Hyperbolic shear polaritons in low-symmetry crystals.

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 phase1-4. 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 scales5. 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 response6,7. Hyperbolic shear polaritons complement previous observations of hyperbolic phonon polaritons in orthorhombic1,3,4 and hexagonal8,9 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 minerals10, many common oxides11 and organic crystals12, greatly expanding the material base and extending design opportunities for compact photonic devices.

Assessing the Release of Microplastics and Nanoplastics from Plastic Containers and Reusable Food Pouches: Implications for Human Health.

This study investigated the release of microplastics and nanoplastics from plastic containers and reusable food pouches under different usage scenarios, using DI water and 3% acetic acid as food simulants for aqueous foods and acidic foods. The results indicated that microwave heating caused the highest release of microplastics and nanoplastics into food compared to other usage scenarios, such as refrigeration or room-temperature storage. It was found that some containers could release as many as 4.22 million microplastic and 2.11 billion nanoplastic particles from only one square centimeter of plastic area within 3 min of microwave heating. Refrigeration and room-temperature storage for over six months can also release millions to billions of microplastics and nanoplastics. Additionally, the polyethylene-based food pouch released more particles than polypropylene-based plastic containers. Exposure modeling results suggested that the highest estimated daily intake was 20.3 ng/kg·day for infants drinking microwaved water and 22.1 ng/kg·day for toddlers consuming microwaved dairy products from polypropylene containers. Furthermore, an in vitro study conducted to assess the cell viability showed that the extracted microplastics and nanoplastics released from the plastic container can cause the death of 76.70 and 77.18% of human embryonic kidney cells (HEK293T) at 1000 µg/mL concentration after exposure of 48 and 72 h, respectively.

Giant photonic spin Hall effect induced by hyperbolic shear polaritons.

Recently, broken symmetry within crystals has been attracting tremendous research interest since it can be utilized to effectively manipulate the propagation of photons. In particular, low-symmetry Bravais crystals can support hyperbolic shear polaritons (HShPs), holding great promise for technological upgrading in the emerging research area of spinoptics. Herein, an Otto-type multilayer structure consisting of a KRS5 prism, a sensing medium, and monoclinic ß-Ga2O3 crystals is designed to ameliorate the photonic spin Hall effect (PSHE). The surface of ß-Ga2O3 is the monoclinic (010) plane (x-y plane). We show that giant spin Hall shifts with three (or two) orders of magnitude of the incident wavelength can be obtained in the in-plane (or transverse) directions. The azimuthal dispersions of photonic spin Hall shifts present non-mirror-symmetric patterns upon tuning the rotation angle of ß-Ga2O3 around the z-axis in the plane. All of these exotic optical properties are closely correlated with the broken crystal lattice symmetry and the incurred excitation of HShPs in monoclinic ß-Ga2O3 crystals. By virtue of the remarkably enhanced PSHE, our proposed Otto-type multilayer structure shows a superior biosensing performance in which the maximum sensitivity is two orders of magnitude larger than that of previously reported PSHE biosensors based on two-dimensional materials. In addition, the optimized physical and structural parameters including the incident angle, excitation wavelength, azimuth angle and doping concentration of ß-Ga2O3, thickness and refractive index of sensing medium are also investigated and presented. This work unequivocally confirms the strong influence of crystal symmetry on the PSHE, providing important insights into understanding the rich modulation of spin-orbit interactions of light via shear polaritons and therefore facilitating potential applications in photoelectronic devices.

Mueller matrix imaging microscope using dual continuously rotating anisotropic mirrors.

We demonstrate calibration and operation of a Mueller matrix imaging microscope using dual continuously rotating anisotropic mirrors for polarization state generation and analysis. The mirrors contain highly spatially coherent nanostructure slanted columnar titanium thin films deposited onto optically thick titanium layers on quartz substrates. The first mirror acts as polarization state image generator and the second mirror acts as polarization state image detector. The instrument is calibrated using samples consisting of laterally homogeneous properties such as straight-through-air, a clear aperture linear polarizer, and a clear aperture linear retarder waveplate. Mueller matrix images are determined for spatially varying anisotropic samples consisting of a commercially available (Thorlabs) birefringent resolution target and a spatially patterned titanium slanted columnar thin film deposited onto a glass substrate. Calibration and operation are demonstrated at a single wavelength (530 nm) only, while, in principle, the instrument can operate regardless of wavelength. We refer to this imaging ellipsometry configuration as rotating-anisotropic-mirror-sample-rotating-anisotropic-mirror ellipsometry (RAM-S-RAM-E).

Mueller matrix ellipsometer using dual continuously rotating anisotropic mirrors.

We demonstrate calibration and operation of a single wavelength (660 nm) Mueller matrix ellipsometer in normal transmission configuration using dual continuously rotating anisotropic mirrors. The mirrors contain highly spatially coherent nanostructure slanted columnar titanium thin films deposited onto optically thick gold layers on glass substrates. Upon rotation around the mirror normal axis, sufficient modulation of the Stokes parameters of light reflected at oblique angle of incidence is achieved. Thereby, the mirrors can be used as a polarization state generator and polarization state analyzer in a generalized ellipsometry instrument. A Fourier expansion approach is found sufficient to render and calibrate the effects of the mirror rotations onto the polarized light train within the ellipsometer. The Mueller matrix elements of a set of anisotropic samples consisting of a linear polarizer and a linear retarder are measured and compared with model data, and very good agreement is observed.

Composition-Dependent Charge Transport in Boron Carbides Alloyed with Aromatics: Plasma Enhanced Chemical Vapor Deposition Aniline/Orthocarborane Films.

Boron carbide films, alloyed with aniline moieties, were deposited by plasma enhanced chemical vapor deposition (PECVD) from aniline and orthocarborane precursors and were found to exhibit composition-dependent drift carrier lifetimes as derived from I( V) and C( V)) measurements. For a film with an aniline/carborane ratio of 5:1, the effective drift carrier lifetimes are ∼80 µs at low bias voltage but quickly drop to a few microseconds with increasing bias. A film with a 10:1 aniline/carborane ratio, however, exhibited lifetimes of ∼6 µs, or less, at 1 kHz, and much smaller values at 10 kHz. These lifetimes are orders of magnitude longer than those in polyaniline films and comparable to those in PECVD carborane films without aromatic content. X-ray photoelectron spectroscopy (XPS), FTIR, and ellipsometry, combined with density functional theory (DFT)-based cluster calculations, indicate that aniline and orthocarborane moieties are largely intact within the films. Bonding occurs primarily between aniline C sites and carborane B sites, and the aniline coordination number per carborane icosahedron is ∼2 as the aniline/carborane ratio is increased from 3:1 to 10:1. This aniline/carborane coordination ratio independent of aniline/orthocarborane stoichiometry is consistent with the dependence of charge transport properties on aniline film content at high bias voltage.

Salt Sensitivity of the Thermoresponsive Behavior of PNIPAAm Brushes.

We report investigations on the salt sensitivity of the thermoresponsive behavior of PNIPAAm brushes applying the quartz crystal microbalance coupled with spectroscopic ellipsometry technique. This approach enables a detailed study of the optical and mechanical behavior of the polymer coatings. Additional conclusions can be drawn from the difference between both techniques due to a difference in the contrast mechanism of both methods. A linear shift of the phase-transition temperature to lower temperatures with the addition of sodium chloride was found, similar to the behavior of free polymer chains in solution. The thermal hysteresis was found to be decreased by the addition of sodium chloride to the solution, hinting to the interaction of the ions with the amide groups of the polymer, whereby the formation of hydrogen bonds is hindered. The results of this study are of relevance to the application of PNIPAAm brushes in biological fluids and demonstrate the additional potential of the ion sensitivity besides the better known thermosensitivity.

Coordinate-Invariant Lyddane-Sachs-Teller Relationship for Polar Vibrations in Materials with Monoclinic and Triclinic Crystal Systems.

A coordinate-invariant generalization of the Lyddane-Sachs-Teller relation is presented for polar vibrations in materials with monoclinic and triclinic crystal systems. The generalization is derived from an eigendielectric displacement vector summation approach, which is equivalent to the microscopic Born-Huang description of polar lattice vibrations in the harmonic approximation. An expression for a general oscillator strength is also described for materials with monoclinic and triclinic crystal systems. A generalized factorized form of the dielectric response characteristic for monoclinic and triclinic materials is proposed. The generalized Lyddane-Sachs-Teller relation is found valid for monoclinic ß-Ga_{2}O_{3}, where accurate experimental data became available recently from a comprehensive generalized ellipsometry investigation [Phys. Rev. B 93, 125209 (2016)]. Data for triclinic crystal systems can be measured by generalized ellipsometry as well, and are anticipated to become available soon and results can be compared with the generalized relations presented here.

Optical Hall effect-model description: tutorial.

The optical Hall effect is a physical phenomenon that describes the occurrence of magnetic-field-induced dielectric displacement at optical wavelengths, transverse and longitudinal to the incident electric field, and analogous to the static electrical Hall effect. The electrical Hall effect and certain cases of the optical Hall effect observations can be explained by extensions of the classic Drude model for the transport of electrons in metals. The optical Hall effect is most useful for characterization of electrical properties in semiconductors. Among many advantages, while the optical Hall effect dispenses with the need of electrical contacts, electrical material properties such as effective mass and mobility parameters, including their anisotropy as well as carrier type and density, can be determined from the optical Hall effect. Measurement of the optical Hall effect can be performed within the concept of generalized ellipsometry at an oblique angle of incidence. In this paper, we review and discuss physical model equations, which can be used to calculate the optical Hall effect in single- and multiple-layered structures of semiconductor materials. We define the optical Hall effect dielectric function tensor, demonstrate diagonalization approaches, and show requirements for the optical Hall effect tensor from energy conservation. We discuss both continuum and quantum approaches, and we provide a brief description of the generalized ellipsometry concept, the Mueller matrix calculus, and a 4×4 matrix algebra to calculate data accessible by experiment. In a follow-up paper, we will discuss strategies and approaches for experimental data acquisition and analysis.

Combined QCM-D/GE as a tool to characterize stimuli-responsive swelling of and protein adsorption on polymer brushes grafted onto 3D-nanostructures.

A combined setup of quartz crystal microbalance and generalized ellipsometry can be used to comprehensively investigate complex functional coatings comprising stimuli-responsive polymer brushes and 3D nanostructures in a dynamic, noninvasive in situ measurement. While the quartz crystal microbalance detects the overall change in areal mass, for instance, during a swelling or adsorption process, the generalized ellipsometry data can be evaluated in terms of a layered model to distinguish between processes occurring within the intercolumnar space or on top of the anisotropic nanocolumns. Silicon films with anisotropic nanocolumnar morphology were prepared by the glancing angle deposition technique and further functionalized by grafting of poly-(acrylic acid) or poly-(N- isopropylacrylamide) chains. Investigations of the thermoresponsive swelling of the poly-(N-isopropylacrylamide) brush on the Si nanocolumns proved the successful preparation of a stimuli-responsive coating. Furthermore, the potential of these novel coatings in the field of biotechnology was explored by investigation of the adsorption of the model protein bovine serum albumin. Adsorption, retention, and desorption triggered by a change in the pH value is observed using poly-(acrylic acid) functionalized nanostructures, although generalized ellipsometry data revealed that this process occurs only on top of the nanostructures. Poly-(N-isopropylacrylamide) is found to render the nanostructures non-fouling properties.

Controlling the broadband enhanced light chirality with L-shaped dielectric metamaterials.

The inherently weak chiroptical responses of natural materials limit their usage for controlling and enhancing chiral light-matter interactions. Recently, several nanostructures with subwavelength scale dimensions were demonstrated, mainly due to the advent of nanofabrication technologies, as a potential alternative to efficiently enhance chirality. However, the intrinsic lossy nature of metals and the inherent narrowband response of dielectric planar thin films or metasurface structures pose severe limitations toward the practical realization of broadband and tailorable chiral systems. Here, we tackle these problems by designing all-dielectric silicon-based L-shaped optical metamaterials based on tilted nanopillars that exhibit broadband and enhanced chiroptical response in transmission operation. We use an emerging bottom-up fabrication approach, named glancing angle deposition, to assemble these dielectric metamaterials on a wafer scale. The reported strong chirality and optical anisotropic properties are controllable in terms of both amplitude and operating frequency by simply varying the shape and dimensions of the nanopillars. The presented nanostructures can be used in a plethora of emerging nanophotonic applications, such as chiral sensors, polarization filters, and spin-locked nanowaveguides.

The Role of Optical Phonon Confinement in the Infrared Dielectric Response of III-V Superlattices.

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.

Chiroptical Second-Harmonic Tyndall Scattering from Silicon Nanohelices.

Chirality is omnipresent in the living world. As biomimetic nanotechnology and self-assembly advance, they too need chirality. Accordingly, there is a pressing need to develop general methods to characterize chiral building blocks at the nanoscale in liquids such as water─the medium of life. Here, we demonstrate the chiroptical second-harmonic Tyndall scattering effect. The effect was observed in Si nanohelices, an example of a high-refractive-index dielectric nanomaterial. For three wavelengths of illumination, we observe a clear difference in the second-harmonic scattered light that depends on the chirality of the nanohelices and the handedness of circularly polarized light. Importantly, we provide a theoretical analysis that explains the origin of the effect and its direction dependence, resulting from different specific contributions of "electric dipole-magnetic dipole" and "electric dipole-electric quadrupole" coupling tensors. Using numerical simulations, we narrow down the number of such terms to 8 in forward scattering and to a single one in right-angled scattering. For chiral scatterers such as high-refractive-index dielectric nanoparticles, our findings expand the Tyndall scattering regime to nonlinear optics. Moreover, our theory can be broadened and adapted to further classes where such scattering has already been observed or is yet to be observed.

Quantum Composites with Charge-Density-Wave Fillers.

A unique class of advanced materials-quantum composites based on polymers with fillers composed of a van der Waals quantum material that reveals multiple charge-density-wave quantum condensate phases-is demonstrated. Materials that exhibit quantum phenomena are typically crystalline, pure, and have few defects because disorder destroys the coherence of the electrons and phonons, leading to collapse of the quantum states. The macroscopic charge-density-wave phases of filler particles after multiple composite processing steps are successfully preserved in this work. The prepared composites display strong charge-density-wave phenomena even above room temperature. The dielectric constant experiences more than two orders of magnitude enhancement while the material maintains its electrically insulating properties, opening a venue for advanced applications in energy storage and electronics. The results present a conceptually different approach for engineering the properties of materials, extending the application domain for van der Waals materials.

Ferromagnetic resonators synthesized by metal-organic decomposition epitaxy.

Metal-organic decomposition epitaxy is an economical wet-chemical approach suitable to synthesize high-quality low-spin-damping films for resonator and oscillator applications. This work reports the temperature dependence of ferromagnetic resonances and associated structural and magnetic quantities of yttrium iron garnet nanofilms that coincide with single-crystal values. Despite imperfections originating from wet-chemical deposition and spin coating, the quality factor for out-of-plane and in-plane resonances approaches 600 and 1000, respectively, at room temperature and 40 GHz. These values increase with temperature and are 100 times larger than those offered by commercial devices based on complementary metal-oxide semiconductor voltage-controlled oscillators at comparable production costs.

Generalized ellipsometry in-situ quantification of organic adsorbate attachment within slanted columnar thin films.

We apply generalized ellipsometry, well-known to be sensitive to the optical properties of anisotropic materials, to determine the amount of fibronectin protein that adsorbs onto a Ti slanted columnar thin film from solution. We find that the anisotropic optical properties of the thin film change upon organic adsorption. An optical model for ellipsometry data analysis incorporates an anisotropic Bruggeman effective medium approximation. We find that differences in experimental data from before and after fibronectin adsorption can be solely attributable to the uptake of fibronectin within the slanted columnar thin film. Simultaneous, in-situ generalized ellipsometry and quartz crystal microbalance measurements show excellent agreement on the amount and rate of fibronectin adsorption. Quantitative characterization of organic materials within three-dimensional, optically anisotropic slanted columnar thin films could permit their use in optical sensor applications.

Stretchable Thin Film Mechanical-Strain-Gated Switches and Logic Gate Functions Based on a Soft Tunneling Barrier.

Mechanical-strain-gated switches are cornerstone components of material-embedded circuits that perform logic operations without using conventional electronics. This technology requires a single material system to exhibit three distinct functionalities: strain-invariant conductivity and an increase or decrease of conductivity upon mechanical deformation. Herein, mechanical-strain-gated electric switches based on a thin-film architecture that features an insulator-to-conductor transition when mechanically stretched are demonstrated. The conductivity changes by nine orders of magnitude over a wide range of tunable working strains (as high as 130%). The approach relies on a nanometer-scale sandwiched bilayer Au thin film with an ultrathin poly(dimethylsiloxane) elastomeric barrier layer; applied strain alters the electron tunneling currents through the barrier. Mechanical-force-controlled electric logic circuits are achieved by realizing strain-controlled basic (AND and OR) and universal (NAND and NOR) logic gates in a single system. The proposed material system can be used to fabricate material-embedded logics of arbitrary complexity for a wide range of applications including soft robotics, wearable/implantable electronics, human-machine interfaces, and Internet of Things.

Tunable cavity-enhanced terahertz frequency-domain optical Hall effect.

Presented here is the development and demonstration of a tunable cavity-enhanced terahertz (THz) frequency-domain optical Hall effect (OHE) technique. The cavity consists of at least one fixed and one tunable Fabry-Pérot resonator. The approach is suitable for the enhancement of the optical signatures produced by the OHE in semi-transparent conductive layer structures with plane parallel interfaces. Tuning one of the cavity parameters, such as the external cavity thickness, permits shifting of the frequencies of the constructive interference and provides substantial enhancement of the optical signatures produced by the OHE. A cavity-tuning optical stage and gas flow cell are used as examples of instruments that exploit tuning an external cavity to enhance polarization changes in a reflected THz beam. Permanent magnets are used to provide the necessary external magnetic field. Conveniently, the highly reflective surface of a permanent magnet can be used to create the tunable external cavity. The signal enhancement allows the extraction of the free charge carrier properties of thin films and can eliminate the need for expensive superconducting magnets. Furthermore, the thickness of the external cavity establishes an additional independent measurement condition, similar to, for example, the magnetic field strength, THz frequency, and angle of incidence. A high electron mobility transistor (HEMT) structure and epitaxial graphene are studied as examples. The tunable cavity-enhancement effect provides a maximum increase of more than one order of magnitude in the change of certain polarization components for both the HEMT structure and epitaxial graphene at particular frequencies and external cavity sizes.