Highly confined epsilon-near-zero and surface phonon polaritons in SrTiO3 membranes.

Recent theoretical studies have suggested that transition metal perovskite oxide membranes can enable surface phonon polaritons in the infrared range with low loss and much stronger subwavelength confinement than bulk crystals. Such modes, however, have not been experimentally observed so far. Here, using a combination of far-field Fourier-transform infrared (FTIR) spectroscopy and near-field synchrotron infrared nanospectroscopy (SINS) imaging, we study the phonon polaritons in a 100 nm thick freestanding crystalline membrane of SrTiO3 transferred on metallic and dielectric substrates. We observe a symmetric-antisymmetric mode splitting giving rise to epsilon-near-zero and Berreman modes as well as highly confined (by a factor of 10) propagating phonon polaritons, both of which result from the deep-subwavelength thickness of the membranes. Theoretical modeling based on the analytical finite-dipole model and numerical finite-difference methods fully corroborate the experimental results. Our work reveals the potential of oxide membranes as a promising platform for infrared photonics and polaritonics.

Phonon promoted charge density wave in topological kagome metal ScV6Sn6.

Charge density wave (CDW) orders in vanadium-based kagome metals have recently received tremendous attention, yet their origin remains a topic of debate. The discovery of ScV6Sn6, a bilayer kagome metal featuring an intriguing [Formula: see text] CDW order, offers a novel platform to explore the underlying mechanism behind the unconventional CDW. Here, we combine high-resolution angle-resolved photoemission spectroscopy, Raman scattering and density functional theory to investigate the electronic structure and phonon modes of ScV6Sn6. We identify topologically nontrivial surface states and multiple van Hove singularities (VHSs) in the vicinity of the Fermi level, with one VHS aligning with the in-plane component of the CDW vector near the [Formula: see text] point. Additionally, Raman measurements indicate a strong electron-phonon coupling, as evidenced by a two-phonon mode and new emergent modes. Our findings highlight the fundamental role of lattice degrees of freedom in promoting the CDW in ScV6Sn6.

Thermal and electrostatic tuning of surface phonon-polaritons in LaAlO3/SrTiO3 heterostructures.

Phonon polaritons are promising for infrared applications due to a strong light-matter coupling and subwavelength energy confinement they offer. Yet, the spectral narrowness of the phonon bands and difficulty to tune the phonon polariton properties hinder further progress in this field. SrTiO3 - a prototype perovskite oxide - has recently attracted attention due to two prominent far-infrared phonon polaritons bands, albeit without any tuning reported so far. Here we show, using cryogenic infrared near-field microscopy, that long-propagating surface phonon polaritons are present both in bare SrTiO3 and in LaAlO3/SrTiO3 heterostructures hosting a two-dimensional electron gas. The presence of the two-dimensional electron gas increases dramatically the thermal variation of the upper limit of the surface phonon polariton band due to temperature dependent polaronic screening of the surface charge carriers. Furthermore, we demonstrate a tunability of the upper surface phonon polariton frequency in LaAlO3/SrTiO3 via electrostatic gating. Our results suggest that oxide interfaces are a new platform bridging unconventional electronics and long-wavelength nanophotonics.

Multiple antiferromagnetic phases and magnetic anisotropy in exfoliated CrBr3 multilayers.

In twisted two-dimensional (2D) magnets, the stacking dependence of the magnetic exchange interaction can lead to regions of ferromagnetic and antiferromagnetic interlayer order, separated by non-collinear, skyrmion-like spin textures. Recent experimental searches for these textures have focused on CrI3, known to exhibit either ferromagnetic or antiferromagnetic interlayer order, depending on layer stacking. However, the very strong uniaxial anisotropy of CrI3 disfavors smooth non-collinear phases in twisted bilayers. Here, we report the experimental observation of three distinct magnetic phases-one ferromagnetic and two antiferromagnetic-in exfoliated CrBr3 multilayers, and reveal that the uniaxial anisotropy is significantly smaller than in CrI3. These results are obtained by magnetoconductance measurements on CrBr3 tunnel barriers and Raman spectroscopy, in conjunction with density functional theory calculations, which enable us to identify the stackings responsible for the different interlayer magnetic couplings. The detection of all locally stable magnetic states predicted to exist in CrBr3 and the excellent agreement found between theory and experiments, provide complete information on the stacking-dependent interlayer exchange energy and establish twisted bilayer CrBr3 as an ideal system to deterministically create non-collinear magnetic phases.

Molecule-like and lattice vibrations in metal clusters.

We report distinct molecule-like and lattice (breathing) vibrational signatures of atomically precise, ligand-protected metal clusters using low-temperature Raman spectroscopy. Our measurements provide fingerprint Raman spectra of a series of noble metal clusters, namely, Au25(SR)18, Ag25(SR)18, Ag24Au1(SR)18, Ag29(S2R)12 and Ag44(SR)30 (-SR = alkyl/arylthiolate, -S2R = dithiolate). Distinct, well-defined, low-frequency Raman bands of these clusters result from the vibrations of their metal cores whereas the higher-frequency bands reflect the structure of the metal-ligand interface. We observe a distinct breathing vibrational mode for each of these clusters. Detailed analyses of the bands are presented in the light of DFT calculations. These vibrational signatures change systematically when the metal atoms and/or the ligands are changed. Most importantly, our results show that the physical, lattice dynamics model alone cannot completely describe the vibrational properties of ligand-protected metal clusters. We show that low-frequency Raman spectroscopy is a powerful tool to understand the vibrational dynamics of atomically precise, molecule-like particles of other materials such as molecular nanocarbons, quantum dots, and perovskites.

Raman Spectroscopic Fingerprints of Atomically Precise Ligand Protected Noble Metal Clusters: Au38 (PET)24 and Au38-x Agx (PET)24.

Distinct Raman spectroscopic signatures of the metal core of atomically precise, ligand-protected noble metal nanoclusters are reported using Au38 (PET)24 and Au38-x Agx (PET)24 (PET = 2-phenylethanethiolate, -SC2 H4 C6 H5 ) as model systems. The fingerprint Raman features (occurring <200 cm-1 ) of these clusters arise due to the vibrations involving metal atoms of their Au23 or Au23-x Agx cores. A distinct core breathing vibrational mode of the Au23 core has been observed at 90 cm-1 . Whereas the breathing mode shifts to higher frequencies with increasing Ag content of the cluster, the vibrational signatures due to the outer metal-ligand staple motifs (between 200 and 500 cm-1 ) do not shift significantly. DFT calculations furthermore reveal weak Raman bands at higher frequencies compared to the breathing mode, which are associated mostly with the rattling of two central gold atoms of the bi-icosahedral Au23 core. These vibrations are also observed in the experimental spectrum. The study indicates that low-frequency Raman spectra are a characteristic fingerprint of atomically precise clusters, just as electronic absorption spectroscopy, in contrast to the spectrum associated with the ligand shell, which is observed at higher frequencies.

Translucent in air and iridescent in water: structural analysis of a salamander egg sac.

Females of some Asian salamanders of the genus Hynobius deposit in streams their eggs embedded in a translucent envelope called an 'egg sac'. The edges of the envelope exhibit a spectacular blue-to-yellow iridescent glow, which instantaneously disappears when the sac is removed from water. First, our scanning electron microscopy analyses reveal that the inner surface of the 100 µm-thick envelope displays striations (length scale of about 3 µm), which are themselves covered by much smaller (190 ± 30 nm) and quasi-periodic corrugations. The latter could constitute a surface diffraction grating generating iridescence by light interference. Second, our transmission electron microscopy and focused-ion-beam scanning electron microscopy analyses show that the bulk of the egg sac wall is composed of meandering fibres with a quasi-periodic modulation of 190 ± 60 nm along the thickness of the envelope, generating a photonic crystal. Third, Fourier power analyses of 450 electron microscopy images with varying incident angles indicate that changing the surrounding medium from water to air shifts most of the backscattered power spectrum to the ultraviolet range, hence, explaining that the egg sac loses visible iridescence when removed out of the water. Fourth, the results of our photography and optical spectroscopy experiments of submerged and emerged egg sacs rule out the possibility that the iridescence is due to a thin film or a multilayer, whereas the observed non-specular response is compatible with the backscattering expected from surface diffraction gratings and volumetric photonic crystals with spatial 1D modulation. Finally, although we mention several potential biological functions of the egg sac structural colours and iridescence, we emphasise that these optical properties might be the by-products of the envelope material internal structure selected during evolution for its mechanical properties.

High sensitivity variable-temperature infrared nanoscopy of conducting oxide interfaces.

Probing the local transport properties of two-dimensional electron systems (2DES) confined at buried interfaces requires a non-invasive technique with a high spatial resolution operating in a broad temperature range. In this paper, we investigate the scattering-type scanning near field optical microscopy as a tool for studying the conducting LaAlO3/SrTiO3 interface from room temperature down to 6 K. We show that the near-field optical signal, in particular its phase component, is highly sensitive to the transport properties of the electron system present at the interface. Our modeling reveals that such sensitivity originates from the interaction of the AFM tip with coupled plasmon-phonon modes with a small penetration depth. The model allows us to quantitatively correlate changes in the optical signal with the variation of the 2DES transport properties induced by cooling and by electrostatic gating. To probe the spatial resolution of the technique, we image conducting nano-channels written in insulating heterostructures with a voltage-biased tip of an atomic force microscope.

Suppressed Magnetic Circular Dichroism and Valley-Selective Magnetoabsorption due to the Effective Mass Anisotropy in Bismuth.

We measure the far-infrared reflectivity and Kerr angle spectra on a high-quality crystal of pure semimetallic bismuth as a function of magnetic field, from which we extract the conductivity for left- and right-handed circular polarizations. The high spectral resolution allows us to separate the intraband Landau level transitions for electrons and holes. The hole transition exhibits 100% magnetic circular dichroism; it appears only for one polarization as expected for a circular cyclotron orbit. However, the dichroism for electron transitions is reduced to only 13±1%, which is quantitatively explained by the large effective mass anisotropy of the electron pockets of the Fermi surface. This observation is a signature of the mismatch between the metric experienced by the photons and the electrons. It allows for a contactless measurement of the effective mass anisotropy and provides a direction towards valley polarized magnetooptical pumping with elliptically polarized light.

Versatile setup for optical spectroscopy under high pressure and low temperature.

We present an optical setup for spectroscopic measurements in the infrared and of Raman shift under high pressure and at low temperature. Using a membrane-driven diamond anvil cell, the pressure can be tuned in situ up to 20 GPa and the temperatures ranges from room temperature down to 18 K in transmission mode and 13 K in reflection mode. In transmission, the setup is entirely working under vacuum to reduce the water absorption features and obtain a higher spectral stability. Since the infrared throughput obtained with a thermal source is limited, the use of a synchrotron source allowed to enhance the performance, as illustrated with results obtained with various materials. The analysis of the reflectivity is adapted so that it benefits from ambient pressure data and produces quantitative optical conductivity curves that can be easily compared to the results at ambient pressure.

Crystal Structure, Transport, and Magnetic Properties of an Ir(6+) Compound Ba8Al2IrO14.

The novel iridate Ba8Al2IrO14 was prepared as single crystals by self-flux method, thereby providing a rare example of an all-Ir(VI) compound that can be synthesized under ambient pressure conditions. The preparation of all-Ir(6+) iridate without using traditional high-pressure techniques has to our knowledge previously only been reported in Nd2K2IrO7 and Sm2K2IrO7. The monoclinic crystal structure (space group C2/m, No.12) is stable down to 90 K and contains layers of IrO6 octahedra separated by Ba and AlO4 tetrahedra. The material exhibits insulating behavior with a narrow band gap of ∼0.6 eV. The positive Seebeck coefficient indicates hole-like dominant charge carriers. Susceptibility measurement shows antiferromagnetic coupling with no order down to 2 K.

Photonic crystals cause active colour change in chameleons.

Many chameleons, and panther chameleons in particular, have the remarkable ability to exhibit complex and rapid colour changes during social interactions such as male contests or courtship. It is generally interpreted that these changes are due to dispersion/aggregation of pigment-containing organelles within dermal chromatophores. Here, combining microscopy, photometric videography and photonic band-gap modelling, we show that chameleons shift colour through active tuning of a lattice of guanine nanocrystals within a superficial thick layer of dermal iridophores. In addition, we show that a deeper population of iridophores with larger crystals reflects a substantial proportion of sunlight especially in the near-infrared range. The organization of iridophores into two superposed layers constitutes an evolutionary novelty for chameleons, which allows some species to combine efficient camouflage with spectacular display, while potentially providing passive thermal protection.

Precise colocalization of interacting structural and pigmentary elements generates extensive color pattern variation in Phelsuma lizards.

BACKGROUND: Color traits in animals play crucial roles in thermoregulation, photoprotection, camouflage, and visual communication, and are amenable to objective quantification and modeling. However, the extensive variation in non-melanic pigments and structural colors in squamate reptiles has been largely disregarded. Here, we used an integrated approach to investigate the morphological basis and physical mechanisms generating variation in color traits in tropical day geckos of the genus Phelsuma. RESULTS: Combining histology, optics, mass spectrometry, and UV and Raman spectroscopy, we found that the extensive variation in color patterns within and among Phelsuma species is generated by complex interactions between, on the one hand, chromatophores containing yellow/red pteridine pigments and, on the other hand, iridophores producing structural color by constructive interference of light with guanine nanocrystals. More specifically, we show that 1) the hue of the vivid dorsolateral skin is modulated both by variation in geometry of structural, highly ordered narrowband reflectors, and by the presence of yellow pigments, and 2) that the reflectivity of the white belly and of dorsolateral pigmentary red marks, is increased by underlying structural disorganized broadband reflectors. Most importantly, these interactions require precise colocalization of yellow and red chromatophores with different types of iridophores, characterized by ordered and disordered nanocrystals, respectively. We validated these results through numerical simulations combining pigmentary components with a multilayer interferential optical model. Finally, we show that melanophores form dark lateral patterns but do not significantly contribute to variation in blue/green or red coloration, and that changes in the pH or redox state of pigments provide yet another source of color variation in squamates. CONCLUSIONS: Precisely colocalized interacting pigmentary and structural elements generate extensive variation in lizard color patterns. Our results indicate the need to identify the developmental mechanisms responsible for the control of the size, shape, and orientation of nanocrystals, and the superposition of specific chromatophore types. This study opens up new perspectives on Phelsuma lizards as models in evolutionary developmental biology.