer exhibits highest Seebeck coefficient with a maximum value of 671 µV/K. Under tensile strain the highest power factor are 12.38×1011 Wm-1K-2s-1, 10.74×1011 Wm-1K-2s-1 and 6.51×1011 Wm-1K-2s-1 for PbBi2Te2S2, PbBi2Te2Se2 and PbBi2Te4 at 3%, 2% and 1% tensile strains, respectively. These values are 85.9%, 55.0% and 3.3% larger than those of the unstrained structures.

A graphene-Mo2C heterostructure for a highly responsive broadband photodetector.

Photodetectors based on intrinsic graphene can operate over a broad wavelength range with ultrafast response, but their responsivity is much lower than commercial silicon photodiodes. The combination of graphene with two-dimensional (2D) semiconductors may enhance the light absorption, but there is still a cutoff wavelength originating from the bandgap of semiconductors. Here, we report a highly responsive broadband photodetector based on the heterostructure of graphene and transition metal carbides (TMCs, more specifically Mo2C). The graphene-Mo2C heterostructure enhanced light absorption over a broad wavelength range from ultraviolet to infrared. In addition, there is very small resistance for photoexcited carriers in both graphene and Mo2C. Consequently, photodetectors based on the graphene-Mo2C heterostructure deliver a very high responsivity from visible to infrared telecommunication wavelengths.

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.

Interface nano-optics with van der Waals polaritons.

Polaritons are hybrid excitations of matter and photons. In recent years, polaritons in van der Waals nanomaterials-known as van der Waals polaritons-have shown great promise to guide the flow of light at the nanoscale over spectral regions ranging from the visible to the terahertz. A vibrant research field based on manipulating strong light-matter interactions in the form of polaritons, supported by these atomically thin van der Waals nanomaterials, is emerging for advanced nanophotonic and opto-electronic applications. Here we provide an overview of the state of the art of exploiting interface optics-such as refractive optics, meta-optics and moiré engineering-for the control of van der Waals polaritons. This enhanced control over van der Waals polaritons at the nanoscale has not only unveiled many new phenomena, but has also inspired valuable applications-including new avenues for nano-imaging, sensing, on-chip optical circuitry, and potentially many others in the years to come.

Ghost hyperbolic surface polaritons in bulk anisotropic crystals.

Polaritons in anisotropic materials result in exotic optical features, which can provide opportunities to control light at the nanoscale1-10. So far these polaritons have been limited to two classes: bulk polaritons, which propagate inside a material, and surface polaritons, which decay exponentially away from an interface. Here we report a near-field observation of ghost phonon polaritons, which propagate with in-plane hyperbolic dispersion on the surface of a polar uniaxial crystal and, at the same time, exhibit oblique wavefronts in the bulk. Ghost polaritons are an atypical non-uniform surface wave solution of Maxwell's equations, arising at the surface of uniaxial materials in which the optic axis is slanted with respect to the interface. They exhibit an unusual bi-state nature, being both propagating (phase-progressing) and evanescent (decaying) within the crystal bulk, in contrast to conventional surface waves that are purely evanescent away from the interface. Our real-space near-field imaging experiments reveal long-distance (over 20 micrometres), ray-like propagation of deeply subwavelength ghost polaritons across the surface, verifying long-range, directional and diffraction-less polariton propagation. At the same time, we show that control of the out-of-plane angle of the optic axis enables hyperbolic-to-elliptic topological transitions at fixed frequency, providing a route to tailor the band diagram topology of surface polariton waves. Our results demonstrate a polaritonic wave phenomenon with unique opportunities to tailor nanoscale light in natural anisotropic crystals.

Strain Effects on the Electronic and Thermoelectric Properties of n(PbTe)-m(Bi2Te3) System Compounds.

Owing to their low lattice thermal conductivity, many compounds of the n(PbTe)-m(Bi2Te3) homologous series have been reported in the literature with thermoelectric (TE) properties that still need improvement. For this purpose, in this work, we have implemented the band engineering approach by applying biaxial tensile and compressive strains using the density functional theory (DFT) on various compounds of this series, namely Bi2Te3, PbBi2Te4, PbBi4Te7 and Pb2Bi2Te5. All the fully relaxed Bi2Te3, PbBi2Te4, PbBi4Te7 and Pb2Bi2Te5 compounds are narrow band-gap semiconductors. When applying strains, a semiconductor-to-metal transition occurs for all the compounds. Within the range of open-gap, the electrical conductivity decreases as the compressive strain increases. We also found that compressive strains cause larger Seebeck coefficients than tensile ones, with the maximum Seebeck coefficient being located at -2%, -6%, -3% and 0% strain for p-type Bi2Te3, PbBi2Te4, PbBi4Te7 and Pb2Bi2Te5, respectively. The use of the quantum theory of atoms in molecules (QTAIM) as a complementary tool has shown that the van der Waals interactions located between the structure slabs evolve with strains as well as the topological properties of Bi2Te3 and PbBi2Te4. This study shows that the TE performance of the n(PbTe)-m(Bi2Te3) compounds is modified under strains.

Influence of the stacking sequence on layered-chalcogenide properties: first principles investigation of Pb2Bi2Te5.

The Pb2Bi2Te5 compound has been reported in the literature with two stacking sequences -Te-Pb-Te-Bi-Te-Bi-Te-Pb-Te- and -Te-Bi-Te-Pb-Te-Pb-Te-Bi-Te- labelled in this work as A and B, respectively. The electronic and the thermoelectric properties of the Pb2Bi2Te5 compound with the 2 different stacking sequences have been determined from a series of first principles calculations using density functional theory (DFT). The related compounds PbTe and Bi2Te3 have also been investigated for comparison. Different exchange-correlation functionals have been tested, without spin-orbit coupling, which has been found to have important effects. The elastic moduli, dielectric constants, Born effective charges, and phonon dispersion within the quasi-harmonic approximation have also been calculated and based on these calculations results, the thermal conductivity has been determined by solving the Boltzmann transport equation. Additionally, the QTAIM theory was employed to explain the differences in the properties of the 2 stackings. The most interesting compound for thermoelectric applications has been found to be Pb2Bi2Te5 with the stacking B sequence. The highest zT values have been found to be 4.02 in the a-axis direction and 2.26 in the c-axis one.

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.